CN117264278A - New application of hydroxyphenyl triazine compound, polyamide material and preparation method - Google Patents
New application of hydroxyphenyl triazine compound, polyamide material and preparation method Download PDFInfo
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- CN117264278A CN117264278A CN202211742749.4A CN202211742749A CN117264278A CN 117264278 A CN117264278 A CN 117264278A CN 202211742749 A CN202211742749 A CN 202211742749A CN 117264278 A CN117264278 A CN 117264278A
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- glass fiber
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- fiber reinforced
- polyamide
- triazine compound
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 87
- 229920002647 polyamide Polymers 0.000 title claims abstract description 87
- 239000000463 material Substances 0.000 title claims abstract description 79
- -1 hydroxyphenyl triazine compound Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000003365 glass fiber Substances 0.000 claims abstract description 70
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 230000008859 change Effects 0.000 claims abstract description 16
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims description 29
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 18
- 239000000314 lubricant Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- 239000005083 Zinc sulfide Substances 0.000 claims description 13
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 13
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 13
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 claims description 12
- 239000000049 pigment Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000004806 packaging method and process Methods 0.000 claims description 7
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 4
- GISSTDJFFFXCLC-UHFFFAOYSA-N CC1=C(C=CC(=C1)C)C=1C(=C(C=C(C=1)OCCCCCCCC)O)C1=NC=NC=N1 Chemical compound CC1=C(C=CC(=C1)C)C=1C(=C(C=C(C=1)OCCCCCCCC)O)C1=NC=NC=N1 GISSTDJFFFXCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229920006528 PA66/6 Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical class OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 238000006731 degradation reaction Methods 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 16
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 150000008040 ionic compounds Chemical class 0.000 description 6
- 150000003384 small molecules Chemical class 0.000 description 6
- 238000005562 fading Methods 0.000 description 5
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000013522 chelant Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 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 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000088 plastic resin Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006114 semi-crystalline semi-aromatic polyamide Polymers 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The application discloses a novel application of a hydroxyphenyl triazine compound, a polyamide material and a preparation method, wherein the hydroxyphenyl triazine compound is used as a thermal stability auxiliary agent in a glass fiber reinforced polyamide material, and the glass fiber reinforced polyamide material comprises the following components in parts by weight: 48-99.8 parts of polyamide resin, 0-50 parts of glass fiber, 0.05-0.5 part of hydroxyphenyl triazine compound and 0.1-2 parts of other auxiliary agents. The glass fiber reinforced polyamide material reduces the color change of the polyamide in the high-temperature process by adding the hydroxyphenyl triazine compound.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a novel application of a hydroxyphenyl triazine compound, a polyamide material and a preparation method.
Background
As engineering plastic, the polyamide has obvious advantages of tough texture, good physical and mechanical properties, low friction coefficient and low abrasion, and can be used for manufacturing various transmission parts. However, if an amorphous polyamide is exposed to a relatively high temperature above its glass transition temperature, or a semi-crystalline polyamide is exposed to a relatively high temperature in its melting temperature range, the polyamide may undergo a phenomenon of discoloration due to thermal degradation. In addition, small molecules generated by thermal degradation of the polyamide can further react with the toner to cause color change or fading of the toner, thereby causing color distortion of the polyamide to influence the quality of the product.
To improve the discoloration problem of polyamides, the person skilled in the art improves this problem by adding antioxidants to the polyamide. The commonly used antioxidants are a compound of phenolic antioxidants and phosphite antioxidants, but the antioxidant cannot improve the problem of discoloration of polyamide at high temperature.
Therefore, how to prepare polyamides that are color stable at high temperatures is a technical problem that needs to be solved by the person skilled in the art.
Disclosure of Invention
The application provides a novel application of a hydroxyphenyl triazine compound, a polyamide material and a preparation method thereof, wherein the glass fiber reinforced polyamide material is used for reducing the color change of polyamide in a high-temperature process by adding the hydroxyphenyl triazine compound.
The application provides the following scheme: a novel application of a hydroxyphenyl triazine compound is provided, wherein the hydroxyphenyl triazine compound is used as a thermal stability auxiliary agent in a glass fiber reinforced polyamide material.
