CN111440436A - High-impact-strength polyamide composition and application thereof - Google Patents
High-impact-strength polyamide composition and application thereof Download PDFInfo
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- CN111440436A CN111440436A CN201911311245.5A CN201911311245A CN111440436A CN 111440436 A CN111440436 A CN 111440436A CN 201911311245 A CN201911311245 A CN 201911311245A CN 111440436 A CN111440436 A CN 111440436A
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- 239000000203 mixture Substances 0.000 title claims abstract description 45
- 239000004952 Polyamide Substances 0.000 title claims abstract description 33
- 229920002647 polyamide Polymers 0.000 title claims abstract description 33
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 26
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 25
- 229920001971 elastomer Polymers 0.000 claims abstract description 22
- 239000000806 elastomer Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 12
- 239000003607 modifier Substances 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- 239000001993 wax Substances 0.000 claims description 25
- 150000001336 alkenes Chemical class 0.000 claims description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- -1 fatty acid ester Chemical class 0.000 claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 7
- 239000000194 fatty acid Substances 0.000 claims description 7
- 229930195729 fatty acid Natural products 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- WQNHWIYLCRZRLR-UHFFFAOYSA-N 2-(3-hydroxy-2,5-dioxooxolan-3-yl)acetic acid Chemical compound OC(=O)CC1(O)CC(=O)OC1=O WQNHWIYLCRZRLR-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 150000002193 fatty amides Chemical class 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 210000000707 wrist Anatomy 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012761 high-performance material Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 239000004135 Bone phosphate Substances 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- 241000218033 Hibiscus Species 0.000 description 1
- 235000005206 Hibiscus Nutrition 0.000 description 1
- 235000007185 Hibiscus lunariifolius Nutrition 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 210000001320 hippocampus Anatomy 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high impact strength polyamide composition and application, wherein the polyamide composition is prepared from 75-80 parts by weight of polyamide 66 resin, 0-5 parts by weight of polyamide 6 resin, 5-20 parts by weight of first elastomer, 5-10 parts by weight of second elastomer, 0.2-0.7 part by weight of flow modifier and 0-1 part by weight of extrusion addition auxiliary agent; the first elastomer is unsaturated acid anhydride grafted ethylene-propylene-non-conjugated diene copolymer, and the second elastomer is one or the mixture of unsaturated acid anhydride grafted ethylene copolymer and ethylene copolymer. The polyamide composition has higher elongation at break, thereby expanding the application scene.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polyamide composition with high impact strength and application thereof.
Background
Polyamide 66, commonly known as nylon 66(PA66), is a thermoplastic resin containing amide groups (-CONH-) in the repeating structural unit of the molecular backbone. It is usually prepared in the form of cylindrical pellets, and the molecular weight of polyamide used as a plastic is generally 1.5 to 2 ten thousand. High tensile strength, wear resistance, good electrical insulation, high fluidity of molten resin, and suitability for injection molding.
Unfortunately, polyamide 66 has unsatisfactory impact strength and has a notched izod impact strength of less than 5KJ per square meter when dry at ambient temperature, which presents a risk for use in some areas where toughness is a concern. It is well known to those skilled in the art that the impact properties of polyamide 66 can be significantly increased by using acid or anhydride modified elastomers, in particular maleic anhydride graft modified elastomers, typically copolymers of ethylene, such as POE, which is a copolymer of ethylene with 1-butene or 1-octene, which is currently the most cost-advantageous solution in engineering, and also good toughening effects on polyamide 66, such as ionomers, as reported in dupont patent CN1622979 for toughening PA6 materials with ionomers.
Although maleic anhydride graft-modified ethylene copolymer elastomers can significantly improve the toughness of polyamide 66, the elongation at break of polyamide 66 compositions toughened and modified with such elastomers is unsatisfactory, for example, with the addition of 20 weight percent maleic anhydride graft POE to polyamide 66, the notched izod impact strength of the material can exceed 80 KJ/square meter at ambient temperature, but the elongation at break can only be obtained at values of about 30%. While a high elongation at break is preferred in application scenarios to prevent high speed impacts, which means that the material will be less likely to generate angular splatter of debris, thereby reducing the risk level.
