WO2023185517A1 - 一种高结合力的生物基耐高温聚酰胺及其制备方法和应用 - Google Patents

一种高结合力的生物基耐高温聚酰胺及其制备方法和应用 Download PDF

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WO2023185517A1
WO2023185517A1 PCT/CN2023/082363 CN2023082363W WO2023185517A1 WO 2023185517 A1 WO2023185517 A1 WO 2023185517A1 CN 2023082363 W CN2023082363 W CN 2023082363W WO 2023185517 A1 WO2023185517 A1 WO 2023185517A1
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temperature
resistant polyamide
bio
based high
binding
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PCT/CN2023/082363
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English (en)
French (fr)
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阎昆
徐显骏
姜苏俊
曹民
麦杰鸿
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珠海万通特种工程塑料有限公司
金发科技股份有限公司
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Publication of WO2023185517A1 publication Critical patent/WO2023185517A1/zh

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    • 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
    • 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
    • H01L33/483—Containers
    • 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
    • H01L33/58—Optical field-shaping elements
    • H01L33/60—Reflective elements

Definitions

  • the invention belongs to the application field of engineering plastics, and specifically relates to a high-binding bio-based high-temperature resistant polyamide and its preparation method and application.
  • the LED reflective bracket plays both electrical and thermal conductive roles. It is an indispensable key auxiliary material for LED devices.
  • the materials used for LED brackets mainly include high-temperature-resistant polyamide (PPA) and high-temperature-resistant polyester (cyclohexyl dimethyl terephthalate, PCT).
  • High-temperature-resistant polyamide mainly including PA46, PA6T and PA9T
  • PA46, PA6T and PA9T has high initial whiteness, good heat resistance and high fluidity, is suitable for injection molding process, and has low cost. It is currently the mainstream material for LED brackets.
  • LED encapsulants mainly include epoxy resin and silicone.
  • Silicone has outstanding mechanical properties, aging resistance, good thermal stability, weather resistance, flexibility, high light transmittance, small internal stress and low moisture absorption. , compared with epoxy resin, its performance can better meet the packaging needs of high-power, high-brightness LED products. Therefore, silicone is rapidly replacing epoxy resin and becoming a new generation of more ideal LED packaging materials.
  • the main material of LED reflective brackets for display screens is PA6T/66 (a copolymer of hexamethylenediamine, terephthalic acid and adipic acid) because PA6T/66 has a higher amide bond than PA9T and PA10T.
  • the density can form hydrogen bonds with the silicon hydrogen groups and silanol groups in the silica gel matrix, which improves the binding force between the LED reflective bracket and the silica gel to a certain extent.
  • LED lamp beads have begun to be used in the field of outdoor display screens.
  • LED lamp beads need to be exposed to high temperature and high humidity for a long time, or rain erosion.
  • the bonding force between PA6T/66 and silicone is still not enough to meet the requirements, and there is separation between plastic and silicone.
  • PA6T/66 has a high water absorption rate and is prone to dimensional deformation in outdoor high-humidity environments, leading to lamp bead cracking.
  • hexamethylenediamine monomer in PA6T/66 is generally derived from petroleum. Under the current situation of excessive consumption of petroleum resources, sharp increase in carbon dioxide emissions, and intensified greenhouse effect, it does not meet the requirements of green and sustainable development.
  • the purpose of the present invention is to overcome the defects or deficiencies in the prior art that the bonding force between polyamide and silica gel is not strong and does not meet the requirements of green and sustainable development, and to provide a bio-based high-temperature resistant polyamide with high bonding force.
  • the polyamide provided by the invention uses a specific proportion of furandicarboxylic acid and terephthalic acid as dibasic acid, and uses bio-based pentanediamine as diamine, which not only effectively improves the binding force with silica gel, but also has a high melting point.
  • Another object of the present invention is to provide a method for preparing the above-mentioned high-binding bio-based high-temperature-resistant polyamide.
  • Another object of the present invention is to provide the application of high-binding bio-based high-temperature-resistant polyamide in the preparation of LED reflective brackets.
  • a high-binding bio-based high-temperature resistant polyamide including the following molar fractions of components:
  • the dibasic acid is composed of furandicarboxylic acid and terephthalic acid, and the mole fraction of furandicarboxylic acid in the dibasic acid monomer is 10 to 50%.