Further, the glass fiber reinforced polyamide material comprises the following components in parts by weight:
48-99.8 parts of polyamide resin, 0-50 parts of glass fiber, 0.05-0.5 part of hydroxyphenyl triazine compound and 0.1-2 parts of other auxiliary agents.
Further, the hydroxyphenyl triazine compound comprises at least one of 2- [2, 4-bis (2, 4-xylyl) -2- (1, 3, 5-triazinyl) 5-octyloxyphenol (UV 1164), 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-n-hexyloxyphenol (Tinuvin 1577), 2- [4, 6-bis (4-biphenyl) -1,3, 5-triazin-2- ] -5- [ (2-ethylhexyl) oxy ] phenol (Tinuvin 1600).
Further, the polyamide resin comprises at least one of PA6, PA66, PA46, PA56, PA66/6, PA6T, PA9T, PA610, PA611 and PA 612.
Further, the other auxiliary agents comprise at least one of toner, lubricant and antioxidant.
Further, the other auxiliary agent comprises a toner including at least one of zinc sulfide and monoazo pigment.
Further, the other auxiliary agent comprises a lubricant, and the lubricant comprises at least one of stearate, N-ethylene bis-stearamide, pentaerythritol stearate, silicone powder and polyethylene wax.
Further, the other auxiliary agents comprise antioxidants, and the antioxidants comprise at least one of an antioxidant S2225P, an antioxidant 168, an antioxidant 1010 and an antioxidant 1098.
Further, the glass fiber has an aspect ratio of 20 to 40.
The application also provides the glass fiber reinforced polyamide material, wherein the glass fiber reinforced polyamide material has a color change color difference delta E of 0.15-0.92 at the temperature of 250-280 ℃.
In addition, the application also provides a preparation method of the glass fiber reinforced polyamide material, which comprises the following steps:
according to parts by weight, uniformly mixing 48-99.8 parts of polyamide resin, 0-50 parts of glass fiber, 0.05-0.5 part of hydroxyphenyl triazine compound and 0.1-2 parts of other auxiliary agents by a mixer to obtain a mixture;
adding the mixture into a double-screw extruder for melt blending, and extruding a material strip, wherein the extrusion temperature of the material strip is 240-260 ℃;
and (3) granulating the material strips by a granulator, drying by a lifter, and packaging to obtain a finished product.
Further, the screw speed of the twin-screw extruder is 300-500rPm.
According to a specific embodiment provided by the application, the application discloses the following technical effects:
the glass fiber reinforced polyamide material provided by the application reduces the color change of polyamide at high temperature by adding the hydroxyphenyl triazine compound. The hydroxyl hydrogen on the benzene ring of the hydroxyphenyl triazine compound and the intramolecular hydrogen bond formed between the adjacent nitrogen atoms form a chelate ring, the chelate ring is broken by the hydrogen bond to open under high temperature molecular thermal vibration, and an ionic compound is formed, and the ionic compound has the capability of capturing free radicals, so that the ionic compound has a certain function of inhibiting or delaying the degradation of polyamide, and the thermal stability of the polyamide is improved. The thermal stability of the polyamide is improved, on one hand, the problem of discoloration of the polyamide caused by thermal degradation can be avoided; on the other hand, the problem of color change of the polyamide caused by the change of the toner due to the further reaction of small molecules generated by thermal degradation of the polyamide and the toner can be avoided.
Of course, not all of the above-described advantages need be achieved at the same time in practicing any one of the products of the present application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flowchart of a preparation method of a glass fiber reinforced polyamide material provided by the application.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application are within the scope of the protection of the present application.
As described in the background art, the polyamide may be discolored due to thermal degradation during high temperature, and small molecules generated by thermal degradation of the polyamide may further react with the toner to cause discoloration or fading of the toner, thereby causing color distortion of the polyamide to affect product quality. The application reduces the color change of the polyamide during the high temperature process by adding the hydroxyphenyl triazine compound into the glass fiber reinforced polyamide material. Based on the above, the application provides a new application of the hydroxyphenyl triazine compound, a polyamide material and a preparation method.
As a preferred embodiment, in the embodiment of the present application, the glass fiber reinforced polyamide material includes the following components in parts by weight: 48-99.8 parts of polyamide resin, 0-50 parts of glass fiber, 0.05-0.5 part of hydroxyphenyl triazine compound and 0.1-2 parts of other auxiliary agents.
