CN113929901B - Polyamide resin, composition and preparation method thereof - Google Patents
Polyamide resin, composition and preparation method thereof Download PDFInfo
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- CN113929901B CN113929901B CN202111244466.2A CN202111244466A CN113929901B CN 113929901 B CN113929901 B CN 113929901B CN 202111244466 A CN202111244466 A CN 202111244466A CN 113929901 B CN113929901 B CN 113929901B
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000002425 crystallisation Methods 0.000 claims abstract description 60
- 230000008025 crystallization Effects 0.000 claims abstract description 58
- 239000004952 Polyamide Substances 0.000 claims abstract description 40
- 229920002647 polyamide Polymers 0.000 claims abstract description 40
- 150000004985 diamines Chemical class 0.000 claims description 50
- 238000002844 melting Methods 0.000 claims description 40
- 230000008018 melting Effects 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 25
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000012360 testing method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000012763 reinforcing filler Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 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 claims description 7
- 239000005711 Benzoic acid Substances 0.000 claims description 7
- 235000010233 benzoic acid Nutrition 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims description 3
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 abstract description 19
- 238000011161 development Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 24
- 238000000465 moulding Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001746 injection moulding Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- GAGWMWLBYJPFDD-UHFFFAOYSA-N 2-methyloctane-1,8-diamine Chemical compound NCC(C)CCCCCCN GAGWMWLBYJPFDD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- MSVPBWBOFXVAJF-UHFFFAOYSA-N tetradecane-1,14-diamine Chemical compound NCCCCCCCCCCCCCCN MSVPBWBOFXVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012463 white 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
-
- 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
- C08G69/28—Preparatory processes
-
- 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
Abstract
The invention relates to the field of high-temperature resistant polyamide, and discloses a polyamide resin, a composition and a preparation method thereof. The invention also provides a preparation method of the polyamide resin, and the polyamide resin, the preparation method of the high-temperature resistant polyamide resin, the polyamide composition containing the polyamide resin and the preparation method of the polyamide composition are applied to LED illumination reflection brackets. The polyamide resin and the polyamide composition have specific molecular chain structures and crystallization states, so that the polyamide resin and the polyamide composition show rapid crystallization rate, and are suitable for the development trend of small size and thinning of LED illumination reflection brackets.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to the field of high-temperature resistant polyamide, and specifically relates to a polyamide resin, a composition thereof and a preparation method thereof.
Background
Compared with semi-aromatic high-temperature resistant polyamide polymerized by terephthalic acid or isophthalic acid, the high-temperature resistant polyamide polymerized by 1, 4-cyclohexane dicarboxylic acid monomer has no benzene ring in the molecular structure and weak electron-withdrawing effect. Therefore, when the high-temperature resistant polyamide polymerized by the 1, 4-cyclohexane dicarboxylic acid monomer is subjected to long-term ultraviolet aging, electrons are not easily obtained, the molecular structure is more stable, and the ultraviolet aging resistance is better.
Such as: in patent CN102482492B, a polyamide containing a 1, 4-cyclohexanedicarboxylic acid structure developed by japan colali corporation is used as a material for an LED illumination reflective support, which can maintain high reflectance and whiteness after being irradiated with an LED lamp for a long period of time.
As consumer demand increases, LED light beads gradually decrease in size, and LED lighting reflective brackets gradually develop toward smaller size and thinner wall; in order to improve the production efficiency and reduce the production energy consumption, the injection molding factory gradually increases the mold cavity number of the LED illumination reflecting support from below 800 to above 1500, and cold mold molding replaces high-mold temperature molding. However, the existing high temperature resistant polyamide material polymerized by 1, 4-cyclohexane dicarboxylic acid monomer has slower crystallization rate, long cooling time in cold die forming, failure in rapid forming, incomplete cooling, and easy product sticking to the die, high material belt pulling and other problems.