  • the inventor of the present invention has found through research that the types of dibasic acid monomers and diamine monomers have a great influence on the binding force between the obtained polyamide and silica gel.
  • a specific molar ratio of furandicarboxylic acid and terephthalic acid is selected as the dibasic acid monomer, and pentanediamine is used as the diamine monomer
  • the resulting polyamide has better binding force with silica gel and has a higher melting point. , good high temperature resistance; in addition, it also has low water absorption and low shrinkage, and is suitable as an LED reflective bracket material, especially for outdoor LED reflective bracket materials. This is because the polyamide obtained from the above-mentioned specific monomers has a more suitable amide bond density.
  • the polyamide has It has strong molecular polarity, which can form stronger intermolecular force with silica gel molecules and has better binding force; on the other hand, it can effectively reduce water absorption and shrinkage. If the molar dosage of furandicarboxylic acid is too low, the melting point of the resulting polyamide will be too high and the processing performance will be poor, making it unsuitable for preparing LED reflective brackets; if the molar dosage of furandicarboxylic acid is too high, the melting point of the resulting polyamide will be too low and the resistance will be poor. The temperature performance is poor, the water absorption rate is too high, and the shrinkage rate is large. If other diamine monomers are used, the amide bond density will be reduced and the binding force with silica gel will be weak.
  • the mole fraction of furandicarboxylic acid in the dibasic acid monomer is 20 to 40%.
  • the melting point of the high-binding bio-based high-temperature-resistant polyamide is 280 to 330°C.
  • Polyamide melting point test method refer to ASTM D3418-2003; the specific test method is: use Perkin Elmer Dimond DSC analyzer to test the melting point of the sample; nitrogen atmosphere, flow rate is 50mL/min; during the test, first raise the temperature to 350°C at 20°C/min , keep at 350°C for 2 minutes, remove the resin heat history, then cool to 50°C at 20°C/min, hold at 50°C for 2 minutes, and then heat up to 350°C at 20°C/min. Set the endothermic peak temperature at this time to Melting point Tm.
  • the content of terminal amino groups of the high-binding bio-based high-temperature-resistant polyamide is 40 to 56 mol/t.
  • Test method for polyamide terminal amino group content titrate the sample terminal amino group content with a fully automatic potentiometric titrator; take 0.5g of polyamide, add 45mL of phenol and 3mL of anhydrous methanol, heat to reflux, observe that the sample is completely dissolved, and then cool to room temperature. Titrate the terminal amino group content with calibrated hydrochloric acid standard solution.
  • the content of terminal carboxyl groups of the high-binding bio-based high-temperature-resistant polyamide is 72 to 90 mol/t.
  • Test method for the terminal carboxyl group content of polyamide Use a fully automatic potentiometric titrator to titrate the terminal carboxyl group content of the sample; take 0.5g of the polymer, add 50mL of o-cresol, dissolve it under reflux, let it cool, quickly add 400 ⁇ L of formaldehyde solution, and use calibrated KOH -Titrate the terminal carboxyl group content with ethanol solution.
  • the relative viscosity of the high-binding bio-based high-temperature-resistant polyamide is 2.00 to 2.30.
  • Polyamide relative viscosity test method refer to GB12006.1-2009, polyamide viscosity determination method; the specific test method is: measure the relative viscosity of polyamide with a concentration of 0.25g/dl in 98% concentrated sulfuric acid at 25 ⁇ 0.01°C Viscosity ⁇ r;
  • the preparation method of the above-mentioned high-binding bio-based high-temperature-resistant polyamide includes the following steps: S1: Mix pentanediamine and dibasic acid, then add an end-capping agent, a catalyst and water, and stir the reaction under an inert atmosphere to obtain a pre-prepared polyamide. Polymer products;
  • Catalysts and end-capping agents commonly used in the field of preparing polyamide can be used in the present invention.
  • the catalyst described in S1 is a phosphorus compound.
  • the catalyst described in S1 is one or more of the following substances and their salts or esters: phosphoric acid, phosphorous acid, hypophosphorous acid, benzene phosphonic acid or benzene phosphinic acid.
  • the salt is a salt formed with a cation having a valence of 1+ to 3+ (for example, Na + , K + , Mg 2+ , Ga 2+ , Zn 2+ or Al 3+ ).
