CN114507343B - Polyamide and preparation method and application thereof - Google Patents
Polyamide and preparation method and application thereof Download PDFInfo
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- CN114507343B CN114507343B CN202210231046.9A CN202210231046A CN114507343B CN 114507343 B CN114507343 B CN 114507343B CN 202210231046 A CN202210231046 A CN 202210231046A CN 114507343 B CN114507343 B CN 114507343B
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 95
- 229920002647 polyamide Polymers 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 15
- 230000008018 melting Effects 0.000 claims abstract description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 31
- 150000004985 diamines Chemical class 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000005711 Benzoic acid Substances 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 235000010233 benzoic acid Nutrition 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000000889 atomisation Methods 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- -1 alicyclic diamine Chemical class 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 239000002667 nucleating agent Substances 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 11
- 230000032683 aging Effects 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004383 yellowing Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 229920006351 engineering plastic Polymers 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 14
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 14
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- JMLPVHXESHXUSV-UHFFFAOYSA-N dodecane-1,1-diamine Chemical compound CCCCCCCCCCCC(N)N JMLPVHXESHXUSV-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 230000006750 UV protection Effects 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 3
- 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
- 239000002253 acid Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920006119 nylon 10T Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000004224 protection Effects 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XJIAZXYLMDIWLU-UHFFFAOYSA-N undecane-1,1-diamine Chemical compound CCCCCCCCCCC(N)N XJIAZXYLMDIWLU-UHFFFAOYSA-N 0.000 description 2
- YQPCHPBGAALCRT-UHFFFAOYSA-N 2-[1-(carboxymethyl)cyclohexyl]acetic acid Chemical compound OC(=O)CC1(CC(O)=O)CCCCC1 YQPCHPBGAALCRT-UHFFFAOYSA-N 0.000 description 1
- LYQWYIYZAKISGW-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nonane-2,4-dione Chemical compound O=C1OC(=O)C2CCC1CC2 LYQWYIYZAKISGW-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
-
- 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
- C08L2205/24—Crystallisation aids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Polyamides (AREA)
Abstract
The invention discloses polyamide and a preparation method and application thereof, and belongs to the technical field of special engineering plastics. The polyamide has the following characteristics: (1) the relative viscosity eta r in sulfuric acid at 25 ℃ is 2.0-2.2; (2) the crystallization temperature Tc is more than or equal to 285 ℃; (3) The ratio of total carbon atoms to total amide bonds is 9.1 to 9.3; (4) Melting Peak temperature T m2 Is 315-340 ℃. The polyamide provided by the invention has high ultraviolet aging resistance, has good color stability in a UV environment, is not easy to generate yellowing, and meets the application and production requirements of the LED reflecting bracket in terms of molding cycle, water absorption, heat resistance and mechanical property.
Description
Technical Field
The invention belongs to the technical field of special engineering plastics, and particularly relates to polyamide and a preparation method and application thereof.
Background
The LED light source has many advantages such as low energy consumption, durability, high design flexibility, etc., and has been widely used in various fields, such as LED televisions, LED illumination, automobile illumination, traffic lights, etc. The LED reflector is an indispensable accessory for the LED light source, and needs to be exposed to the light environment, especially to the sun for a long time when used outdoors. Since the LED reflector is generally made of a polyamide material, the polyamide contains an amide bond, and the color stability in the UV environment is poor, the LED reflector inevitably turns yellow in use. Patent CN103539935B discloses a method for improving whiteness of semi-aromatic polyamide, but has a conjugated structure, and is liable to undergo yellowing when irradiated with ultraviolet light. Therefore, it is desirable to provide a polyamide material with better color stability in UV environment to improve the color stability of the LED reflector in UV environment.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a UV aging resistant polyamide and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polyamide having the following characteristics:
(1) The relative viscosity eta r in sulfuric acid at 25 ℃ is 2.0-2.2;
(2) The crystallization temperature Tc is more than or equal to 285 ℃;
(3) The ratio of total carbon atoms to total amide bonds is 9.1 to 9.3;
(4) Melting Peak temperature T m2 Is 315-340 ℃.
