CN116589675A - Polyamide resin and polymerization method and application thereof - Google Patents
Polyamide resin and polymerization method and application thereof Download PDFInfo
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- CN116589675A CN116589675A CN202310479493.0A CN202310479493A CN116589675A CN 116589675 A CN116589675 A CN 116589675A CN 202310479493 A CN202310479493 A CN 202310479493A CN 116589675 A CN116589675 A CN 116589675A
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims description 8
- 238000006116 polymerization reaction Methods 0.000 title description 5
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical group N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004427 diamine group Chemical group 0.000 claims abstract description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 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
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 22
- 239000004952 Polyamide Substances 0.000 abstract description 12
- 229920002647 polyamide Polymers 0.000 abstract description 12
- 238000001953 recrystallisation Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 238000010998 test method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- MSVPBWBOFXVAJF-UHFFFAOYSA-N tetradecane-1,14-diamine Chemical compound NCCCCCCCCCCCCCCN MSVPBWBOFXVAJF-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000010354 integration Effects 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 description 2
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
The application discloses a polyamide resin, which comprises the following repeating units in percentage by mol: diacid unit: 1, 4-cyclohexanedicarboxylic acid; diamine unit: 1, 10-decanediamine and 1, 12-dodecanediamine, wherein the 1, 10-decanediamine accounts for 76-82% of the mass fraction of the diamine. So that the proportion of the trans-form structure in the polyamide resin of the present application is 81 to 85% by weight of the polyamide resin. The application can obtain specific trans-structure proportion by controlling the mass fraction of each unit in the polyamide, damages the regularity of a molecular chain, has higher initial light transmittance, can not generate recrystallization after SMT treatment, and can still keep higher light transmittance.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to polyamide resin, a polymerization method and application 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.
With the improvement of the living standard of people, the consumption demand of the LED lamp beads is improved, the semitransparent LED lamp bead varieties are gradually derived, the LED lamp bead variety can be applied to high-end fields such as outdoor transparent display screens, markets and counter display screens, and the commodity added value is higher. The product not only requires the material to have higher temperature resistance, but also has better light transmittance after SMT (infrared reflow soldering) encapsulation. However, conventional PPA materials are difficult to make transparent; even through structure adjustment, the resin is transparent in an initial state, recrystallization phenomenon can occur when SMT packaging is carried out subsequently, molecular chain rearrangement occurs, the molecular chain regularity is improved, the crystallinity is improved, and the transparent characteristic is lost, similar to the case of PCT materials. Currently, no suitable material exists in the market to meet the requirements of the semitransparent LED field.
Therefore, it is desirable to develop a polyamide resin matrix that has high temperature resistance and that maintains high transparency after SMT to meet the needs of translucent LED applications.
Disclosure of Invention
The application aims to provide a polyamide resin which is high in temperature resistance, high in initial light transmittance and free from recrystallization after SMT treatment, and a polymerization method and application thereof.
The application is realized by the following technical scheme:
a polyamide resin characterized by comprising the following recurring units in mole percent:
diacid unit: 1, 4-cyclohexanedicarboxylic acid;
diamine unit: 1, 10-decanediamine and 1, 12-dodecanediamine, wherein the 1, 10-decanediamine accounts for 76-82% of the mass fraction of the diamine.
Preferably, 1, 10-decanediamine comprises 78-80% by weight of diamine.
In the polyamide resin, the proportion of the trans-form structure to the mass fraction of the polyamide resin is 81-85%. The testing method comprises the following steps: 5mg of polyamide resin is taken and dissolved in 10mg of deuterated trifluoroacetic acid, and nuclear magnetic hydrogen spectrum test is carried out on the sample by using a Bruker DPX400 nuclear magnetic resonance apparatus. In the nuclear magnetic resonance hydrogen spectrum chart, the position of 1.96ppm is a cis structure peak, the position of 1.83ppm is a trans structure peak, and nuclear magnetic integration is carried out on the two peaks, so that the trans structure proportion of the resin can be obtained.
The melting point range of the polyamide resin is 321-334 ℃. 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 resin heat history is removed at 350 ℃ for 2min, then the resin is cooled to 50 ℃ at 20 ℃/min, the resin is kept at 50 ℃ for 2min, the temperature is raised to 350 ℃ at 20 ℃/min, and the endothermic peak temperature at the moment is set as T melting point.
The relative viscosity of the polyamide resin was in the range of 1.8 to 2.8, and the relative viscosity of the polyamide having a concentration of 0.25 g/dl was measured in 98% concentrated sulfuric acid at 25.+ -. 0.01 ℃ with reference to GB 12006.1-89.