  • esters are triphenyl phosphate, triphenyl phosphite, etc.
  • the end-capping agent is one or more of aliphatic, cycloaliphatic or aromatic monocarboxylic acids or monoamines, or monofunctional compounds that can react with amino groups or carboxyl groups.
  • the monocarboxylic acid is one of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, lauric acid, stearic acid, 2-ethylhexanoic acid, cyclohexanoic acid or benzoic acid, or several kinds
  • the monoamine is butylamine, pentylamine, hexylamine, 2-ethylhexylamine, n-octylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, stearylamine
  • amine cyclohexylamine, 3-(cyclohexylamino)propylamine, methylcyclohexylamine, dimethylcyclohexylamine, benzylamine or 2-phenylethylamine.
  • the monofunctional compound is one or more of anhydride, isocyanate, acid halide or ester.
  • the process of the stirring reaction described in S1 is: raising the temperature to 210 ⁇ 270°C under stirring conditions, the pressure is 2.0 ⁇ 3.1MPa, then continuing to stir under constant pressure for 0.5 ⁇ 3h, and drying the reaction product to obtain the predetermined reaction product. Polymer.
  • the weight amount of the catalyst is 0.01-0.5% of the total weight amount of pentamethylenediamine, dibasic acid and benzoic acid, preferably 0.1%.
  • the molar amount of the end-capping agent is 0 to 5% of the total molar amount of pentanediamine and dibasic acid, preferably 2.5%.
  • the weight amount of the water is 10 to 50% of the total weight in the entire stirred reaction system, preferably 30%; the water is preferably deionized water.
  • the process of the thickening reaction is: solid-phase thickening of the prepolymer under vacuum conditions of 200-270°C and 10-1000 Pa for 5-20 hours; preferably, the prepolymer is solid-phase thickened under vacuum conditions of 250°C and 50 Pa. Add viscosity for 10 hours.
  • High-binding bio-based high-temperature-resistant polyamide has the advantages of strong binding force, high temperature resistance, low water absorption, and low shrinkage. It can be widely used in the preparation of LED reflective brackets, especially in the preparation of outdoor LED reflective brackets to achieve outdoor LED displays. applications on the screen.
  • the present invention has the following beneficial effects:
  • the polyamide provided by the invention uses a specific proportion of furandicarboxylic acid and terephthalic acid as dibasic acids, which not only effectively improves the binding force with silica gel, has a high melting point, better high temperature resistance, and also has lower Water absorption, low shrinkage, suitable as LED reflective bracket material, especially outdoor LED reflective bracket material.
  • Furandicarboxylic acid purity 98%, purchased from Ningbo Institute of Materials, Chinese Academy of Sciences;
  • Terephthalic acid purity 98%, purchased from Sigma-Aldrich;
  • Adipic acid purity 98%, purchased from Sigma-Aldrich;
  • Pentylenediamine purity 98%, purchased from Shanghai Kaisa Chemical Co., Ltd.;
  • Hexamethylenediamine purity 98%, purchased from Sigma-Aldrich;
  • Decanediamine purity 98%, purchased from Wuxi Yinda Nylon Co., Ltd.;
  • Silicone LED packaging silicone commercially available from Shenzhen Yongxinren Technology Co., Ltd., UH-6950-1 (AB glue).
  • the preparation method of the polyamide of each embodiment and comparative example of the present invention is: weigh each raw material according to the proportion, put it in a pressure kettle equipped with magnetic coupling stirring, condenser tube, gas phase port, feeding port, and pressure explosion-proof port according to the table Add the reaction raw materials (diamine, dibasic acid) in the proportion; then add benzoic acid, sodium hypophosphite (catalyst) and deionized water; the amount of benzoic acid is 2.5 of the total amount of diamine and dibasic acid.
  • the weight of sodium hypophosphite is 0.1% of the weight of other materials except ionized water, and the weight of deionized water is 30% of the total weight of materials; vacuum and fill with high-purity nitrogen as a protective gas, and raise it to 230°C under stirring.
  • the pressure is 2.2MPa; the reaction is continued to stir for 2 hours at a constant temperature of 230°C and a constant pressure of 2.2MPa. The pressure is kept constant by removing the water formed. After the reaction is completed, the material is discharged.