Disclosure of Invention
In view of the above, the invention needs to provide a polyamide composition with high impact strength and an application thereof, and after a flow modifier is added into a system, the prepared polyamide composition has higher elongation at break compared with the conventional toughened polyamide 66 composition, and the technical problem that the existing toughened polyamide 66 has low elongation at break is solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high impact strength polyamide composition is prepared by 75-80 parts of polyamide 66 resin, 0-5 parts of polyamide 6 resin, 5-20 parts of first elastomer, 5-10 parts of second elastomer, 0.2-0.7 part of flow modifier and 0-1 part of extrusion addition auxiliary agent according to parts by weight;
the first elastomer is unsaturated acid anhydride grafted ethylene-propylene-non-conjugated diene copolymer, and the second elastomer is one or the mixture of unsaturated acid anhydride grafted ethylene copolymer and ethylene copolymer.
Further, the relative viscosity of the polyamide 66 resin is 2.4-3.2, and the terminal amino group value is not less than 60 mmol/kg.
Further, the unsaturated anhydride grafted ethylene-propylene-non-conjugated diene copolymer and the unsaturated anhydride grafted ethylene copolymer have unsaturated anhydrides which are respectively and independently selected from at least one of maleic anhydride and citric anhydride.
Further, the unsaturated acid anhydride grafted ethylene-propylene-non-conjugated diene copolymer has a density of 0.8 to 0.9g/cm3And the melt index under the conditions of 230 ℃ and 2.16kg is lower than 1g/10 min.
Further, the ethylene copolymer in the ethylene copolymer and the unsaturated acid anhydride grafted ethylene copolymer is at least one selected from the group consisting of a copolymer of ethylene and propylene, a copolymer of ethylene and 1-butene and a copolymer of ethylene and 1-octene, and the density of the ethylene copolymer and the ethylene copolymer is 0.8-0.9g/cm3The melt index under the conditions of 230 ℃ and 2.16kg is lower than 30g/10min, wherein the content of the comonomer is 20-50%.
Further, the flow modifier is one or a mixture of more than two of aliphatic long-chain dibasic acids.
Preferably, the aliphatic long-chain dibasic acid has 10 to 18 carbon atoms and a melting point of between 120 ℃ and 150 ℃.
Further, the extrusion additive comprises at least one of an antioxidant, a lubricant and a light stabilizer.
Further, the lubricant includes one or a mixture of two or more of a fatty acid ester, a fatty amide, a low molecular weight paraffin wax, a modified low molecular weight paraffin wax, a silicone, a low molecular weight olefin wax, an acidified olefin wax, and an oxidized olefin wax, and the lubricant does not include carboxylates of alkali metals and alkaline earth metals.
The invention also discloses the application of the high impact strength polyamide composition in preparing a sheath of a skating shoe, a sports shoe sole, a wrist strap or an automobile part.
Compared with the prior art, the components used in the polyamide composition are commercially available and widely available, and the polyamide composition is directly prepared by melt blending and extrusion, has a simple preparation process and strong operability, and is suitable for large-scale industrial production.
Compared with the conventional toughened polyamide 66 material, the polyamide composition has higher elongation at break due to the addition of the flow modifier in the system, and is very suitable for products with high requirements on impact strength and elongation at break.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description of specific embodiments. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention discloses a high-impact-strength polyamide composition which is prepared from 75-80 parts by weight of polyamide 66 resin, 0-5 parts by weight of polyamide 6 resin, 5-20 parts by weight of first elastomer, 5-10 parts by weight of second elastomer, 0.2-0.7 part by weight of flow modifier and 0-1 part by weight of extrusion addition auxiliary agent;
the first elastomer is unsaturated acid anhydride grafted ethylene-propylene-non-conjugated diene copolymer, and the second elastomer is one or the mixture of unsaturated acid anhydride grafted ethylene copolymer and ethylene copolymer.