The polyamide resin comprises at least one of PA6, PA66, PA46, PA56, PA66/6, PA6T, PA T, PA610, PA611 and PA 612. In the embodiment of the present application, the polyamide resin is preferably PA6.
After the polyamide is reinforced by glass fiber, the integral strength of the polyamide can be greatly improved. The aspect ratio of the glass fibers, which in the preferred embodiment of the present application is 20-40, affects the load bearing and compression resistance of the formed material. More specifically, the glass fibers have aspect ratios of 20, 30, 40, preferably 30, and are not exhaustive herein.
Because the polyamide can be discolored due to thermal degradation in the high-temperature processing process, and small molecules generated by the thermal degradation of the polyamide can further react with the toner to cause the color change or the color fading of the toner, the color distortion of the polyamide is caused to influence the quality of a product. To solve this problem, the present application reduces the color change of the polyamide at high temperature by adding a hydroxyphenyl triazine compound to the glass fiber reinforced polyamide material. The hydroxyl hydrogen on the benzene ring of the hydroxyphenyl triazine compound and the intramolecular hydrogen bond formed between the adjacent nitrogen atoms form a chelate ring, the chelate ring is broken by the hydrogen bond to open under high temperature molecular thermal vibration, and an ionic compound is formed, and the ionic compound has the capability of capturing free radicals, so that the ionic compound has a certain function of inhibiting or delaying the degradation of polyamide, and the thermal stability of the polyamide is improved. The thermal stability of the polyamide is improved, on one hand, the problem of discoloration of the polyamide caused by thermal degradation can be avoided; on the other hand, the problem of color change of the polyamide caused by the change of the toner due to the further reaction of small molecules generated by thermal degradation of the polyamide and the toner can be avoided. The glass fiber reinforced polyamide material provided by the embodiment of the application has the color change color difference delta E of 0.15-0.92 at the temperature of 250-280 ℃. Further, the hydroxyphenyl triazine compound comprises at least one of 2- [2, 4-bis (2, 4-xylyl) -2- (1, 3, 5-triazinyl) 5-octyloxyphenol (UV 1164), 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-n-hexyloxyphenol (Tinuvin 1577), 2- [4, 6-bis (4-biphenyl) -1,3, 5-triazin-2- ] -5- [ (2-ethylhexyl) oxy ] phenol (Tinuvin 1600).
Wherein the other auxiliary agent comprises at least one of toner, lubricant and antioxidant.
The toner includes at least one of zinc sulfide and monoazo pigment, and is used for coloring polyamide resin. For example, zinc sulfide may be added to make the final product appear white in this application, while monoazo pigments may be added to make the final product appear yellow.
The problems of rough products, lack of gloss, exposed glass fibers and the like are caused by the high melt viscosity of the polyamide in the processing process. To solve these problems, lubricants are typically added during the preparation process. The lubricant is added into the glass fiber reinforced polyamide material, so that on one hand, the bonding state of glass fibers and polyamide resin can be improved, and further, the dispersibility of the glass fibers in the polyamide resin is improved; on the other hand, the processing fluidity of the glass fiber reinforced polyamide material can be improved, and the surface smoothness of the material can be improved. The lubricant comprises at least one of calcium stearate, stearic acid, N-ethylene bis-stearamide, pentaerythritol stearate, silicone powder and polyethylene wax, and can be selected by a user according to actual requirements without specific limitation.
The antioxidant can effectively reduce the thermal oxidation reaction speed of plastic macromolecules, delay the thermal and oxygen degradation processes of plastic resin, remarkably improve the heat resistance of the plastic resin and prolong the service life of plastic products. In the embodiment of the invention, the antioxidant comprises at least one of antioxidant S2225P, antioxidant 168, antioxidant 1010 and antioxidant 1098, and the antioxidant can be selected by a user according to actual requirements without specific limitation.
