WO2023045819A1 - 一种呋喃二酸基聚酰胺树脂及其制备方法和一种聚酰胺模塑组合物 - Google Patents

一种呋喃二酸基聚酰胺树脂及其制备方法和一种聚酰胺模塑组合物 Download PDF

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WO2023045819A1
WO2023045819A1 PCT/CN2022/118963 CN2022118963W WO2023045819A1 WO 2023045819 A1 WO2023045819 A1 WO 2023045819A1 CN 2022118963 W CN2022118963 W CN 2022118963W WO 2023045819 A1 WO2023045819 A1 WO 2023045819A1
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acid
polyamide resin
diacid
flame retardant
hypophosphite
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PCT/CN2022/118963
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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
杨汇鑫
蒋智强
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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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Priority to KR1020247013574A priority Critical patent/KR20240060707A/ko
Publication of WO2023045819A1 publication Critical patent/WO2023045819A1/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
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/5205—Salts of P-acids with N-bases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a furandic acid-based polyamide resin, a preparation method thereof and a polyamide molding composition.
  • Bio-based high-temperature resistant polyamides mainly refer to polyamides polymerized from bio-based aliphatic diamines or bio-based aromatic ring diacids. Bio-based monomers are usually extracted from animals and plants. On the one hand, they can achieve green and sustainable development. On the other hand, it can make high-temperature-resistant polyamide products more diversified to meet the needs of more subdivided industries.
  • bio-based monomers decanediamine, pentamethylenediamine and furandicarboxylic acid are considered to be the bio-based high-temperature polyamide monomer materials most likely to achieve substantial breakthroughs.
  • Decanediamine is derived from plant castor oil and has been mass-produced in China, but its price is high and its market competitiveness is weak.
  • Pentamethylenediamine is derived from the fermentation of glutamic acid and has been mass-produced in China with a relatively low price and good market competitiveness.
  • Furandicarboxylic acid is currently known, the only bio-based aromatic ring diacid monomer that is most likely to be industrialized in the near future. At present, the research on furandicarboxylic acid at home and abroad is in the stage of pilot scale research and development.
  • Chinese patent application CN106536187A discloses a furan-based polyamide, which uses a bio-based monomer 2,5-furandicarboxylic acid, and the diamine is aliphatic diamine, aromatic diamine, etc., which has the advantage of good gas barrier .
  • its gas barrier properties are mainly achieved by increasing the amide bond density by polymerizing short carbon chain diamines (1,3-propylenediamine).
  • the flame retardancy of the furan polyamide is poor.
  • the object of the present invention is to provide a furandic acid-based polyamide, which has the advantages of good flame retardancy, high melting point, low water absorption and bio-based.
  • Another object of the present invention is to provide a composition containing the above-mentioned furandic acid-based polyamide.
  • (A) accounts for 5-25 mol% of diacid units.
  • (A) accounts for 5-15 mol% of diacid units.
  • the preferred (A) has a lower water absorption rate and shrinkage rate under the content of diacid units.
  • the relative viscosity of the furandic acid-based polyamide resin is 1.8-2.4.
  • the melting point of the furandic acid-based polyamide resin is 290-336°C.
  • the water absorption rate of the furandic acid-based polyamide resin is less than or equal to 1.5%.
  • the transverse/longitudinal shrinkage ratio of the furandic acid-based polyamide resin is less than or equal to 0.2%/0.5%.
  • reaction raw materials diamine, diacid
  • benzoic acid sodium hypophosphite (catalyst)
  • deionized Water the amount of benzoic acid substance is 2-3% of the amount of diamine, diacid total substance, sodium hypophosphite weight is 0.05-0.15% of other feeding weight except deionized water, and deionized water weight is 2% of total feeding weight 25-35%;
  • Vacuumize and fill with high-purity nitrogen as a protective gas heat up to 210-230°C within 2 hours under stirring, and stir the reaction mixture at 210-230°C for 0.5-2 hours.
  • the temperature of the reactant is raised to 220-240°C under stirring, and the reaction is continued at a constant temperature of 220-240°C and a constant pressure of 2.1-2.3MPa for 1-3 hours, maintained by removing the formed water
  • the pressure is constant, and the material is discharged after the reaction is completed.