The invention adds elastomer and flow modifier into the system to make the polyamide composition have high impact strength and high elongation at break.
Further, the relative viscosity of the polyamide 66 resin is 2.4-3.2, and the terminal amino value is not lower than 60 mmol/kg. In particular, the relative viscosity is measured here by dissolving 1% by mass of polyamide 66 resin in a solution of sulphuric acid, in particular according to standard ISO 307. Preferably, in some embodiments of the present invention, the polyamide 66 resin has a relative viscosity of 2.4 to 3.0, more preferably 2.5 to 2.8. Further, in some embodiments of the present invention, it is preferable that the amino terminal group number of the polyamide 66 is not less than 80 mmol/kg.
In a further embodiment, the unsaturated anhydride grafted ethylene-propylene-non-conjugated diene copolymer and the unsaturated anhydride grafted ethylene copolymer have at least one unsaturated anhydride independently selected from maleic anhydride and citric anhydride.
In the field of high molecular materials, a low melt index means a higher molecular weight and thus a better toughening effect, and therefore, in some embodiments of the present invention, the unsaturated anhydride grafted ethylene-propylene-non-conjugated diene copolymer has a density of 0.8 to 0.9g/cm3And the melt index under the conditions of 230 ℃ and 2.16kg is lower than 1g/10 min. More preferably, the unsaturated anhydride grafted ethylene-propylene-non-conjugated diene copolymer has a melt index of less than 0.5g/10 min.
In a further scheme, the ethylene copolymer in the ethylene copolymer and the unsaturated acid anhydride grafted ethylene copolymer is at least one of a copolymer of ethylene and propylene, a copolymer of ethylene and 1-butene and a copolymer of ethylene and 1-octene, and the density of the ethylene copolymer and the ethylene copolymer is 0.8-0.9g/cm3The melt index of 2.16kg is lower than 30g/10min at 230 ℃, wherein the content of the comonomer is 20-50 percent. In some embodiments of the invention, the comonomer content is preferably between 30% and 40% and its melt index is lower than 10g/10 min. This is because in the field of polymer material modification, the content of comonomer directly determines the glass of the toughening agentThe lower the glass transition temperature, the better the toughening effect, and therefore in some embodiments of the invention, the above preferences are made.
In a further scheme, the flow modifier is one or a mixture of more than two of aliphatic long-chain dibasic acids. The long-chain aliphatic dibasic acid generally refers to a saturated straight-chain dibasic acid containing 10 or more carbon atoms and having carboxyl functional groups at two ends, and the invention innovatively adds the long-chain aliphatic dibasic acid into the polyamide composition and surprisingly finds that the elongation at break of the polyamide composition can be obviously improved.
Preferably, in some embodiments of the present invention, the aliphatic long-chain dibasic acid has 10 to 18 carbon atoms and a melting point of between 120 ℃ and 150 ℃. More preferably, the aliphatic long-chain dibasic acid has 10 to 13 carbon atoms and a melting point of between 120 ℃ and 135 ℃.
In a further aspect, the extrusion additive includes at least one of an antioxidant, a lubricant, and a light stabilizer.
Preferably, the lubricant comprises one or a mixture of two or more of fatty acid ester, fatty amide, low molecular weight paraffin wax, modified low molecular weight paraffin wax, silicone, low molecular weight olefin wax, acidified olefin wax, and oxidized olefin wax. In particular, the extrusion additive does not nucleate polyamides when tested thermally in a differential scanning calorimeter, and the lubricant does not include alkali and alkaline earth metal carboxylates, such as stearic acid, palmitic acid, erucic acid, montanic acid, and the like.
Specifically, the carboxylic acid for synthesizing the fatty acid ester is a mono-or dibasic acid, and may be selected from stearic acid, palmitic acid, lauric acid, heptadecanoic acid, montanic acid, and the like.
The fatty alcohol used in the synthesis of the fatty acid ester is mono-to tetra-basic and may be selected from ethylene glycol, propylene glycol, glycerol, preferably glycerol or pentaerythritol.