Corresponding to the glass fiber reinforced polyamide material, the application also provides a preparation method of the glass fiber reinforced polyamide material. As shown in fig. 1, the preparation method of the glass fiber reinforced polyamide material comprises the following steps:
s1: according to parts by weight, uniformly mixing 48-99.8 parts of polyamide resin, 0-50 parts of glass fiber, 0.05-0.5 part of hydroxyphenyl triazine compound and 0.1-2 parts of other auxiliary agents by a mixer to obtain a mixture;
s2: adding the mixture into a double-screw extruder for melt blending, and extruding a material strip, wherein the extrusion temperature of the material strip is 240-260 ℃;
s3: and (3) granulating the material strips by a granulator, drying by a lifter, and packaging to obtain a finished product.
Preferably, the screw speed of the twin-screw extruder is 300-500rpm.
Any combination of the above optional solutions may be adopted to form an optional embodiment of the present application, which is not described herein in detail.
The advantageous effects of the present application will be further described below in conjunction with examples and comparative examples.
The raw materials used in the examples and comparative examples are now described as follows:
PA6 resin: the production of the ancient Chebyshev nitrogen, and the viscosity is 2.5;
glass fiber: taishan glass fiber Co., ltd., taishan short fiber EC10-3.0-T435TM;
2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-n-hexyloxyphenol (Tinuvin 1577): the Shanghai uncut Uv1577;
2- [4, 6-bis (4-biphenyl) -1,3, 5-triazine-2- ] -5- [ (2-ethylhexyl) oxy ] phenol (Tinuvin 1600): BASF, UV1600;
zinc sulfide: german Ha Shali, zinc sulfide HD-S;
monoazo pigments: langsheng production, bayplast yellow G;
lubricant N, N-ethylene bis stearamide: acrawax C, produced by Dragon sand, america;
antioxidant S2225P: S2225P, produced by Yabao, USA.
The material performance testing method comprises the following steps:
1. resistance to thermal oxidation yellowing: the glass fiber reinforced polyamide material was injection molded into color plates at 250 ℃, 265 ℃, 280 ℃ respectively, color measurement was performed by a spectrocolorimeter, D65 was selected as a light source, color difference data was characterized by the CIELab method, and the color quality of the color plates obtained in comparative examples 1-2 and examples 1-6 was tested by measuring the CIELab value.
Wherein, the value of L is the brightness of the color brightness, 0.ltoreq.l.ltoreq.100, 0=black, 100=white; a and b represent positions on the red/green axis and the yellow/blue axis, respectively, the greater the absolute value of the a or b axis, the higher the saturation, and the color difference value Δe is calculated by the following formula:
ΔE＝[(ΔL*) 2 +(Δa*) 2 +(Δb*) 2 ] 1/2 。
comparative example 1
The glass fiber reinforced polyamide material comprises the following components in parts by weight:
69.2 parts of PA6 resin, 30 parts of glass fiber, 0.3 part of lubricant N, N-ethylene bis-stearamide and 0.5 part of antioxidant S2225P.
The preparation method of the glass fiber reinforced polyamide material comprises the following steps:
according to parts by weight, uniformly mixing 69.2 parts of PA6 resin, 30 parts of glass fiber, 0.3 part of lubricant N, N-ethylene bis-stearamide and 0.5 part of antioxidant S2225P by a mixer to obtain a mixture;
adding the mixture into a double-screw extruder for melt blending, and extruding a material strip, wherein the extrusion temperature of the material strip is 245 ℃;
and (3) granulating the material strips by a granulator, drying by a lifter, and packaging to obtain a finished product.
Comparative example 2
The glass fiber reinforced polyamide material comprises the following components in parts by weight:
68.5 parts of PA6 resin, 30 parts of glass fiber, 0.3 part of N, N-ethylene bisstearamide serving as a lubricant, 0.5 part of antioxidant S2225P, 0.5 part of zinc sulfide and 0.2 part of monoazo pigment.
The preparation method of the glass fiber reinforced polyamide material comprises the following steps:
according to parts by weight, 68.5 parts of PA6 resin, 30 parts of glass fiber, 0.3 part of lubricant N, N-ethylene bis-stearamide, 0.5 part of antioxidant S2225P, 0.5 part of zinc sulfide and 0.2 part of monoazo pigment are uniformly mixed by a mixer to obtain a mixture;
adding the mixture into a double-screw extruder for melt blending, and extruding a material strip, wherein the extrusion temperature of the material strip is 245 ℃;
and (3) granulating the material strips by a granulator, drying by a lifter, and packaging to obtain a finished product.