  • the prepolymer is vacuum-dried at 70-90 ° C to obtain a pre-polymerized product.
  • the pre-polymerized product is 8-12 hours, furandic acid-based polyamide resin was obtained.
  • a polyamide molding composition by weight, comprising the following components:
  • Halogen-free flame retardant 10-30 parts
  • the halogen-free flame retardant is selected from phosphine flame retardants, hypophosphite flame retardants, hypophosphite flame retardants, phosphonite flame retardants, phosphite flame retardants, phosphite flame retardants, Flame retardants, phosphite flame retardants, phosphine oxide flame retardants, hypophosphite flame retardants, hypophosphite flame retardants, phosphonate flame retardants, phosphonate flame retardants, phosphate flame retardants or At least one of the polyphosphate flame retardants;
  • the hypophosphite flame retardant is selected from aluminum hypophosphite, calcium hypophosphite, aluminum dimethyl hypophosphite, aluminum diethyl hypophosphite or methyl ethyl hypophosphite At least one of aluminum phosphate;
  • the phosphate flame retardant is selected from bisphenol A bis(diphenyl phosphate), phenoxyphosphazen
  • Described reinforcing material is selected from at least one in fibrous filler, non-fibrous filler;
  • Described fibrous filler is selected from glass fiber, carbon fiber, basalt fiber, bamboo fiber, hemp fiber, cellulose fiber, aromatic At least one in the fiber;
  • the non-fibrous filler is selected from alumina, carbon black, clay, zirconium phosphate, kaolin, calcium carbonate, copper powder, diatomaceous earth, graphite, mica, silica, titanium dioxide, zeolite, At least one of talc, wollastonite, glass beads, and glass powder.
  • the polyamide molding composition of the present invention can be used to prepare various types of electronic connector devices such as USB, TYPE-C, and DDR that require SMT (Surface Mount Technology). These electronic components have high requirements on the melting point, water absorption rate and dimensional stability of the material, and can be widely used in the fields of electronics and automobiles.
  • SMT Surface Mount Technology
  • the present invention has the following beneficial effects
  • diacid unit all contains the ring of rigidity, and wherein the rigidity of cyclohexane is higher than aromatic ring, can form more hard carbon layers during burning, and polyamide of the present invention
  • the amide bond density of amide resin is high, which can form a relatively excellent synergistic effect with the flame retardant, so the flame retardant effect is better.
  • the melting point of the prepared polyamide is between 290°C and 336°C, and it has good temperature resistance and processability.
  • the furandic acid-based polyamide of the present invention has the advantages of low water absorption and high dimensional stability.
  • the raw material sources used in the present invention are as follows:
  • 2,5-furandicarboxylic acid 98% purity, purchased from Ningbo Institute of Materials, Chinese Academy of Sciences;
  • 1,4-cyclohexanedicarboxylic acid 98% purity, purchased from Sigma-Aldrich;
  • 1,6-Adipic acid 98% purity, purchased from Sigma-Aldrich;
  • Terephthalic acid 98% purity, purchased from Sigma-Aldrich;
  • 1,10-decanediamine 98% purity, purchased from Wuxi Yinda Nylon Co., Ltd.;
  • 1,5-pentanediamine 98% purity, purchased from Shanghai Kaisai Chemical Co., Ltd.;
  • 1,6-hexanediamine 98% purity, purchased from Sigma-Aldrich;
  • Benzoic acid analytically pure, purchased from Sigma-Aldrich Company;
  • Halogen-free flame retardant A aluminum diethylphosphinate, OP1230, the mass percentage of phosphorus is 23-24%, purchased from Clariant Company;
  • Halogen-free flame retardant B melamine polyphosphate, MELAPUR200-70, the mass percentage of nitrogen is 42-44%, the mass percentage of phosphorus is 12-14%, purchased from BASF company;
  • Reinforcement material glass fiber, ECS11-4.5-560A, with an average diameter of 11 microns, purchased from Jushi, China.