  • the prepolymer is vacuum dried at 80°C for 24 hours, a prepolymerized product is obtained, and the prepolymerized product is solid-phase tackified under vacuum conditions of 250° C. and 50 Pa for 10 hours to obtain polyamide.
  • Silicone bonding strength The polyamide resin composition sample was injection molded, and the sample size was 80 ⁇ 20 ⁇ 2.0mm. Test method: After mixing the silica gel A and B at a mass ratio of 1:4, drop 0.02g onto one end of the sample surface, press the silica gel with one end of the other sample, and fix it with a clamp. Then put the sample into the oven and pre-cure at 80°C for 1 hour, then raise the temperature to 150°C and continue curing for 4 hours before ending. The cured specimens were subjected to a tensile test at a tensile speed of 10 mm/min, and the breaking force was recorded. In the present invention, the bonding strength between polyamide and silica gel is characterized by the breaking force. When the breaking force is not less than 600, it is considered to meet the usage requirements.
  • This embodiment provides a series of high-binding bio-based high-temperature resistant polyamides as shown in Table 1.
  • This comparative example provides a series of polyamides, and the amounts of each component in the formula are as shown in Table 2.
  • Example 3 has the best comprehensive performance and is suitable for use as an outdoor LED reflective bracket material. In Comparative Example 1, too few moles of furandicarboxylic acid and too many moles of terephthalic acid were used.
  • the melting point of the polyamide resin was 345°C, close to the decomposition temperature of the polyamide resin, and the processability was poor.
  • Comparative Example 2 too many moles of furandicarboxylic acid and too few moles of terephthalic acid were used.
  • the melting point was 274°C, and the temperature resistance was poor. Although it had a certain silica gel binding force, the water absorption rate was 4.4%.