Therefore, how to increase the crystallization rate of the high temperature resistant polyamide material polymerized by 1, 4-cyclohexane dicarboxylic acid monomer and shorten the molding cooling period so as to adapt to the development trend of the thin wall and multiple mold cavities of the LED reflecting bracket is one of the important research directions to be solved in the field.
Disclosure of Invention
The invention aims to solve the technical problems that a polyamide material cannot be rapidly molded and is incompletely cooled, so that a product sticks to a die and a material belt is pulled up.
In order to solve the technical problem described above, in a first aspect, the present invention provides a polyamide resin comprising repeating units of:
(a) 1, 4-cyclohexanedicarboxylic acid;
(b) A linear diamine having 8 or more carbon atoms;
(c) A diamine having 8 or more carbon atoms, which is different from the diamine (b);
the mole fraction of (b) to the total diamine of (b) and (c) is 80 to 90 mole percent;
the number of carbon atoms of (b) differs from the number of carbon atoms of (c) by 0 to 4.
The polyamide resin of the present invention uses a linear diamine having 8 or more carbon atoms as a main diamine and uses a diamine having 8 or more carbon atoms, which is different from the main diamine, as a co-diamine, such as: polyamide resins prepared from 1, 10-decanediamine, 1, 9-nonanediamine, 1, 12-dodecanediamine and 2-methyl-1, 8-octanediamine have high molecular chain flexibility due to low amide bond density; and the carbon atoms of the main diamine and the co-diamine are different by 0-4, the molecular chain structure and the flexibility of the main diamine and the co-diamine are close, the crystallization performance is better, and the crystallization rate is high.
As a preferable embodiment of the polyamide resin of the present invention, the diamine has 8 to 12 carbon atoms, and the production cost is low, so that the production efficiency is high and the practicability is high.
As a preferred embodiment of the polyamide resin of the present invention, the T-melting point of the resin is controlled as follows: 315 ℃ < T melting point <340 ℃. The T crystallization temperature of the resin is controlled as follows: (T melting point-T crystallization temperature). Times.T crystallization peak half-width <350.
The T melting point is the peak value of a melting peak on a DSC test second temperature rise curve, and the T crystallization temperature is the peak value of a crystallization peak on a DSC test second temperature drop curve. 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: testing the melting point of the sample by using a Perkin Elmer Dimond DSC analyzer; a nitrogen atmosphere with a flow rate of 50mL/min; during testing, the temperature is firstly increased to 350 ℃ at 20 ℃/min, the temperature is kept at 350 ℃ for 2min, the thermal history of the resin is removed, then the resin is cooled to 50 ℃ at 20 ℃/min, and the exothermic peak temperature at the moment is set as the T crystallization temperature; setting the initial temperature of an exothermic peak as a melting point T1, setting the final temperature of the exothermic peak as a melting point T2, and setting the half-peak width of a T crystallization peak as (T1-T2)/2; after maintaining at 50℃for 2min, the temperature was raised to 350℃at 20℃per min, and the endothermic peak temperature at this time was set to T-melting point.
According to the research of the invention, the actual reaction of (T melting point-T crystallization temperature) x T crystallization peak half-width is the crystallization behavior of the high-temperature resistant polyamide polymerized by 1, 4-cyclohexane dicarboxylic acid monomer. The crystallization behavior is closely related to the crystal melting behavior and the structural characteristics of the molecular chains. The factors influencing the half-peak width of the T crystallization peak, the T melting point and the T crystallization temperature are various, such as the difference of the monomer proportion, the degree of monomer self-polymerization, the change of the molecular weight and the molecular chain sequence structure, whether the molecular chain segments are uniform and the molecular chains are regular, the entanglement or branching degree of the molecular chains, the rotation capacity of the molecular chains, the movement capacity of the molecular chains, the preparation process and other factors, so that the finally prepared high temperature resistant polyamide molecular chain structure has great difference, and the crystallization behavior is influenced.