  • the polyamide resin of embodiment and comparative example obtains according to same polymerization method: in the autoclave that is equipped with magnetic coupling stirring, condensing tube, gas phase port, feeding port, pressure explosion-proof port, add reaction raw material (diamine , diacid); Add benzoic acid, sodium hypophosphite (catalyst) and deionized water again; 0.08% of the feed weight, deionized water weight of 25% of the total feed weight; vacuumize and fill high-purity nitrogen as a protective gas, heat up to 230°C within 2 hours under stirring, and stir the reaction mixture at 220°C for 0.5-2 Hours, then the temperature of the reactant was raised to 240°C under stirring; the reaction continued for 1-3 hours at a constant temperature of 240°C and a constant pressure of 2.3MPa, and the pressure was kept constant by removing the formed water, and the reaction After completion, the material is discharged, and the prepolymer is vacuum-dried at 70-90°C to obtain a prepo
  • Relative viscosity test method of polyamide resin refer to GB12006.1-89, determination method of polyamide viscosity number; specific test method is: measure the concentration of 0.25g/dl in 98% concentrated sulfuric acid at 25 ⁇ 0.01°C Relative viscosity ⁇ r of polyamide;
  • Polyamide melting point test method refer to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; the specific test method is: use Perkin Elmer Dimond DSC analyzer to test the melting point of the sample; nitrogen atmosphere, the flow rate is 50mL/min; during the test, the temperature was first raised to 350°C at 20°C/min, and kept at 350°C for 2 minutes to remove the thermal history of the resin, then cooled to 50°C at 20°C/min, kept at 50°C for 2 minutes, and then heated at 20°C/min Min is heated to 350°C, and the endothermic peak temperature at this time is set as the melting point Tm;
  • Flame retardant performance refer to the UL94V-0 test standard, the standard strip sample size is 125 ⁇ 5mm in length, 13.0 ⁇ 0.5mm in width and 0.8mm in thickness; 5 samples are at 23 ⁇ 2°C, 50 ⁇ 5 %, with a minimum processing time of 48 hours.
  • the root splines are all T1+T2+T3 ⁇ 10s, and there is no dripping to ignite the cotton below, then the V-0 condition is considered to be met.