Example 1
The glass fiber reinforced polyamide material comprises the following components in parts by weight:
69.1 parts of PA6 resin, 30 parts of glass fiber, 0.3 part of lubricant N, N-ethylene bis-stearamide, 0.5 part of antioxidant S2225P and 0.1 part of Tinuvin 1577.
The preparation method of the glass fiber reinforced polyamide material comprises the following steps:
according to parts by weight, 69.1 parts of PA6 resin, 30 parts of glass fiber, 0.3 part of lubricant N, N-ethylene bis-stearamide, 0.5 part of antioxidant S2225P and 0.1 part of Tinuvin1577 are uniformly mixed by a mixer to obtain a mixture;
adding the mixture into a double-screw extruder for melt blending, and extruding a material strip, wherein the extrusion temperature of the material strip is 245 ℃;
and (3) granulating the material strips by a granulator, drying by a lifter, and packaging to obtain a finished product.
Example 2
The difference compared to example 1 is Tinuvin 1577.3 parts.
Example 3
The difference compared to example 1 is that 0.1 part Tinuvin1577 is replaced with 0.1 part Tinuvin1600.
Example 4
The difference compared to example 1 is that 0.1 part Tinuvin1577 is replaced with 0.3 part Tinuvin1600.
Example 5
The glass fiber reinforced polyamide material comprises the following components in parts by weight:
68.4 parts of PA6 resin, 30 parts of glass fiber, 0.3 part of N, N-ethylene bisstearamide serving as a lubricant, 0.5 part of antioxidant S2225P, 0.5 part of zinc sulfide, 0.2 part of monoazo pigment and 0.1 part of Tinuvin 1577.
The preparation method of the glass fiber reinforced polyamide material comprises the following steps:
according to parts by weight, 68.4 parts of PA6 resin, 30 parts of glass fiber, 0.3 part of lubricant N, N-ethylene bis-stearamide, 0.5 part of antioxidant S2225P, 0.5 part of zinc sulfide, 0.2 part of monoazo pigment and 0.1 part of Tinuvin1577 are uniformly mixed by a mixer to obtain a mixture;
adding the mixture into a double-screw extruder for melt blending, extruding a material strip, wherein the extrusion temperature of the material strip is 245 ℃:
and (3) granulating the material strips by a granulator, drying by a lifter, and packaging to obtain a finished product.
Example 6
The difference compared to example 5 is Tinuvin 1577.3 parts.
Example 7
In comparison with example 5, the difference is that 0.1 part of Tinuvin1577 is replaced with 0.1 part of Tinuvin1600.
Example 8
In comparison with example 5, the difference is that 0.1 part of Tinuvin1577 is replaced with 0.3 part of Tinuvin1600.
The test results of examples 1-8 and comparative examples 1-2 are shown in Table 1.
TABLE 1 test results of the properties of glass fiber reinforced polyamide materials prepared in examples 1-8 and comparative examples 1-2
From the test results of table 1, it can be seen that:
1. from the test results of comparative example 1 and examples 1-2, the b-value of the glass fiber reinforced polyamide material decreased more as the injection molding temperature increased from 250 ℃ to 280 ℃, indicating that the thermal degradation of the PA6 resin was more severe. After Tinuvin1577 is added, the b-value reduction amplitude of the glass fiber reinforced polyamide material is obviously reduced and delta E is reduced, and in a certain range, as the quality of Tinuvin1577 is increased, the b-value reduction amplitude of the glass fiber reinforced polyamide material is further reduced and delta E is reduced, namely the Tinuvin1577 can reduce the color change of the PA6 resin caused by thermal degradation in the thermal processing process.
2. As is clear from the test results of comparative example 1 and examples 3 to 4, the b-value decrease amplitude of the glass fiber reinforced polyamide material is significantly reduced and Δe is smaller after Tinuvin1600 is added as the injection molding temperature is increased from 250 ℃ to 280 ℃, and the b-value decrease amplitude of the glass fiber reinforced polyamide material is further reduced and Δe is smaller as the quality of Tinuvin1600 is increased within a certain range, i.e., tinuvin1600 is capable of reducing the color change of PA6 resin due to thermal degradation during thermal processing.