And (T melting point-T crystallization temperature) x T crystallization peak half-width actually reflects the overall crystallization rate of the material: t melting point-T crystallization temperature, when the material is cooled, crystallization starts to occur at a temperature below the melting point; the half-width of the T crystallization peak reflects how short the material can be crystallized in the temperature range.
The present invention has been found that when the thermal performance parameters of the high temperature resistant polyamide polymerized from 1, 4-cyclohexanedicarboxylic acid monomers are simultaneously: when 315 ℃ and (T melting point-T crystallization temperature) multiplied by half-peak width of T crystallization peak is less than 350, the prepared LED reflective support material has optimal molding characteristics:
when the T melting point is lower than 315 ℃, the material has insufficient temperature resistance and cannot be applied to the field of LED reflection brackets; when the T melting point is higher than 340 ℃, the melting point of the material is close to the decomposition temperature, decomposition occurs during injection molding, and the material cannot be applied to the field of LED reflecting supports; only when 315 ℃ and the T melting point is lower than 340 ℃, the material has excellent heat resistance and does not decompose during injection molding.
When the half-peak width of the (T melting point-T crystallization temperature) multiplied by T crystallization peak is less than 350, the material can not only begin to crystallize at a higher temperature below the melting point, but also complete crystallization in a shorter temperature interval, and the comprehensive crystallization rate is higher. When the half-peak width of the (T melting point-T crystallization temperature) x T crystallization peak is more than 350, the material is lower in crystallization starting temperature, the material needs to be cooled for a longer time to start crystallization, and after crystallization starts, crystallization cannot be completed in a shorter time, so that the overall crystallization rate is slower, the cooling time required in cold die forming is longer, rapid forming cannot be realized, and if cooling is incomplete, the problems of die sticking, material belt pulling-up and the like of a product are easily caused, and the material belt cooling device is not suitable for the small-size and thinning development trend of an LED illumination reflection bracket.
In a second aspect, the present invention also provides a method for preparing a polyamide resin, comprising the steps of:
(1) Weighing the monomers according to the proportion; adding benzoic acid, sodium hypophosphite and water to obtain a reaction mixture;
(2) Vacuumizing, filling a protective gas, and stirring the reaction mixture at 220-225 ℃; stirring at constant temperature of 230-235 ℃ and constant pressure of 2.0-2.2 MPa, and discharging to obtain prepolymer;
(3) Vacuum drying the prepolymer to obtain a prepolymer product;
(4) The prepolymer is solid-phase tackified for 8-10 hours under the vacuum condition of 50-55 Pa at the temperature of 250-255 ℃ to obtain the polyamide resin.
In the preferred embodiment of the method for producing a polyamide resin according to the present invention, in the step (1), the amount of the benzoic acid substance is 2 to 2.5% of the amount of the monomer substance, the sodium hypophosphite is 0.1 to 0.15% by weight based on the total amount of the raw materials excluding the water, and the water is 25 to 35% by weight based on the total amount of the raw materials.
In a third aspect, the present invention also provides a polyamide composition comprising said high temperature resistant polyamide resin.
As a preferred embodiment of the polyamide composition according to the invention, the composition further comprises pigments and/or reinforcing fillers.
As a preferred embodiment of the polyamide composition of the present invention, the weight ratio of the high temperature resistant polyamide resin, the pigment and the reinforcing filler is, in parts by weight, that of the high temperature resistant polyamide resin: and (3) pigment: reinforcing filler = (50-55): (30-35): (10-15).
In a fourth aspect, the present invention also provides a process for preparing a polyamide composition comprising the steps of:
adding the polyamide resin and other components into an extruder, extruding, cooling, granulating and drying to obtain the polyamide resin.
In a fifth aspect, the present invention applies the polyamide resin, the method for producing the polyamide resin, the polyamide composition, and the method for producing the polyamide composition to an LED illumination reflective support so as to be suitable for the trend of small-size and thin-wall of LED illumination reflective supports.