The fatty amines used in the synthesis of the fatty acid amides may be mono-to tri-basic and include stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, preferably ethylenediamine or hexamethylenediamine.
The lubricant can also be compounded in fatty acid ester or amide according to any proportion.
The low molecular weight olefin WAX, the acidified olefin WAX and the oxidized olefin WAX are obtained by a series of cracking reactions, the molecular weight of the low molecular weight olefin WAX is larger than that of white oil, the low molecular weight olefin WAX, the acidified olefin WAX and the oxidized olefin WAX are solid, in some embodiments of the invention, the preferred molecular weight is less than 3000g/mol, the acidified olefin WAX and the oxidized olefin WAX are obtained by further modifying on the basis of olefin WAX, and the low molecular weight olefin WAX, the acidified olefin WAX and the oxidized olefin WAX are commonly known as German Laine oxidized WAX PED 521 and Mitsui chemical acidified WAX Hi-WAX 4202E, and the details are.
The invention also provides the use of the high impact polyamide composition for producing a boot for skates, a sports shoe sole, a wrist strap or an automobile part, which can be used in application scenarios for preventing high-speed impacts.
The technical scheme of the invention is more clearly and more completely explained by combining the specific embodiments.
The polyamide compositions of the following examples E1-E7 and comparative examples C1-C7 were prepared with the components and amounts added in tables 2 and 3, the specific materials for each component in tables 1 and 2 being:
component A
A1: PA66, designation EP158NH, relative viscosity 2.8, terminal amino content 84mmol/kg, available from Wenzhou Huafeng group;
a2: PA66, designation EPR27, relative viscosity 2.7, terminal amino group content 52mmol/kg, available from Hippocampus Hibiscus engineering plastics, Inc.
A3: PA6, designation YH800, relative viscosity 2.8, available from Yueyang petrochemical Co., Ltd, Hunan;
component B
B1: maleic anhydride grafted ethylene-propylene-non-conjugated diene copolymer, EPDM-g-MAH, designation N416, melt index of 0.2g/10min (melt index test conditions 230 ℃/2.16kg), available from DuPont, USA as a high performance material;
b2: maleic anhydride modified ethylene-octene copolymer, POE-g-MAH, designation N493D, melt index of 1g/10min (melt index test conditions 230 ℃/2.16kg), purchased from DuPont, USA high performance materials;
component B3: ethylene-octene copolymer, POE, designation 8842, melt index of 1g/10min (melt index test conditions 230 ℃/2.16kg), available from Dow chemical, USA;
and (3) component C: the melting point of the dodecanedioic acid, referred to as DDDA for short, is 139 ℃, and the limited content is more than or equal to 98 percent.
According to the components and the component ratios in tables 2 and 3, the component A and the component B are mixed and then added into a first main hopper of a double-screw extruder with the screw diameter of 35mm, the length-diameter ratio of the screw is 48:1, the whole extruder is divided into 12 sections of barrels, the component C is fed from a second side feeding hopper, the second side feeding hopper is arranged at an 8 th section of barrel, and the extrusion temperature is set from a first area in sequence as follows: 200 ℃, 280 ℃, 260 ℃ for the head temperature and 500rpm for the screw speed. The composition is obtained by melting, plasticizing, extruding and granulating.