  • the shrinkage rate is 1.0%/1.5%, both of which are relatively high. It is difficult to be used in the field of outdoor LED reflective bracket materials.
  • Comparative Examples 3 and 4 are conventional PA5T/56 and PA6T/66 formulas respectively.
  • Comparative Example 5 is PA10T. Although it has excellent low water absorption, low shrinkage, and high dimensional stability, the silicone bonding breaking force is only 275N, and the bonding force with silicone is very poor, so it cannot be used in the field of outdoor LED reflective brackets. Comparative Example 6 uses hexamethylene diamine as the diamine and has poor binding force with silica gel; Comparative Example 7 uses decanediamine as the diamine and has poor binding force with silica gel.
  • Comparative Example 8 only uses terephthalic acid, the melting point of the polyamide resin is too high, and the processability is poor; Comparative Example 9 only uses furandicarboxylic acid, the melting point of the polyamide resin is too low, the temperature resistance is poor, the water absorption rate is high, and the shrinkage rate is large. .

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Abstract

本发明涉及一种高结合力的生物基耐高温聚酰胺及其制备方法和应用。该高结合力的生物基耐高温聚酰胺包括戊二胺和二元酸。本发明提供的聚酰胺，以特定比例的呋喃二甲酸和对苯二甲酸作为二元酸，以生物基来源的戊二胺作为二元胺，不仅有效提升了与硅胶的结合力，熔点高，具有较佳的耐高温性能，还具有较低的吸水率，较低的收缩率，适合作为LED反射支架材料，特别是户外LED反射支架材料用。

Description

一种高结合力的生物基耐高温聚酰胺及其制备方法和应用 技术领域
本发明属于工程塑料应用领域，具体涉及一种高结合力的生物基耐高温聚酰胺及其制备方法和应用。
背景技术
LED反射支架作为芯片承载体，既起导电作用又起导热作用，是LED器件不可或缺的关键辅料。用作LED支架的材料主要有耐高温聚酰胺(PPA)、和耐高温聚酯(对苯二甲酰环己基二甲酯，PCT)。耐高温聚酰胺(主要包括PA46、PA6T和PA9T)具有较高的初始白度，耐热性好、流动性高，适合注塑成型工艺，并且成本较低，目前是LED支架的主流材料。
LED封装胶主要包括环氧树脂和硅胶，硅胶拥有优异的机械性能、耐老化性能、良好的热稳定性、耐候性、柔韧性、高透光率、以及内应力小和低吸湿性等显著特点，与环氧树脂相比，其性能更能满足大功率、高亮度LED产品的封装需要。因而，硅胶正迅速取代环氧树脂，成为新一代更为理想的LED封装材料。
目前显示屏用途的LED反射支架的主要材料是PA6T/66(己二胺、对苯二甲酸和己二元酸的共聚物)，因为相比于PA9T和PA10T，PA6T/66具有更高的酰胺键密度，可以与硅胶基体中的硅氢基团和硅醇基团形成氢键结合，在一定程度上提高了LED反射支架与硅胶的结合力。
然而，随着LED的快速发展，LED灯珠已经开始应用于户外显示屏领域。对于户外显示屏应用领域，LED灯珠需要长时间处于高温暴晒、或雨水侵蚀等高温高湿环境，这种情况下，PA6T/66与硅胶的结合力仍不足以满足要求，存在塑胶与硅胶分离的问题。并且PA6T/66的吸水率较高，在户外的高湿环境中，容易发生尺寸形变，导致灯珠开裂问题。目前没有合适的应用于LED户外显示屏的耐高温聚酰胺树脂基体。