The polymerization method of the polyamide resin comprises the following steps: adding a reaction monomer, benzoic acid, sodium hypophosphite and deionized water into a pressure kettle; the amount of the benzoic acid substance is 1.5-3.0% of the amount of the reaction monomer substance, the weight of sodium hypophosphite is 0.05-0.15% of the weight of other materials except deionized water, and the weight of deionized water is 25-35% of the total material; vacuumizing, filling inert gas (high-purity nitrogen can be used as shielding gas), heating to 215-225 ℃ within 1.5-2.5 hours, and reacting for 0.5-1.5 hours under the temperature range; then continuously reacting for 1-3 hours at 225-235 ℃ and under the pressure of 2.0-2.4 MPa, removing formed water in the reaction process, discharging after the reaction is finished, and vacuum drying the prepolymer to obtain a prepolymer product, wherein the prepolymer product is subjected to solid-phase tackifying for 8-12 hours at 240-260 ℃ and under the pressure of 45-55 Pa to obtain the polyamide resin.
The application of the polyamide resin disclosed by the application is used for preparing semitransparent LED related parts such as an LED lamp bracket.
The application has the following beneficial effects
Experiments show that the cis/trans structure of the polyamide resin is derived from 1, 4-cyclohexanedicarboxylic acid, and the 1, 4-cyclohexanedicarboxylic acid forms the diacid units of the polyamide resin, and a specific trans structure proportion can be obtained by controlling the molar content of each unit in the polyamide (the research shows that the trans structure proportion of the polyamide resin of which the 1, 4-cyclohexanedicarboxylic acid forms the diacid units is related to the structure and the proportion of diamine monomers, and the possible reason is that the longer the molecular chain of the diamine monomers is, the higher the trans structure stability is, and the higher the trans structure proportion is), the molecular chain regularity is damaged, the higher the initial light transmittance is, the recrystallization phenomenon is not generated after the SMT treatment, and the higher light transmittance can be still kept.
Description of the embodiments
The present application will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present application, but are not intended to limit the application in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present application.
1, 4-cyclohexanedicarboxylic acid: purity 98%, SKY CHDA, purchased from SK Chemicals;
1, 10-decanediamine: purity 97%, D100615, purchased from Shanghai aladine Biochemical technologies Co., ltd;
1, 12-dodecanediamine: purity 98%, D106441, purchased from Shanghai aladine Biochemical technologies Co., ltd;
1, 6-hexanediamine: purity 99%, H103910, purchased from Shanghai aladine Biochemical technologies Co., ltd;
1, 14-tetradecanediamine: purity 95%, SY250668, purchased from Shanghai Shaoshao far reagent limited company;
benzoic acid: purity 99.5%,242381, purchased from Sigma-Aldrich company;
sodium hypophosphite: purity 98%, S475696, available from Shanghai Ala Biotechnology Co., ltd.
Preparation method of polyamide resin of examples and comparative examples: adding a reaction monomer, benzoic acid, sodium hypophosphite and deionized water into a pressure kettle; the amount of benzoic acid material was 1.5% of the amount of reactive monomer material, the weight of sodium hypophosphite was 0.10% of the weight of the feed except deionized water, and the weight of deionized water was 30% of the total feed weight; vacuumizing, filling high-purity nitrogen as a protective gas, heating to 220 ℃ in about 2 hours, and reacting for 1 hour in the temperature range; then continuously reacting for 2 hours at 230 ℃ and under the pressure of 2.2 MPa, removing formed water in the reaction process, discharging after the reaction is finished, and vacuum drying the prepolymer to obtain a prepolymer product, wherein the prepolymer product is subjected to solid-phase tackifying for 8-12 hours at the temperature of 250 ℃ and the pressure of 50Pa to obtain the polyamide resin.
The testing method comprises the following steps:
(1) Polyamide relative viscosity test method: referring to GB12006.1-89, a polyamide viscosity number determination method; the specific test method comprises the following steps: the relative viscosity of the polyamide at a concentration of 0.25 g/dl was measured in 98% concentrated sulfuric acid at 25.+ -. 0.01 ℃.
(2) Polyamide resin melting point 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: 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 resin heat history is removed at 350 ℃ for 2min, then the resin is cooled to 50 ℃ at 20 ℃/min, the resin is kept at 50 ℃ for 2min, the temperature is raised to 350 ℃ at 20 ℃/min, and the endothermic peak temperature at the moment is set as T melting point.