  • the melting point of the furandic acid-based polyamide resin in Comparative Example 1/2 exceeds the decomposition temperature, so it has no use value.
  • Table 3 The distribution ratio (parts by weight) of each component of the polyamide composition of Examples 9-16 and Comparative Examples 9-16 and the test results of various properties

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyamides (AREA)

Abstract

本发明公开了一种呋喃二酸基聚酰胺树脂，呋喃二酸基聚酰胺树脂衍生自包括以下重复单元：（A）2,5-呋喃二甲酸，（B）1,4-环己烷二甲酸，（C）1,10-癸二胺；按二酸单元总摩尔百分比计，（A）占二酸单元5-45mol％。一方面通过选用生物基的2,5-呋喃二甲酸，提升了环保性，具有290-336℃的熔点、吸水性较低、尺寸稳定性好的优点（相比于同样的酰胺键密度聚酰胺吸水率更低）；另一方面，环己烷刚性高于芳香环，燃烧时可以形成更多的硬质碳层，并且呋喃二酸基聚酰胺的酰胺键密度相对较高，可以与阻燃剂形成较为优异的协效作用，两者协同下阻燃效果优秀。

Description

一种呋喃二酸基聚酰胺树脂及其制备方法和一种聚酰胺模塑组合物 技术领域
本发明涉及高分子材料技术领域，特别是涉及一种呋喃二酸基聚酰胺树脂及其制备方法和一种聚酰胺模塑组合物。
背景技术
传统聚酰胺单体主要来源于石油，现如今人类面临着石油资源消耗过量、二氧化碳排放剧增、温室效应加剧的问题。降低石油基单体用量，可抑制二氧化碳排放，防止温室效应，解决环境污染和资源紧张问题，构建可持续发展社会。生物基耐高温聚酰胺，主要是指来自生物基脂肪族二胺或生物基芳环二酸聚合而成的聚酰胺，生物基单体通常由动植物提取，一方面可实现绿色可持续发展，另一方面可使耐高温聚酰胺产品更加多元化，满足更加细分行业的需求。
经市场调研和分析，生物基单体癸二胺、戊二胺和呋喃二甲酸被认为是最有可能实现实质性突破的生物基耐高温聚酰胺单体材料。癸二胺来源于植物蓖麻油，在国内已实现量产，但其售价较高，市场竞争力较弱。戊二胺来源于谷氨酸发酵，在国内实现量产，价格较低，具有良好的市场竞争力。呋喃二甲酸是目前已知的、唯一的、近期最有可能实现产业化的生物基芳环二酸单体，目前国内外在呋喃二甲酸的研究均处于中试研发阶段。
中国专利申请CN106536187A公开了一种基于呋喃的聚酰胺，采用了生物基单体2,5-呋喃二羧酸，二胺为脂肪族二胺、芳族二胺等，具有良好的阻隔气体的优点。但是，其气体阻隔性主要是通过聚合短碳链二胺(1,3-丙二胺、)来提升酰胺键密度来实现的。但是该呋喃聚酰胺的阻燃性较差。
发明内容
本发明的目的在于，提供一种呋喃二酸基聚酰胺，具有阻燃性能好、高熔点、低吸水率、生物基的优点。
本发明的另一目的在于，提供一种含有上述呋喃二酸基聚酰胺的组合物。
本发明是通过以下技术方案实现的：
一种呋喃二酸基聚酰胺树脂，呋喃二酸基聚酰胺树脂衍生至包括以下重复单元：(A)2,5-呋喃二甲酸，(B)1,4-环己烷二甲酸，(C)1,10-癸二胺；按二酸单元总摩尔百分比计，(A)占二酸单元5-45mol％。
优选的，按二酸单元总摩尔百分比计，(A)占二酸单元5-25mol％。
更优选的，按二酸单元总摩尔百分比计，(A)占二酸单元5-15mol％。
优选的(A)占二酸单元含量下，吸水率、收缩率更低。
所述呋喃二酸基聚酰胺树脂的相对粘度为1.8～2.4。
所述呋喃二酸基聚酰胺树脂的熔点290-336℃。
所述呋喃二酸基聚酰胺树脂的吸水率小于等于1.5％。
所述呋喃二酸基聚酰胺树脂的横/纵向收缩率小于等于0.2％/0.5％。
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比例加入反应原料(二胺、二酸)；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胺、二酸总物质的量的2-3％，次磷酸钠重量为除去离子水外其他投料重量的0.05-0.15％，去离子水重量为总投料重量的25-35％；抽真空充入高纯氮气作为保护气，在搅拌下2小时内升温到210-230℃，将反应混合物在210-230℃搅拌0.5-2小时。然后在搅拌下使反应物的温度升高到220-240℃，反应在220-240℃的恒温和2.1-2.3MPa的恒压下继续进行1-3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70-90℃下真空干燥，得到预聚产物，所述预聚产物在240-260℃、40-60Pa真空条件下固相增粘8-12小时，得到呋喃二酸基聚酰胺树脂。
一种聚酰胺模塑组合物，按重量份计，包括以下组分：
本发明上述呋喃二酸基聚酰胺树脂      40-70份；