Compared with the prior art, the invention has the beneficial effects that:
1. the polyamide resin provided by the invention takes linear diamine with more than 8 carbon atoms as main diamine and diamine with more than 8 carbon atoms which is different from the main diamine as co-diamine, and the prepared polyamide resin has low density of amide bonds, high flexibility of molecular chains, and controllable melting point at 315 ℃ and lower than 340 ℃, and is suitable for the field of LED illumination reflection brackets; and the main diamine and the co-diamine have similar carbon atoms, so that the molecular chain has similar structure and flexibility, better crystallization performance and high crystallization rate.
2. The invention screens the mole ratio of the main diamine and the co-diamine, and discovers that when the mole fraction of the main diamine in the diamine is 80-90 mole percent, the thermal performance of the polyamide resin simultaneously meets the following conditions: the polyamide composition prepared by the method has the molding cycle of less than 15s (including 15 s) and high molding efficiency when the LED illumination reflecting support is molded.
3. The polyamide resin and the polyamide composition have specific molecular chain structures and crystallization states, so that the polyamide resin and the polyamide composition show rapid crystallization rate, are suitable for the development trend of small size and thinning of LED illumination reflection brackets, and are suitable for the field of LED illumination reflection brackets.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the description of the present invention, it should be understood that the apparatus or device referred to is a conventional apparatus or device unless otherwise indicated; the monomers or compounds referred to, unless otherwise specified, are all commercially available conventional test monomers or compounds; the methods involved, unless otherwise specified, are all conventional methods.
The method for testing the related index in the embodiment is as follows:
1. the thermal performance parameter test method of the polyamide resin comprises the following steps: 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: testing the melting point of the sample by using 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, the temperature is kept at 350 ℃ for 2min, the thermal history of the resin is removed, the resin is cooled to 50 ℃ at 20 ℃/min, the temperature is kept at 50 ℃ for 2min, the temperature is raised to 350 ℃ at 20 ℃/min, the temperature of the heat absorption peak at the moment is set as a T melting point, the temperature is kept at 350 ℃ for 2min, the temperature is cooled to 50 ℃ at 20 ℃/min, the temperature of the heat release peak at the moment is set as a T crystallization temperature, and the peak width at half the height position of the heat release peak is set as the half peak width of the T crystallization peak.
LED reflection bracket molding cycle: placing the obtained 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 model 2835 of the LED bracket and the number of mold cavities 1584; cooling water is introduced into the mold for cooling in the injection molding process; the time required to injection mold a molded defect-free article is noted as the molding cycle t.
The raw materials used in the following examples and comparative examples are described below, but are not limited to these materials:
diacid: 1, 4-cyclohexanedicarboxylic acid, commercially available;
diamine: 1, 10-decanediamine, 1, 9-nonanediamine, 1, 12-dodecanediamine, 2-methyl-1, 8-octanediamine, 1, 14-tetradecanediamine, 1, 6-hexanediamine, commercially available;
benzoic acid: analytically pure, purchased from Sigma-Aldrich company;
sodium hypophosphite: analytically pure, purchased from Sigma-Aldrich company;
reinforcing filler: glass fiber, T435N, available from Taishan glass fiber Co., ltd;
and (3) pigment: titanium dioxide, R105, available from dupont limited.