In the application, the method for testing the relative viscosity eta r of the polyamide in sulfuric acid at 25 ℃ is as follows: the concentrated sulfuric acid method of the Ubbelohde viscometer is adopted, 0.25 g+/-0.0002 g of the dried polyamide sample is accurately weighed, 25mL of concentrated sulfuric acid (98%) is added for dissolution, and the flow-through time T0 of the concentrated sulfuric acid and the flow-through time T of the polyamide solution are measured and recorded in a constant temperature water tank at 25 ℃.
Relative viscosity ηr=t/T0.
The polyamide has a crystallization temperature Tc and a melting peak temperature T m2 Reference is made to ASTM D3418-2003,Standard Test Method for Transition Tem for test methods of (C)peratures of Polymers By Differential Scanning Calorimetry。
The relative viscosity eta r, the crystallization temperature Tc and the melting peak temperature T of the polyamide m2 When the ratio of total carbon atoms to total amide bonds meets the parameter range, the polyamide has good color stability in a UV environment, is not easy to generate yellowing, and meets the application and production requirements of the LED reflecting bracket in terms of molding cycle, water absorption, heat resistance and mechanical property. The polyamide has a too small relative viscosity eta r, which results in poor color stability in a UV environment and poor initial color; too large a relative viscosity ηr of the polyamide may result in too long a molding cycle of the material. The melting point and crystallization temperature of the polyamide are too low, which can lead to too long molding cycle of the material; too high a melting point and crystallization temperature of the polyamide can result in a material with poor initial color. The excessive ratio of total carbon atoms to total amide bonds of the polyamide can lead to lower crystallization temperature of the polyamide and longer molding cycle of the material; the ratio of total carbon atoms to total number of amide bonds of the polyamide being too small, results in a melting peak temperature T of the polyamide m2 Higher, resulting in a material with poorer initial color and poorer UV resistance.
Preferably, the polyamide has a terminal amino group content M N 30-80 mmol/kg, and terminal carboxyl group content M c 50 to 100mmol/kg.
Preferably, the synthetic monomers of the polyamide comprise diamine and diamine, the molar ratio of the diamine to the diamine is 1.00-1.04, the diamine is alicyclic diamine and/or alicyclic diamine derivatives, and the diamine is straight-chain diamine with the carbon number X more than or equal to 10. When polyamide is prepared using a formulation with a molar ratio (diamine/diacid) greater than 1.04, this results in an amino-terminated group M of the polyamide N Higher content of carboxyl end group M c The UV resistance of the composition is poor due to the low content. When polyamide is prepared using a formulation with a molar ratio (diamine/diacid) of less than 1.00, this results in a composition with a poor initial color.
The cycloaliphatic diacid includes, but is not limited to, 1,4 cyclohexane dicarboxylic acid, 1,4 cyclohexane diacetic acid, 1,3 cyclohexane dicarboxylic acid, and the like.
The alicyclic dibasic acid derivatives include, but are not limited to, 1,4 cyclohexane dicarboxylic anhydride and the like.
Such diamines include, but are not limited to, decandiamine, undecanediamine, dodecandiamine, and the like.
The invention also provides a preparation method of the polyamide, which comprises the following steps:
(1) Atomizing and salifying prepolymerization: uniformly mixing metered diamine and an auxiliary agent, adding the mixture into a container A, heating the container A to 30-100 ℃, adding metered diacid and benzoic acid into a container B, heating the container B to 130-200 ℃, pressing substances in the container A and the container B into an atomization device of a prepolymerization kettle at the same flow rate through nitrogen, spraying out from an atomization opening under the current carrying effect of the nitrogen, atomizing to form salt, heating the prepolymerization kettle to 190-220 ℃ after the reaction is completed, reacting at constant temperature to obtain polyamide prepolymer, discharging and granulating;
(2) Solid phase tackifying stage: and (3) putting the polyamide prepolymer granules prepared in the step (1) into a rotary drum, heating to a temperature of 40-60 ℃ below the melting point of the polyamide prepolymer, keeping the temperature for 2-4 hours, stopping heating, and filling nitrogen into the rotary drum for cooling to obtain the polyamide.