另外，PA6T/66中的己二胺单体一般来源于石油，在目前石油资源消耗过量、二氧化碳排放剧增、温室效应加剧的现状下，不符合绿色可持续发展的要求。
目前已有专利公开了一种全生物基聚酰胺及其制备方法，以生物基的呋喃二 甲酸和脂肪族二胺作为原料，得到高性能的环境友好型的聚酰胺。但该聚酰胺的与硅胶的结合力不佳。
因此，开发一种与硅胶的结合力强的生物基聚酰胺，以满足户外显示屏的性能及符合绿色可持续发展的要求具有重要的研究意义和应用价值。
发明内容
本发明的目的在于克服现有技术的聚酰胺与硅胶的结合力不强，且不符合绿色可持续发展的要求的缺陷或不足，提供一种高结合力的生物基耐高温聚酰胺。本发明提供的聚酰胺，以特定比例的呋喃二甲酸和对苯二甲酸作为二元酸，以生物基来源的戊二胺作为二元胺，不仅有效提升了与硅胶的结合力，熔点高，具有较佳的耐高温性能，还具有较低的吸水率，较低的收缩率，适合作为LED反射支架材料，特别是户外LED反射支架材料用；并且，生物基来源的戊二胺的选用，还在一定程度上解决了环境污染和资源紧张问题，有利于构建可持续发展社会，符合绿色可持续发展的要求。
本发明的另一目的在于提供上述高结合力的生物基耐高温聚酰胺的制备方法。
本发明的另一目的在于提供高结合力的生物基耐高温聚酰胺在制备LED反射支架中的应用。
为实现上述发明目的，本发明采用如下技术方案：
一种高结合力的生物基耐高温聚酰胺，包括如下摩尔份数的组分：
二元酸    100份，
戊二胺    95～105份，
所述二元酸由呋喃二甲酸和对苯二甲酸组成，所述二元酸单体中呋喃二甲酸的摩尔分数为10～50％。
本发明的发明人研究发现，二元酸单体和二元胺单体的种类对得到的聚酰胺与硅胶的结合力具有较大的影响。当选用特定摩尔配比的呋喃二甲酸和对苯二甲酸作为二元酸单体，以戊二胺作为二元胺单体时，得到的聚酰胺与硅胶具有较佳的结合力，且熔点高、耐高温性能好；另外，还具有较低的吸水率，较低的收缩率，适合作为LED反射支架材料，特别是户外LED反射支架材料用。这是因为由上述特定单体得到的聚酰胺具有较合适的酰胺键密度，一方面，使得聚酰胺具 有较强的分子极性，可以与硅胶分子形成更强的分子间作用力，具有较好的结合力；另一方面可有效降低吸水率和收缩率。如果呋喃二甲酸的摩尔用量太低，得到的聚酰胺的熔点过高，加工性能差，不适合制备LED反射支架；如呋喃二甲酸的摩尔用量过高，得到的聚酰胺的熔点过低，耐温性能差，且吸水率过高，收缩率较大。如选用其它二胺单体，酰胺键密度降低，与硅胶的结合力较弱。
优选地，所述二元酸单体中呋喃二甲酸的摩尔分数为20～40％。
优选地，所述高结合力的生物基耐高温聚酰胺的熔点为280～330℃。
聚酰胺熔点测试方法：参照ASTM D3418-2003；具体测试方法是：采用Perkin Elmer Dimond DSC分析仪测试样品的熔点；氮气气氛，流速为50mL/min；测试时先以20℃/min升温至350℃，在350℃保持2min，除去树脂热历史，然后以20℃/min冷却到50℃，在50℃保持2min，再以20℃/min升温至350℃，将此时的吸热峰温度设为熔点Tm。
优选地，所述高结合力的生物基耐高温聚酰胺的端氨基的含量为40～56mol/t。
聚酰胺端氨基含量的测试方法：用全自动电位滴定仪滴定样品端氨基含量；取0.5g聚酰胺，加苯酚45mL及无水甲醇3mL，加热回流，观察试样完全溶解后，冷至室温，用已标定的盐酸标准溶液滴定端氨基含量。
优选地，所述高结合力的生物基耐高温聚酰胺的端羧基的含量为72～90mol/t。
聚酰胺端羧基含量的测试方法：用全自动电位滴定仪滴定样品端羧基含量；取0.5g聚合物，加邻甲酚50mL，回流溶解，放冷后迅速加入400μL甲醛溶液，用已标定的KOH-乙醇溶液滴定端羧基含量。
优选地，所述高结合力的生物基耐高温聚酰胺的相对粘度为2.00～2.30。
聚酰胺相对粘度测试方法：参照GB12006.1-2009，聚酰胺粘数测定方法；具体测试方法为：在25±0.01℃的98％的浓硫酸中测量浓度为0.25g/dl的聚酰胺的相对粘度ηr；
本领域常规的制备聚酰胺的方法可用于本发明中。本发明在此也提供一种较佳的制备方法。
上述高结合力的生物基耐高温聚酰胺的制备方法，包括如下步骤：S1：将戊二胺、二元酸混合，然后加入封端剂、催化剂和水，在惰性气氛下搅拌反应，得预聚产物；
S2：将预聚产物进行增粘处理，即得所述高结合力的生物基耐高温聚酰胺。
本领域制备聚酰胺常用的催化剂和封端剂均可用于本发明中。
优选地，S1中所述催化剂为磷化合物。