Examples and comparative examples:
1. preparation of Polyamide resins
The polymerization method of the polyamide comprises the following steps:
weighing the monomers according to the proportion in the table 1, and adding the reaction monomers (diamine and diacid) into a pressure kettle provided with a magnetic coupling stirring device, a condensing tube, a gas phase port, a charging port and a pressure explosion-proof port according to the proportion in the table; adding benzoic acid, sodium hypophosphite (catalyst) and deionized water; the amount of the benzoic acid substance is 2.5% of the total amount of diamine and diacid, the weight of sodium hypophosphite is 0.1% of the weight of other materials except deionized water, and the weight of deionized water is 30% of the total weight of materials; vacuumizing, filling high-purity nitrogen as a shielding gas, heating to 220 ℃ in 2 hours under stirring, stirring the reaction mixture at 220 ℃ for 1 hour, and then heating the reactant to 230 ℃ under stirring; the reaction was continued at a constant temperature of 230℃and a constant pressure of 2.2MPa for 2 hours, the pressure was kept constant by removing the water formed, and after the completion of the reaction, the material was discharged, and the prepolymer was dried under vacuum at 80℃for 24 hours to obtain a prepolymer, which was solid-phase-thickened at 250℃under a vacuum of 50Pa for 10 hours to obtain a polyamide resin.
The results of the performance test of the polyamide resins obtained in examples and comparative examples are shown in Table 1.
Table 1: polyamide resins of examples and comparative examples were prepared by mixing the monomers and testing the results
Table 1, below
Table 1, below
2. Preparation of Polyamide compositions
The preparation method of the polyamide composition comprises the following steps:
the components are weighed according to the proportion of Table 2, polyamide resin and white pigment are mixed uniformly in a high-speed mixer, then added into a double-screw extruder through a main feeding port, the extrusion temperature is 350 ℃, the screw rotation speed is 600rpm, reinforcing filler is fed by a side feeding scale side, extruded, cooled by water, granulated and dried to obtain the polyamide composition.
The results of the performance test of the polyamide compositions obtained in examples and comparative examples are shown in Table 2.
Table 2: examples and comparative examples Polyamide moulding compositions component proportions (parts by weight) and results of performance tests
Continuing with table 2:
continuing with table 2:
as can be seen from the test cases of the polyamide resin and the composition of the examples, when the main diamine monomer of the polyamide resin is a linear diamine having 8 or more carbon atoms and the mole fraction of the diamine is 80 to 90mol%, the copolymerized diamine monomer is a diamine having 8 or more carbon atoms different from the main diamine, the carbon atoms of the main diamine and the copolymerized diamine monomer differ by 0 to 4, and the melting point of the polyamide resin satisfies: 315 ℃ < T melting point <340 ℃, and simultaneously: (T melting point-T crystallization temperature). Times.T crystallization peak half-width <350. The polyamide composition prepared by the method has a molding cycle of less than 15s (including 15 s) when the LED illumination reflecting support is molded.
In the polyamide resins of comparative examples 1 and 3, the molar fraction of the diamine monomer in the main body is less than 80%, and the (T-melting point-T-crystallization temperature) ×T-crystallization peak half-width >350 of the polyamide resin has a serious influence on molding efficiency, which is generally considered unacceptable, when the LED illumination reflective bracket is injection-molded, because the molding cycles of the compositions of comparative examples 10 and 12 are 17 seconds or more.
When the LED illumination reflection bracket is subjected to injection molding, the production efficiency is reduced by about 6.7% every 1s of molding period. Typically, the molding cycle is within 15 seconds, and the molding efficiency of the material is acceptable; the molding period is more than 15s, the production efficiency is too low, and the molding process is not acceptable in practical production.
In the polyamide resins of comparative examples 2 and 4, the molar fraction of the diamine monomer of the main body is more than 90%, the T-melting point of the polyamide resin is >340 ℃, and the compositions of comparative examples 11 and 13 cannot be molded because the injection temperature is close to the decomposition temperature of the polyamide resin when the LED illumination reflection bracket is injection molded.
In the polyamide resins of comparative examples 5 to 7, the diamine monomer copolymerized is diamine having less than 8 carbon atoms, and the difference between the carbon chain length and the carbon chain length of the main diamine is large, so that the structure and flexibility of the molecular chain are uneven, and the crystallization performance is deteriorated, therefore, the (T melting point-T crystallization temperature) ×T crystallization peak half-width of the polyamide resin is more than 350, and the molding cycle of the compositions of comparative examples 14 to 16 is more than 25s and the molding efficiency is too low when the LED illumination reflection bracket is molded.