Preferably, the amino end group content M of the polyamide prepolymer YN 1800-2000 mmol/kg.
The auxiliary agent adopted in the preparation method of the polyamide can be selected from antioxidant 1098, sodium hypophosphite serving as a triamine inhibitor, light stabilizer SEED and the like.
The invention also provides application of the polyamide in preparing an LED reflection bracket.
The invention also provides a polyamide composition which comprises the following components in parts by weight: 30-100 parts of polyamide, 0-60 parts of inorganic filler, 0-5 parts of nucleating agent, 0-5 parts of lubricant, 0-5 parts of antioxidant and 0-40 parts of pigment.
In some embodiments of the polyamide composition, the nucleating agent may be a mineral nucleating agent such as talc, the lubricant may be a polyolefin-based lubricant, the antioxidant may be an antioxidant 1098, and the pigment may be titanium pigment.
Preferably, the inorganic filler is at least one of glass fiber, alkaline earth metal oxide (e.g., magnesium oxide).
The invention also provides application of the polyamide composition in preparing an LED reflection bracket.
The invention also provides an LED reflecting support which is made of the polyamide composition.
Compared with the prior art, the invention has the beneficial effects that: the polyamide provided by the invention has high ultraviolet aging resistance, has good color stability in a UV environment, is not easy to generate yellowing, and meets the application and production requirements of the LED reflecting bracket in terms of molding cycle, water absorption, heat resistance and mechanical property.
Detailed Description
The technical solution of the present invention will be further described with reference to the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The starting materials used in the examples and comparative examples were all commercially available and were the same for the parallel experiments.
The performance evaluation method comprises the following steps:
1. the method for testing the end group content comprises the following steps: the test was performed as specified in GB/T14190-2008, method A.
2. Relative viscosity test method: the concentrated sulfuric acid method of the Ubbelohde viscometer is adopted, 0.25 g+/-0.0002 g of the dried polyamide sample is accurately weighed, 25mL of concentrated sulfuric acid (98%) is added for dissolution, and the flow-through time T0 of the concentrated sulfuric acid and the flow-through time T of the polyamide solution are measured and recorded in a constant temperature water tank at 25 ℃.
Relative viscosity ηr=t/T0.
3. Melt crystallization temperature test method: reference is made to ASTM D3418-2003,Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry. The specific test method comprises the following steps: collectingMelting points of the samples were measured with a Perkin Elmer Dimond DSC analyzer; a nitrogen atmosphere with a flow rate of 50mL/min; the temperature is raised to 350 ℃ at 20 ℃/min, maintained at 350 ℃ for 2min, cooled to 50 ℃ at 20 ℃/min, the exothermic peak temperature at the moment is set as crystallization temperature Tc, maintained at 50 ℃ for 2min, and raised to 350 ℃ at 20 ℃/min, and the first endothermic peak temperature at the moment is set as melting point T m1 The method comprises the steps of carrying out a first treatment on the surface of the The second endothermic peak temperature is set to be the melting point T m2 。
4. Polyamide composition molding cycle: placing the prepared polyamide composition in a baking oven at 120 ℃ for 4 hours, and then performing injection molding by using an east ocean CS-100 injection molding machine; the injection molding temperature is higher than the melting point by 20 ℃, the LED bracket model 2121 and the mold cavity number 1440; cooling water is introduced into the mold in the injection molding process, the same injection molding speed, pressure and other processes are adopted, the same mold is continuously injected for 50 times, and the time T for filling 50 parts is recorded on the premise of ensuring the finished parts to be complete. Molding cycle p=t/50.