更为优选地，S1中所述催化剂为如下物质及其盐或酯中的一种或几种：磷酸、亚磷酸、次磷酸、苯膦酸或苯次膦酸。
具体地，其盐为与化合价为1+～3+的阳离子(例如Na+、K+、Mg2+、Ga2+、Zn2+或Al3+)形成的盐。
其酯为磷酸三苯酯、亚磷酸三苯酯等。
优选地，所述封端剂为脂肪族、环脂族或芳香族的一元羧酸或一元胺，或可与氨基或羧基反应的单官能团化合物中的一种或几种。
更为优选地，所述一元羧酸为乙酸、丙酸、丁酸、戊酸、己酸、月桂酸、硬脂酸、2-乙基己酸、环己酸或苯甲酸中的一种或几种
更为优选地，所述一元胺为丁胺、戊胺、己胺、2-乙基己胺、正辛胺、正十二烷胺、正十四烷胺、正十六烷胺、硬脂胺、环己胺、3-(环己基氨基)丙胺、甲基环己胺、二甲基环己胺、苯甲胺或2-苯乙胺中的一种或几种。
更为优选地，所述单官能团化合物为酐、异氰酸酯、酰卤或酯中的一种或几种。
优选地，S1中所述搅拌反应的过程为：在搅拌条件下升温至210～270℃，压力为2.0～3.1MPa，然后恒压下继续搅拌0.5～3h，将反应产物干燥即得所述预聚物。
优选地，所述催化剂的重量用量为戊二胺、二元酸和苯甲酸的重量用量总和的0.01～0.5％，优选为0.1％。
优选地，所述封端剂的摩尔用量为戊二胺和二元酸的摩尔用量总和的0～5％，优选为2.5％。
优选地，所述水的重量用量为整个搅拌反应体系中总重量的10～50％，优选为30％；所述水优选为去离子水。
优选地，所述增粘反应的过程为：将预聚物在200～270℃、10～1000Pa的真空条件下固相增粘5～20小时；优选为在250℃、50Pa真空条件下固相增粘10小时。
上述高结合力的生物基耐高温聚酰胺在制备LED反射支架中的应用也在本发明的保护范围中。
高结合力的生物基耐高温聚酰胺具有结合力强、耐高温、低吸水率，低收缩率的优点，可广泛用于制备LED反射支架，特别是制备户外LED反射支架，实现在LED户外显示屏中的应用。
与现有技术相比，本发明具有如下有益效果：
本发明提供的聚酰胺，以特定比例的呋喃二甲酸和对苯二甲酸作为二元酸，不仅有效提升了与硅胶的结合力，熔点高，具有较佳的耐高温性能，还具有较低的吸水率，较低的收缩率，适合作为LED反射支架材料，特别是户外LED反射支架材料用。
具体实施方式
下面结合实施例进一步阐述本发明。这些实施例仅用于说明本发明而不用于限制本发明的范围。下例实施例中未注明具体条件的实验方法，通常按照本领域常规条件或按照制造厂商建议的条件；所使用的原料、试剂等，如无特殊说明，均为可从常规市场等商业途径得到的原料和试剂。本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
本发明各实施例及对比例选用的部分试剂说明如下：
二元酸：
呋喃二甲酸：纯度98％，购于中科院宁波材料所；
对苯二甲酸：纯度98％，购于Sigma-Aldrich公司；
己二酸：纯度98％，购于Sigma-Aldrich公司；
二元胺：
戊二胺：纯度98％，购于上海凯赛化工有限公司；
己二胺：纯度98％，购于Sigma-Aldrich公司；
癸二胺：纯度98％，购于无锡殷达尼龙有限公司；
苯甲酸：分析纯，市售；
次磷酸钠：分析纯，市售；
苯甲酸：分析纯，市售；
硅胶：来自深圳永信仁科技有限公司商购的LED封装硅胶，UH-6950-1(AB 胶)。
应当理解的是，如未特殊说明，实施例或对比例所包括的某一组分均为相同的市售产品。
本发明各实施例及对比例的聚酰胺的制备方法为：按照配比称取各原料，在配有磁力偶合搅拌、冷凝管、气相口、加料口、压力防爆口的压力釜中按表格中的比例加入反应原料(二元胺、二元酸)；再加入苯甲酸、次磷酸钠(催化剂)和去离子水；苯甲酸物质的量为二元胺、二元酸总物质的量的2.5％，次磷酸钠重量为除去离子水外其他投料重量的0.1％，去离子水重量为总投料重量的30％；抽真空充入高纯氮气作为保护气，在搅拌下升高到230℃，压力2.2MPa；反应在230℃的恒温和2.2MPa的恒压下继续搅拌2小时，通过移去所形成的水而保持压力恒定，反应完成后出料，预聚物于80℃下真空干燥24小时，得到预聚产物，所述预聚产物在250℃、50Pa真空条件下固相增粘10小时，得到聚酰胺。
本发明各实施例及对比例的聚酰胺进行如下测试：
(1)聚酰胺吸水率：将样品注塑成20mm×20mm×2mm的制件，其重量记为a0。然后将其置于95℃水中240h后，称量其重量记为a1。则吸水率＝(a1-a0)/a0*100％。
(2)聚酰胺收缩率：将样品注塑成20mm×10mm×2mm的制件，然后将其置于95℃水中240h后，按照ISO 294-4：2001标准测试其吸水后的收缩率。