In the polyamide resin of comparative example 8, the main diamine monomer is diamine having less than 8 carbon atoms, and the polyamide resin has a high amide bond density and a low molecular chain flexibility, and the resin has a T-melting point of >360 ℃, so that the composition of comparative example 17 cannot be molded when the LED lighting reflective support is injection molded because the injection molding temperature exceeds the decomposition temperature of the polyamide resin.
In the polyamide resin of comparative example 9, the difference in the number of carbon atoms between the main diamine and the copolymerized diamine monomer is 5, the difference in the structure and flexibility of the two molecular chains is relatively large, the crystallization performance is poor, and the crystallization rate is slow. The molding cycle of the composition of comparative example 18 was 24s and the molding efficiency was low when the LED illuminated reflector bracket was injection molded.
In summary, the polyamide resin of the embodiment of the invention uses linear diamine with more than 8 carbon atoms as main diamine and uses diamine with more than 8 carbon atoms different from the main diamine as co-diamine, and the prepared polyamide resin has high flexibility of molecular chains due to low density of amide bonds, and the melting point can be controlled to be 315 ℃ < T melting point <340 ℃, thus being suitable for the field of LED illumination reflection brackets; and the main diamine and the co-diamine have similar carbon atoms, so that the molecular chain has similar structure and flexibility, better crystallization performance and high crystallization rate.
According to the embodiment of the invention, the mole ratio of the main diamine to the co-diamine is screened, and when the mole fraction of the main diamine to the diamine is 80-90 mole percent, the thermal performance of the polyamide resin simultaneously meets the following conditions: the polyamide composition prepared by the method has the molding cycle of less than 15s (including 15 s) and high molding efficiency when the LED illumination reflecting support is molded.
The polyamide resin and the polyamide composition provided by the embodiment of the invention are suitable for the development trend of small size and thin wall of the LED illumination reflection bracket.
Finally, it should be noted that the above 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 (9)
1. A polyamide resin comprising repeating units of:
(a) 1, 4-cyclohexanedicarboxylic acid;
(b) A linear diamine having 8 or more carbon atoms;
(c) A diamine having 8 or more carbon atoms, which is different from the diamine (b);
the mole fraction of the (b) accounting for 80-90 mol% of the total diamine of the (b) and (c) is calculated according to the mole percentage;
the number of carbon atoms of the (b) is different from the number of carbon atoms of the (c) by 0-4;
the (c) is any one of 1, 10-decanediamine, 1, 9-nonanediamine and 1, 12-dodecanediamine;
the T melting point of the resin is as follows: 315 ℃ < T melting point <340 ℃;
the resin has a (T melting point-T crystallization temperature) x T crystallization peak half width <350;
and the T melting point is the peak value of a melting peak on a DSC test second temperature rise curve, and the T crystallization temperature is the peak value of a crystallization peak on a DSC test second temperature drop curve.
2. The polyamide resin according to claim 1, wherein the diamine has 8 to 12 carbon atoms.
3. The method for producing a polyamide resin according to claim 1 or 2, characterized by comprising the steps of:
(1) Weighing the monomer; adding benzoic acid, sodium hypophosphite and water to obtain a reaction mixture;
(2) Vacuumizing, filling a protective gas, and stirring the reaction mixture at 220-225 ℃; stirring at a constant temperature of 230-235 ℃ and a constant pressure of 2.0-2.2 MPa, and discharging to obtain a prepolymer;
(3) Vacuum drying the prepolymer to obtain a prepolymer product;
(4) And (3) carrying out solid-phase tackifying on the prepolymer product for 8-10 hours at the temperature of 250-255 ℃ under the vacuum condition of 50-55 Pa to obtain the polyamide resin.