5. Whiteness value test: measured using Color Eye 7000A Color difference meter. A sample of the polyamide composition was injection molded, and the sample size was 60X 1.0mm. The initial values of L, a and b of the sample were measured, the initial Hunter whiteness value was calculated by the formula 1, and the sample was then subjected to UV irradiation treatment, respectively, to evaluate the UV aging resistance of the sample. The conditions of UV irradiation treatment were as described in reference to GB/T16422.3-2014. A UVA-340 light source was selected, the exposure period was 8 hours, and the test method was a 4 hour condensation test method, the test sample was placed in a test box for 7 days, and then the L, a and b values were measured again, and the Hunter whiteness value after UV irradiation treatment was calculated by the formula 1.
(formula 1) w=100- [ (100-L) 2 +a 2 +b 2 ] 0.5
UV retention (%) =hunter whiteness value after UV irradiation treatment/initial hunter whiteness value×100%
6. R460 reflectance test: measured using Color Eye 7000A Color difference meter. The polyamide composition sample was injection molded, and the sample size was 60X 1.0mm. The reflectance of the initial state of the sample at a wavelength of 460nm was measured. The samples were then individually subjected to UV irradiation treatment, whereby the UV aging resistance of the samples was evaluated. The conditions for the UV irradiation treatment were as described in reference GB/T16422.3-2014. A UVA-340 light source was selected, the exposure period was 8h dry, the test method of 4h condensation, the sample was placed in a test chamber for 7 days, and its reflectance at a wavelength of 460nm was again measured.
Examples 1 to 4
Examples 1 to 4 provide a process for the preparation of polyamides, comprising the following steps:
(1) Atomizing and salifying prepolymerization: firstly, adding metered diamine monomer and auxiliary agent into a container A with a heating device, and heating to 30-100 ℃; then adding the measured dibasic acid and benzoic acid into a container B with a heating device, and heating to 130-200 ℃; pressing substances in a container A and a container B into an atomization device of a prepolymerization kettle at the same flow rate through nitrogen, spraying mixed liquid pumped from the container A and the container B by the atomization device in the prepolymerization kettle at the flow rate of 2.0L/min (the flow rate is 16.5 m/s) from an atomization opening, atomizing to form salt, continuously introducing nitrogen for a period of time after the reaction is finished, heating the prepolymerization kettle to 190-220 ℃, reacting at constant temperature for 1h to obtain polyamide prepolymer, discharging and granulating;
(2) Solid phase tackifying stage: and (3) putting the polyamide prepolymer granules prepared in the step (1) into a rotary drum, heating to 40-60 ℃ below the melting point of the polyamide prepolymer, and reacting for 2 hours at constant temperature to obtain the polyamide.
The specific formulations of examples 1 to 4 are as follows:
example 1: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2185.8g of decanediamine, 1089.2g of dodecanediamine, 6.3g of sodium hypophosphite, 12.5g of 1098 antioxidant and 74.5g of benzoic acid.
Example 2: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2450.0g of decanediamine, 712.2g of dodecanediamine, 6.2g of sodium hypophosphite, 12.5g of 1098 antioxidant and 74.5g of benzoic acid.
Example 3: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2702.2g of decanediamine, 349.1g of dodecanediamine, 6.1g of sodium hypophosphite, 1098 of antioxidant 12.3g and 74.5g of benzoic acid.
Example 4: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2450.0g of decanediamine, 662.3g of undecanediamine, 6.2g of sodium hypophosphite, 1098 antioxidant 12.4g and 74.5g of benzoic acid.
Comparative examples 1 to 9
Comparative examples 1 to 9 provide a process for producing polyamides, the formulation of which is as follows, and the process for producing polyamides is as described in examples 1 to 4.
Comparative example 1: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2450.0g of decanediamine, 712.2g of dodecanediamine, 6.2g of sodium hypophosphite, 12.5g of 1098 antioxidant and 74.5g of benzoic acid. After the completion of the prepolymerization reaction in the same manner as in examples 1 to 4, the prepolymer was pelletized and solid phase tackified at 270℃for 4 hours to obtain a polyamide.