(3)硅胶结合力：将聚酰胺树脂组合物试样采用注塑成型，试样尺寸为80×20×2.0mm。测试方法：将硅胶A胶与B胶以质量比1:4混合均匀后，取0.02g滴至一根试样表面的一端，用另一根试样的一端压紧硅胶，用夹子固定。然后将样件放入烘箱中，在80℃条件下预固化1h，接着升温至150℃继续固化4h后结束。将固化好的样条进行拉伸测试，拉伸速度为10mm/min，记录拉断力。本发明通过拉断力来表征聚酰胺与硅胶的结合力，拉断力不低于600时，认为符合使用要求。
实施例1～7
本实施例提供一系列高结合力的生物基耐高温聚酰胺如表1。
表1实施例1～7(份)

对比例1～9
本对比例提供一系列聚酰胺，其配方中各组分的用量如表2。
表2对比例1～9(份)
各实施例和对比例提供的聚酰胺的测试结果如表1和2。
由上述测试结果可知，各实施例提供的高结合力的生物基耐高温聚酰胺与硅胶具有较佳的结合力，拉断力在633N以上，且熔点在280～330℃之间，具有较佳的耐高温性能和加工性能；另外，吸水率低于4.0％，收缩率小于0.8％/1.3％，其中以实施例3的综合性能最佳，适合作为户外LED反射支架材料用。对比例1中选用过少摩尔用量的呋喃二甲酸及过多摩尔用量的对苯二甲酸，聚酰胺树脂熔点345℃，接近聚酰胺树脂的分解温度，加工性差。对比例2中选用过多摩尔用量的呋喃二甲酸及过少摩尔用量的对苯二甲酸，熔点为274℃，耐温性较差，虽然具有一定的硅胶结合力，但吸水率为4.4％，收缩率为1.0％/1.5％，均较高， 难以用于户外LED反射支架材料领域。对比例3和4分别为常规的PA5T/56、PA6T/66的配方，吸水率大于5.2％，收缩率大于1.5％/1.9％，且硅胶结合拉断力小于556，硅胶结合力较弱，不适合于户外LED的高温高湿恶劣环境。对比例5为PA10T，虽然具有优异的低吸水率与低收缩率，尺寸稳定性高，但是硅胶结合拉断力仅275N，与硅胶的结合力很差，无法应用于户外LED反射支架领域。对比例6以己二胺作为二元胺，与硅胶的结合力差；对比例7以癸二胺作为二元胺，与硅胶的结合力较差。对比例8仅选用对苯二甲酸，聚酰胺树脂熔点过高，加工性差；对比例9仅选用呋喃二甲酸，聚酰胺树脂熔点过低，耐温性较差，且吸水率高，收缩率大。
本领域的普通技术人员将会意识到，这里的实施例是为了帮助读者理解本发明的原理，应被理解为本发明的保护范围并不局限于这样的特别陈述和实施例。本领域的普通技术人员可以根据本发明公开的这些技术启示做出各种不脱离本发明实质的其它各种具体变形和组合，这些变形和组合仍然在本发明的保护范围内。

Claims (10)

  1. 一种高结合力的生物基耐高温聚酰胺，其特征在于，包括如下摩尔份数的组分：
    二元酸    100份，
    戊二胺    95～105份，
    所述二元酸由呋喃二甲酸和对苯二甲酸组成，所述二元酸单体中呋喃二甲酸的摩尔分数为10～50％。
  2. 根据权利要求1所述高结合力的生物基耐高温聚酰胺，其特征在于，所述二元酸单体中呋喃二甲酸的摩尔分数为20～40％。
  3. 根据权利要求1所述高结合力的生物基耐高温聚酰胺，其特征在于，所述高结合力的生物基耐高温聚酰胺的熔点为280～330℃。
  4. 根据权利要求1所述高结合力的生物基耐高温聚酰胺，其特征在于，所述高结合力的生物基耐高温聚酰胺的端氨基的含量为40～56mol/t。
  5. 根据权利要求1所述高结合力的生物基耐高温聚酰胺，其特征在于，所述高结合力的生物基耐高温聚酰胺的端羧基的含量为72～90mol/t。
  6. 根据权利要求1所述高结合力的生物基耐高温聚酰胺，其特征在于，所述高结合力的生物基耐高温聚酰胺的相对粘度为2.00～2.30。
  7. 权利要求1～6任一所述高结合力的生物基耐高温聚酰胺的制备方法，其特征在于，包括如下步骤：
    S1：将戊二胺、二元酸混合，然后加入封端剂、催化剂和水，在惰性气氛下搅拌反应，得预聚产物；
    S2：将预聚产物进行增粘处理，即得所述高结合力的生物基耐高温聚酰胺。
  8. 根据权利要求7所述高结合力的生物基耐高温聚酰胺的制备方法，其特征在于，S1中所述催化剂为包括磷化合物；
    S1中所述封端剂为脂肪族、环脂族或芳香族的一元羧酸或一元胺，或可与氨基或羧基反应的单官能团化合物中的一种或几种。
  9. 根据权利要求7所述高结合力的生物基耐高温聚酰胺的制备方法，其特征在于，S1中所述搅拌反应的过程为：在搅拌条件下升温至210～270℃，压力为2.0～3.1MPa，然后恒压下继续搅拌0.5～3h，将反应产物干燥即得所述预聚物。
  10. 权利要求1～6任一所述高结合力的生物基耐高温聚酰胺在制备LED反射支架 中的应用。
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