(3) Polyamide cis-trans ratio test method: 5mg of polyamide resin is taken and dissolved in 10mg of deuterated trifluoroacetic acid, and nuclear magnetic hydrogen spectrum test is carried out on the sample by using a Bruker DPX400 nuclear magnetic resonance apparatus. In the nuclear magnetic resonance hydrogen spectrum chart, the position of 1.96ppm is a cis structure peak, the position of 1.83ppm is a trans structure peak, and nuclear magnetic integration is carried out on the two peaks, so that the trans structure proportion of the resin can be obtained.
(4) SMT test: the polyamide composition was injection molded into 60mm 0.8mm plaques, which were placed into an SMT instrument for testing. Infrared reflow soldering conditions: the SMT infrared reflow soldering device is provided with the following conditions:
a preheating stage: raising the temperature from room temperature to 150 ℃ over a period of 120 seconds;
b heating stage: raising the temperature from 150 ℃ to 190 ℃ over a period of 90 seconds;
c, reflux stage: raising the temperature to 217 ℃ at a rate of 2.5 ℃ per second, then raising the temperature from 217 ℃ to 260 ℃ and then lowering the temperature to 217 ℃ in 80 seconds;
d, cooling: the temperature is reduced to room temperature at a rate of 2 ℃ or more per second.
(5) Polyamide transmittance test method: referring to ISO13468-1-2019, a polyamide resin was injection molded into a 2mm thick smooth panel, and material initiation and post SMT light transmittance testing was performed using a spectrophotometer.
Table 1: the amount fraction of each unit substance of the polyamide resins of examples and comparative examples 1-2 and the test results
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| 1, 4-Cyclohexanedicarboxylic acid | 50 | 50 | 50 | 50 | 50 | 50 | 50 |
| 1, 10-decanediamine | 38 | 39 | 39.5 | 40 | 41 | 37 | 42 |
| 1, 12-dodecanediamine | 12 | 11 | 10.5 | 10 | 9 | 13 | 8 |
| Relative viscosity | 2.237 | 2.264 | 2.208 | 2.246 | 2.249 | 2.210 | 2.224 |
| Trans structure ratio, mol% | 81.3 | 82.4 | 82.9 | 83.7 | 84.9 | 80.3 | 85.5 |
| Melting point, DEG C | 321 | 325 | 327 | 329 | 334 | 316 | 341 |
| Initial light transmittance% | 72 | 74 | 76 | 77 | 73 | 68 | 66 |
| Light transmittance after SMT% | 71 | 72 | 73 | 75 | 71 | 57 | 55 |
As is clear from examples 1 to 5, the proportion of the trans-structure to the polyamide resin is preferably 82 to 84% in the case where 1, 10-decamethylene diamine is 78 to 80% of the amount of the diamine substance, and the initial light transmittance and the light transmittance after SMT are both high.
As is clear from comparative example 1, when the amount fraction of 1, 10-decanediamine in the diamine substance is less than 78%, the amount fraction ratio of the trans-structure in the polyamide resin substance is less than 81%, the molecular chain regularity of the resin is relatively good, and the initial light transmittance is reduced; and after SMT, the molecular chain regularity is good, and recrystallization is easy to occur again, so that the light transmittance is obviously reduced.
As is clear from comparative example 2, in comparative example 2, the melting point of the resin is higher than 340℃and the injection molding temperature is close to the decomposition temperature of the resin, so that it is difficult to perform injection molding, resulting in low initial light transmittance and low light transmittance after SMT.
Table 2: comparative examples 3 to 5 Polyamide resins each having a content of unit substances in terms of weight fraction and test results
| Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| 1, 4-Cyclohexanedicarboxylic acid | 50 | 50 | 50 |
| 1, 10-decanediamine | 40 | 40 | 50 |
| 1, 6-hexanediamine | 10 | ||
| 1, 14-tetradecanediamine | 10 | ||
| Relative viscosity | 2.289 | 2.266 | 2.204 |
| Trans structure ratio, mol% | 87.5 | 79.2 | 76.2 |
| Melting point, DEG C | 338 | 322 | 351 |
| Initial light transmittance% | 62 | 65 | 60 |
| Light transmittance after SMT% | 49 | 53 | 46 |
As is clear from comparative examples 3 to 5, it is difficult to achieve trans-structure ratios of other kinds of monomers within the scope of the present application, achieving high light transmittance and ensuring light transmittance after SMT.
The initial light transmittance of the polyamide resin is more than or equal to 72 percent, and the light transmittance after SMT is more than or equal to 71 percent.