Comparative example 2: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2450.0g of decanediamine, 712.2g of dodecanediamine, 6.2g of sodium hypophosphite, 12.5g of 1098 antioxidant and 95.8g of benzoic acid. After the completion of the prepolymerization reaction in the same manner as in examples 1 to 4, the prepolymer was pelletized and solid phase tackified at 270℃for 2 hours to obtain a polyamide.
Comparative example 3: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 3062.5g of decanediamine, 6.1g of sodium hypophosphite, 12.3g of 1098 antioxidant and 74.5g of benzoic acid.
Comparative example 4: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 3560.8g of dodecanediamine, 6.6g of sodium hypophosphite, 13.3g of 1098 antioxidant and 74.5g of benzoic acid.
Comparative example 5: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2756.2g of decanediamine, 206.5g of hexamethylenediamine, 6.0g of sodium hypophosphite, 12.1g of 1098 antioxidant and 74.4g of benzoic acid.
Comparative example 6: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2389.9 g of decanediamine, 694.7g of dodecanediamine, 6.2g of sodium hypophosphite, 12.3g of 1098 antioxidant and 74.5g of benzoic acid.
Comparative example 7: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2594.1 g of decanediamine, 754.1g of dodecanediamine, 6.4g of sodium hypophosphite, 12.8g of 1098 antioxidant and 74.5g of benzoic acid.
Comparative example 8: 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2450.0g of decanediamine, 712.2g of dodecanediamine, 6.2g of sodium hypophosphite, 12.5g of 1098 antioxidant and 74.5g of benzoic acid. After the completion of the prepolymerization reaction in the same manner as in examples 1 to 4, the prepolymer was pelletized and solid phase tackified at 270℃for 1 hour to obtain a polyamide.
Comparative example 9: firstly, heating a reaction device to 50-80 ℃, and then adding 3000.0g of 1,4 cyclohexane dicarboxylic acid, 2450.0g of decanediamine, 712.2g of dodecanediamine, 6.2g of sodium hypophosphite, 12.5g of 1098 antioxidant, 74.5g of benzoic acid and 1103.8g of deionized water into the reaction kettle under the protection of high-purity nitrogen to obtain a polyamide salt water solution; transferring the aqueous solution of polyamide salt into a polymerization device, heating the polymerization device to 212 ℃ under the protection of high-purity nitrogen, raising the pressure to 2.0MPa, reacting at constant temperature for 1h, keeping the system pressure unchanged after the reaction is finished, obtaining a dried prepolymer through flash evaporation, discharging and granulating.
The results of the properties of examples 1 to 4 and comparative examples 1 to 9 are shown in Table 1.
In table 1, a represents: the ratio of the number of carbon atoms to the number of amide bonds (carbon atoms/amide bonds);
b represents: molar ratio of diamine to diacid (diamine/diacid).
TABLE 1
Examples 5 to 8 and comparative examples 10 to 18 respectively provide polyamide compositions whose weight part formulations and performance test results are shown in Table 2. Among these, the polyamides of examples 5 to 8 and comparative examples 10 to 18 are the polyamides prepared in examples 1 to 4 and comparative examples 1 to 8, respectively, and the commercially available product PA10T.
TABLE 2
Note that: in table 2 "-" indicates that the component was not added.
It will be appreciated by those skilled in the art that in LED reflector bracket applications, it is generally desirable that the polyamide have an initial hunter value of 96 or more, a hunter value retention of 99% or more after UV irradiation, an R460 reflectance retention of > 98% after UV irradiation, and a molding cycle of 13s or less.