4. The method of producing a polyamide resin according to claim 3, wherein in the step (1), the amount of the benzoic acid substance is 2 to 2.5% of the amount of the monomer substance, the sodium hypophosphite is 0.1 to 0.15% by weight based on the total amount of the raw materials excluding the water, and the water is 25 to 35% by weight based on the total amount of the raw materials.
5. A polyamide composition comprising the polyamide resin according to claim 1 or 2.
6. Polyamide composition according to claim 5, characterized in that it further comprises pigments and/or reinforcing fillers.
7. The polyamide composition according to claim 6, wherein the weight ratio of the polyamide resin, pigment and reinforcing filler is, in parts by weight, polyamide resin: and (3) pigment: reinforcing filler= (50-55): (30-35): (10-15).
8. The method for producing a polyamide composition according to any one of claims 5 to 7, comprising the steps of:
and (3) adding the polyamide resin and other components into an extruder according to the proportion, extruding, cooling, granulating and drying to obtain the polyamide resin.
9. Use of the polyamide resin according to claim 1 or 2, the polyamide composition according to any one of claims 5 to 7 in LED lighting reflective brackets.
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| CN202111244466.2A CN113929901B (en) | 2021-10-25 | 2021-10-25 | Polyamide resin, composition and preparation method thereof |
| PCT/CN2022/127092 WO2023071997A1 (en) | 2021-10-25 | 2022-10-24 | Polyamide resin, and composition thereof and preparation method therefor |
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| CN202111244466.2A CN113929901B (en) | 2021-10-25 | 2021-10-25 | Polyamide resin, composition and preparation method thereof |
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| CN113929901B (en) * | 2021-10-25 | 2024-03-29 | 珠海万通特种工程塑料有限公司 | Polyamide resin, composition and preparation method thereof |
| CN114507343B (en) * | 2022-03-09 | 2024-03-22 | 金发科技股份有限公司 | Polyamide and preparation method and application thereof |
| CN115678268B (en) * | 2022-09-29 | 2024-03-26 | 珠海万通特种工程塑料有限公司 | Polyamide molding composition and preparation method and application thereof |
| CN116589675A (en) * | 2023-04-28 | 2023-08-15 | 珠海万通特种工程塑料有限公司 | Polyamide resin and polymerization method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482492A (en) * | 2009-09-07 | 2012-05-30 | 可乐丽股份有限公司 | Reflector for LED and light-emitting device equipped with same |
| CN104619777A (en) * | 2012-09-14 | 2015-05-13 | 株式会社可乐丽 | Polyamide resin |
| CN104662095A (en) * | 2012-09-28 | 2015-05-27 | 株式会社可乐丽 | Polyamide resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3481730B2 (en) * | 1995-06-26 | 2003-12-22 | 株式会社クラレ | Polyamide composition |
| KR101324739B1 (en) * | 2011-01-28 | 2013-11-05 | 가부시키가이샤 구라레 | Polyamide composition for reflective plate, reflective plate, light-emitting device comprising said reflective plate, and illumination device and image display device comprising said light-emitting device |
| JP6196892B2 (en) * | 2013-11-26 | 2017-09-13 | ロッテ アドバンスト マテリアルズ カンパニー リミテッド | Polyamide resin and polyamide molded body using the same |
| KR102430122B1 (en) * | 2015-06-29 | 2022-08-05 | 주식회사 쿠라레 | Polyamide composition for led reflection plate, led reflection plate, and light-emitting device including reflection plate |
| CN113929901B (en) * | 2021-10-25 | 2024-03-29 | 珠海万通特种工程塑料有限公司 | Polyamide resin, composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102482492A (en) * | 2009-09-07 | 2012-05-30 | 可乐丽股份有限公司 | Reflector for LED and light-emitting device equipped with same |
| CN104619777A (en) * | 2012-09-14 | 2015-05-13 | 株式会社可乐丽 | Polyamide resin |
| CN104662095A (en) * | 2012-09-28 | 2015-05-27 | 株式会社可乐丽 | Polyamide resin composition |
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