The resulting composition was dried and then injection molded to give standard bars of ISO 527 and ISO 180 specifications according to the following procedure, the injection molding conditions being as shown in table 1, and the test results in tables 2 and 3:
TABLE 1 injection parameters
| Drying time | 3 to 5 hours |
| Drying temperature | 100℃ |
| Drying apparatus | Dehumidifying type dryerDrying machine |
| In dry form | Continuous drying (production process) |
| Injection molding temperature-nozzle segment | 285℃ |
| Injection temperature-plasticizing section | 280℃ |
| Injection molding temperature-conveying section | 260℃ |
| Injection pressure | 40～120MPa |
| Time of injection | 2s |
| Dwell time | 5-10s |
| Cooling time | 8-15s |
TABLE 2 Components and parts by weight of the Polyamide compositions of examples E1-E7 and the results of the bar testing
TABLE 3 Components and parts by weight of the Polyamide compositions from examples C1 to C7 and the results of the bar testing
From the data of examples E1-E7 and comparative examples C1-C7, both of which achieve excellent notched Izod impact strength after 20% total elastomer addition, but the elongation at break results are very different, from the comparison of examples E1-E3 and comparative examples C1-C3, it can be seen that PA66 EP158NH with a higher content of terminal amino groups is used as the matrix resin, resulting in elongation at break significantly higher than that of the material with PA66 EPR27 as the matrix resin, and from the comparison of examples E4-E6 and comparative examples C4-C6, it is surprising that the flow modifier DDDA has a significant effect of increasing elongation at break, achieving unexpected technical effects, from the comparison of examples E7 and comparative examples C7, the addition of EPDM-g-MAH or the compounding of EPDM-g-MAH with POE, compared with POE-g-MAH, the elongation at break can be obviously improved.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The high-impact-strength polyamide composition is characterized by being prepared from 75-80 parts by weight of polyamide 66 resin, 0-5 parts by weight of polyamide 6 resin, 5-20 parts by weight of first elastomer, 5-10 parts by weight of second elastomer, 0.2-0.7 part by weight of flow modifier and 0-1 part by weight of extrusion addition auxiliary agent;
the first elastomer is unsaturated acid anhydride grafted ethylene-propylene-non-conjugated diene copolymer, and the second elastomer is one or the mixture of unsaturated acid anhydride grafted ethylene copolymer and ethylene copolymer.
2. The high impact polyamide composition as claimed in claim 1, wherein the polyamide 66 resin has a relative viscosity of 2.4 to 3.2 and an amino terminal group number of not less than 60 mmol/kg.
3. The high impact polyamide composition according to claim 1, wherein the unsaturated anhydride-grafted ethylene-propylene-nonconjugated diene copolymer and the unsaturated anhydride-grafted ethylene copolymer have at least one unsaturated anhydride independently selected from maleic anhydride and citric anhydride.
4. The high impact polyamide composition as claimed in claim 1, wherein the unsaturated anhydride-grafted ethylene-propylene-non-conjugated diene copolymer has a density of 0.8 to 0.9g/cm3And the melt index under the conditions of 230 ℃ and 2.16kg is lower than 1g/10 min.
5. The high impact polyamide composition as claimed in claim 1, wherein the ethylene copolymer and the ethylene copolymer of the unsaturated acid anhydride grafted ethylene copolymer are at least one selected from the group consisting of a copolymer of ethylene and propylene, a copolymer of ethylene and 1-butene, and a copolymer of ethylene and 1-octene, respectively, and have a density of 0.8 to 0.9g/cm3The melt index under the conditions of 230 ℃ and 2.16kg is lower than 30g/10min, wherein the content of the comonomer is 20-50%.
6. The high impact polyamide composition as claimed in claim 1, wherein the flow modifier is one or a mixture of two or more of aliphatic long chain dibasic acids.
7. The high impact polyamide composition as claimed in claim 6, wherein the aliphatic long chain dibasic acid has 10 to 18 carbon atoms and a melting point of 120-150 ℃.
8. The high impact polyamide composition of claim 1, wherein the extrusion additive comprises at least one of an antioxidant, a lubricant, and a light stabilizer.
9. The high impact polyamide composition as claimed in claim 1, wherein the lubricant comprises one or a mixture of two or more of fatty acid ester, fatty amide, low molecular weight paraffin wax, modified low molecular weight paraffin wax, silicone, low molecular weight olefin wax, acidified olefin wax, and oxidized olefin wax, and the lubricant does not comprise carboxylate of alkali metal and alkaline earth metal.
10. Use of a high impact polyamide composition according to any one of claims 1 to 9 for the preparation of a boot for ice skates, a sports shoe sole, a wrist strap or an automobile part.
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