Claims (8)
1. A polyamide resin characterized by comprising the following recurring units in mole percent:
diacid unit: 1, 4-cyclohexanedicarboxylic acid;
diamine unit: 1, 10-decanediamine and 1, 12-dodecanediamine, wherein the 1, 10-decanediamine accounts for 76-82% of the mass fraction of the diamine.
2. The polyamide resin according to claim 1, wherein the 1, 10-decamethylene diamine comprises 78 to 80% by mass of the diamine.
3. The polyamide resin according to claim 1, wherein the polyamide resin has a trans-form of 81 to 85% by weight of the polyamide resin.
4. The polyamide resin of claim 1, wherein the polyamide resin has a melting point in the range of 321-334 ℃.
5. The polyamide resin according to claim 1, wherein the polyamide resin has a relative viscosity in the range of 1.8 to 2.8, measured in 98% concentrated sulfuric acid at 25.+ -. 0.01 ℃ at a concentration of 0.25 g/dl, with reference to GB 12006.1-89.
6. The method for polymerizing a polyamide resin according to any one of claims 1 to 5, comprising the steps of: adding a reaction monomer, benzoic acid, sodium hypophosphite and deionized water into a pressure kettle; the amount of the benzoic acid substance is 1.5-3.0% of the total amount of the reaction monomers, the weight of sodium hypophosphite is 0.05-0.15% of the weight of other materials except deionized water, and the weight of deionized water is 25-35% of the total weight of materials; vacuumizing, filling inert gas as shielding gas, heating to 215-225 ℃ within 1.5-2.5 hours, and reacting for 0.5-1.5 hours under the temperature range; then continuously reacting for 1-3 hours at 225-235 ℃ and under the pressure of 2.0-2.4 MPa, removing formed water in the reaction process, discharging after the reaction is finished, and vacuum drying the prepolymer to obtain a prepolymer product, wherein the prepolymer product is subjected to solid-phase tackifying for 8-12 hours at 240-260 ℃ and under the pressure of 45-55 Pa to obtain the polyamide resin.
7. Use of a polyamide resin according to any one of claims 1-5 for the preparation of a translucent LED-related component.
8. Use of the polyamide resin obtained by the process according to claim 6 for the preparation of translucent LED-related components.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310479493.0A CN116589675A (en) | 2023-04-28 | 2023-04-28 | Polyamide resin and polymerization method and application thereof |
| PCT/CN2024/082157 WO2024222305A1 (en) | 2023-04-28 | 2024-03-18 | Polyamide resin, and polymerization method therefor and use thereof |
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| CN202310479493.0A CN116589675A (en) | 2023-04-28 | 2023-04-28 | Polyamide resin and polymerization method and application thereof |
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| WO (1) | WO2024222305A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150060530A (en) * | 2013-11-26 | 2015-06-03 | 삼성에스디아이 주식회사 | Polyamide resin and polyamide molded body using the same |
| KR20170085473A (en) * | 2017-07-13 | 2017-07-24 | 롯데첨단소재(주) | Copolymerized polyamide resin, method for preparing the same and article comprising the same |
| CN113651955A (en) * | 2021-08-16 | 2021-11-16 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin with good processability and preparation method and application thereof |
| CN113929901A (en) * | 2021-10-25 | 2022-01-14 | 珠海万通特种工程塑料有限公司 | Polyamide resin, composition thereof and preparation method thereof |
-
2023
- 2023-04-28 CN CN202310479493.0A patent/CN116589675A/en active Pending
-
2024
- 2024-03-18 WO PCT/CN2024/082157 patent/WO2024222305A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150060530A (en) * | 2013-11-26 | 2015-06-03 | 삼성에스디아이 주식회사 | Polyamide resin and polyamide molded body using the same |
| CN105814115A (en) * | 2013-11-26 | 2016-07-27 | 三星Sdi株式会社 | Polyamide resin and polyamide molded body using same |
| KR20170085473A (en) * | 2017-07-13 | 2017-07-24 | 롯데첨단소재(주) | Copolymerized polyamide resin, method for preparing the same and article comprising the same |
| CN113651955A (en) * | 2021-08-16 | 2021-11-16 | 中仑塑业（福建）有限公司 | Semi-aromatic polyamide resin with good processability and preparation method and application thereof |
| CN113929901A (en) * | 2021-10-25 | 2022-01-14 | 珠海万通特种工程塑料有限公司 | Polyamide resin, composition thereof and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2024222305A1 (en) | 2024-10-31 |
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