Analysis of results: it can be seen from comparative examples 1 and 10 that when the ηr viscosity of the polyamide is too high, the molding cycle of the composition is long. As can be seen from comparative examples 2 and 11, too low an eta r viscosity of the polyamide results in a composition having poor initial color and poor UV resistance. As can be seen from comparative examples 3 and 12, when the ratio of total carbon atoms to the total number of amide bonds is low, the melting peak temperature T of the polyamide is caused m2 Higher, resulting in a composition with poorer initial color and poorer UV resistance. As can be seen from comparative examples 4 and 13, when the ratio of total carbon atoms to the total number of amide bonds is high, the crystallization temperature Tc of the polyamide is low, resulting in a longer molding cycle of the composition. As can be seen from comparative examples 5 and 14, when a diamine having less than 10 carbon atoms is used to prepare a polyamide, the polyamide has poor aging resistance due to an increased density of amide bonds. As can be seen from comparative examples 6 and 15, when the polyamide is prepared using a formulation having a molar ratio (diamine/diacid) greater than 1.04, the amino end groups M of the polyamide are caused N Higher content of carboxyl end group M c The UV resistance of the composition is poor due to the low content. As can be seen from comparative examples 7 and 16, when polyamide is prepared using a formulation having a molar ratio (diamine/diacid) of less than 1.00, the initial color of the composition is poor. As can be seen from comparative example 8 and comparative example 17, when the terminal amino group M of the polyamide N And terminal carboxyl group M c When the content of (C) is too high, the groupThe initial color and UV resistance of the compound are poor. As can be seen from comparative example 18, the use of conventional PA10T aromatic polyamide has poor UV aging resistance, resulting in poor color of the composition, which cannot meet the high-end applications of LEDs. As can be seen from comparative example 9, the existing conventional prepolymerization method is used for obtaining a polyamide prepolymer, which has precipitation problems, cannot obtain uniform components, and fails to prepare the product, so that the subsequent solid-phase tackifying procedure is not performed.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. A polyamide characterized by the following features:
(1) The relative viscosity eta r in sulfuric acid at 25 ℃ is 2.0-2.2;
(2) The crystallization temperature Tc is more than or equal to 285 ℃;
(3) The ratio of total carbon atoms to total amide bonds is 9.1-9.3;
(4) Melting Peak temperature T m2 315-340 ℃;
(5) Terminal amino group content M of polyamide N 30-80 mmol/kg, and terminal carboxyl group content M c 50-100 mmol/kg;
the synthetic monomers of the polyamide comprise diamine and diamine, the molar ratio of the diamine to the diamine is 1.00-1.04, the diamine is alicyclic diamine and/or alicyclic diamine derivatives, and the diamine is straight-chain diamine with the carbon number X more than or equal to 10.
2. The method for producing a polyamide according to claim 1, comprising the steps of:
(1) Atomizing and salifying prepolymerization: uniformly mixing metered diamine and an auxiliary agent, adding the mixture into a container A, heating the container A to 30-100 ℃, adding metered diacid and benzoic acid into a container B, heating the container B to 130-200 ℃, pressing substances in the container A and the container B into an atomization device of a prepolymerization kettle at the same flow rate through nitrogen, spraying out from an atomization opening under the current carrying effect of the nitrogen, atomizing to form salt, heating the prepolymerization kettle to 190-220 ℃ after the reaction is completed, reacting at constant temperature to obtain polyamide prepolymer, discharging and granulating;
(2) Solid phase tackifying stage: and (3) putting the polyamide prepolymer granules prepared in the step (1) into a rotary drum, heating to a temperature of 40-60 ℃ below the melting point of the polyamide prepolymer, keeping the temperature for 2-4 hours, stopping heating, and filling nitrogen into the rotary drum for cooling to obtain the polyamide.
3. The process for preparing polyamides according to claim 2 wherein the polyamide prepolymer has an amino end group content M YN 1800-2000 mmol/kg.
4. Use of the polyamide according to claim 1 for the preparation of a reflective LED support.
5. A polyamide composition characterized by comprising the following components in parts by weight: 30-100 parts of polyamide, 0-60 parts of inorganic filler, 0-5 parts of nucleating agent, 0-5 parts of lubricant, 0-5 parts of antioxidant and 0-40 parts of pigment, wherein the polyamide is the polyamide according to claim 1.
6. The polyamide composition of claim 5 wherein the inorganic filler is at least one of glass fiber and an alkaline earth metal oxide.
7. Use of the polyamide composition according to claim 5 or 6 for the preparation of a reflective LED support.
8. An LED reflector holder made from a composition comprising the polyamide of claim 5 or 6.
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