3. As can be seen from the test results of comparative example 1 and examples 1 to 4, when Tinuvin1600 of the same mass is added to the glass fiber reinforced polyamide material, the drop of b-value of the glass fiber reinforced polyamide material is smaller and Δe is smaller, which indicates that Tinuvin1600 has better color thermal stability protection effect on the glass fiber reinforced polyamide material, compared with Tinuvin 1577.
4. From the test results of comparative example 2, examples 5-8, it is evident that, in the glass fiber reinforced polyamide material added with zinc sulfide and monoazo pigment, the b-value of the glass fiber reinforced polyamide material decreases more as the injection molding temperature increases from 250 ℃ to 280 ℃, indicating that the small molecules generated by thermal degradation of PA6 resin further react with the zinc sulfide and monoazo pigment, resulting in discoloration or fading of the zinc sulfide and monoazo pigment. The addition of Tinuvin1577 and Tinuvin1600 in the glass fiber reinforced polyamide material can reduce the b-value drop and delta E, so that the fading degree of the material is reduced, and the Tinuvin1600 has better color thermal stability protection effect on the material.
The novel application, polyamide material and preparation method of the hydroxyphenyl triazine compound provided by the application are described in detail, and specific examples are used for illustrating the principles and embodiments of the application, and the description of the examples is only used for helping to understand the method and core ideas of the application; also, as will occur to those of ordinary skill in the art, many modifications are possible in view of the teachings of the present application, both in the detailed description and the scope of its applications. In view of the foregoing, this description should not be construed as limiting the application.
Claims (11)
1. The novel application of the hydroxyphenyl triazine compound is characterized in that the hydroxyphenyl triazine compound is used as a heat stability auxiliary agent in glass fiber reinforced polyamide materials.
2. The new use according to claim 1, wherein the glass fiber reinforced polyamide material comprises the following components in parts by weight:
48-99.8 parts of polyamide resin, 0-50 parts of glass fiber, 0.05-0.5 part of hydroxyphenyl triazine compound and 0.1-2 parts of other auxiliary agents.
3. The novel use according to claim 1, wherein the hydroxyphenyl triazines comprise at least one of 2- [2, 4-bis (2, 4-xylyl) -2- (1, 3, 5-triazinyl) 5-octyloxyphenol (UV 1164), 2- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -5-n-hexyloxyphenol (Tinuvin 1577), 2- [4, 6-bis (4-biphenyl) -1,3, 5-triazin-2- ] -5- [ (2-ethylhexyl) oxy ] phenol (Tinuvin 1600).
4. The new use according to claim 1, wherein the polyamide resin comprises at least one of PA6, PA66, PA46, PA56, PA66/6, PA6T, PA, T, PA, 610, PA611, PA 612.
5. The new use according to claim 1, wherein the other auxiliary agents comprise at least one of toner, lubricant and antioxidant.
6. The new use according to claim 1, wherein the other auxiliary agent comprises a toner comprising at least one of zinc sulfide, monoazo pigment.
7. The new use according to claim 1, wherein the other auxiliary agent comprises a lubricant comprising at least one of stearate, N-ethylenebisstearamide, pentaerythritol stearate, silicone powder, polyethylene wax.
8. The new use of claim 1, wherein the other auxiliary agents comprise antioxidants, and the antioxidants comprise at least one of antioxidants S2225P, antioxidants 168, antioxidants 1010, antioxidants 1098.
9. The new use according to claim 1, wherein the glass fiber has an aspect ratio of 20-40.
10. The glass fiber reinforced polyamide material according to any one of claims 1 to 8, wherein the glass fiber reinforced polyamide material has a color change difference Δe of 0.15 to 0.92 at a temperature of 250 to 280 ℃.
11. A method for preparing a glass fiber reinforced polyamide material according to any one of claims 1 to 8, comprising:
according to parts by weight, uniformly mixing 48-99.8 parts of polyamide resin, 0-50 parts of glass fiber, 0.05-0.5 part of hydroxyphenyl triazine compound and 0.1-2 parts of other auxiliary agents by a mixer to obtain a mixture;
adding the mixture into a double-screw extruder for melt blending, and extruding a material strip, wherein the extrusion temperature of the material strip is 240-260 ℃;
and (3) granulating the material strips by a granulator, drying by a lifter, and packaging to obtain a finished product.
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