无卤阻燃剂                10-30份；
增强材料                  0-50份。
所述无卤阻燃剂选自膦阻燃剂、次亚磷酸酯阻燃剂、次亚磷酸盐阻燃剂、亚膦酸酯阻燃剂、亚膦酸盐阻燃剂、亚磷酸酯阻燃剂、亚磷酸盐阻燃剂、氧化膦阻燃剂、次磷酸酯阻燃剂、次磷酸盐阻燃剂、膦酸酯阻燃剂、膦酸盐阻燃剂、磷酸酯阻燃剂或聚磷酸盐阻燃剂中的至少一种；所述的次磷酸盐阻燃剂选自次磷酸铝、次磷酸钙、二甲基次磷酸铝、二乙基次磷酸铝或甲基乙基次磷酸铝中的至少一种；所述的磷酸酯阻燃剂选自双酚A双(磷酸二苯酯)、苯氧基膦腈、间苯二酚(二苯基磷酸酯)、磷酸三苯酯、三聚氰胺聚磷酸酯或三聚氰胺氰尿酸酯中的至少一种；所述的聚磷酸盐阻燃剂选自聚磷酸铵、三聚氰胺磷酸盐、三聚氰胺焦磷酸盐或三聚氰胺聚磷酸盐中的至少一种。
所述的增强材料选自纤维状填充剂、非纤维状填充剂中的至少一种；所述纤维状填充剂选自玻璃纤维、碳纤维、玄武岩纤维、竹纤维、麻纤维、纤维素纤维、芳纶纤维中的至少一 种；所述非纤维状填充剂选自氧化铝、炭黑、粘土、磷酸锆、高岭土、碳酸钙、铜粉、硅藻土、石墨、云母、硅石、二氧化钛、沸石、滑石、硅灰石、玻璃珠、玻璃粉末中的至少一种。
本发明的聚酰胺模塑组合物能够用于制备需要SMT(表面组装技术)的USB、TYPE-C、DDR等各种类型的电子连接器器件。这些电子元器件对材料的熔点、吸水率与尺寸稳定性有较高要求，可广泛应用于电子电气与汽车等领域。
本发明与现有技术相比，具有如下有益效果
1.本发明的呋喃二酸基聚酰胺树脂中二酸单元均含有刚性的环，其中环己烷的刚性高于芳香环，燃烧时可以形成更多的硬质碳层，并且本发明的聚酰胺树脂酰胺键密度较高，可以与阻燃剂形成较为优异的协效作用，因此阻燃效果较好。
2.本发明通过调节呋喃二甲酸和环己烷二甲酸的比例，制得的聚酰胺熔点在290～336℃之间，具有良好的耐温性与加工性。
3.本发明的呋喃二酸基聚酰胺具有低吸水率、高尺寸稳定性的优点。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
本发明所用原材料来源如下：
2,5-呋喃二甲酸：纯度98％，购于中科院宁波材料所；
1,4-环己烷二甲酸：纯度98％，购于Sigma-Aldrich公司；
1,6-己二酸：纯度98％，购于Sigma-Aldrich公司；
对苯二甲酸：纯度98％，购于Sigma-Aldrich公司；
1,10-癸二胺：纯度98％，购于无锡殷达尼龙有限公司；
1,5-戊二胺：纯度98％，购于上海凯赛化工有限公司；
1,6-己二胺：纯度98％，购于Sigma-Aldrich公司；
苯甲酸：分析纯，购于Sigma-Aldrich公司；
次磷酸钠：分析纯，购于Sigma-Aldrich公司；
无卤阻燃剂A：二乙基次膦酸铝，OP1230，磷的质量百分含量23～24％，购于Clariant公司；
无卤阻燃剂B：三聚氰胺聚磷酸盐，MELAPUR200-70，氮的质量百分比42～44％，磷的质量 百分含量12～14％，购于BASF公司；
增强材料：玻璃纤维，ECS11-4.5-560A，平均直径11微米，购于中国巨石。
实施例和对比例的聚酰胺树脂按照同样的聚合方法得到：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(二胺、二酸)；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胺、二酸总物质的量的2％，次磷酸钠重量为除去离子水外其他投料重量的0.08％，去离子水重量为总投料重量的25％；抽真空充入高纯氮气作为保护气，在搅拌下2小时内升温到230℃，将反应混合物在220℃搅拌0.5-2小时，然后在搅拌下使反应物的温度升高到240℃；反应在240℃的恒温和2.3MPa的恒压下继续进行1-3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70-90℃下真空干燥，得到预聚产物，所述预聚产物在260℃、50Pa真空条件下固相增粘8-12小时，得到呋喃二酸基聚酰胺树脂(或无呋喃二酸的聚酰胺树脂)。
测试方法：
(1)聚酰胺树脂相对粘度测试方法：参照GB12006.1-89，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；
(2)聚酰胺熔点测试方法：参照ASTM D3418-2003，Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry；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；
(3)聚酰胺吸水率：将样品注塑成20mm×20mm×2mm的样板，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％。
(4)聚酰胺收缩率：将样品注塑成20mm×10mm×2mm的样板，然后将其置于95℃水中240h后，按照ISO 294-4-2018标准测试其吸水后的收缩率。
(5)阻燃性能：参照UL94V-0测试标准，标准条形试样尺寸为长125±5mm,宽为13.0±0.5mm.厚度0.8mm；5根试样按23±2℃，50±5％，最少处理48个小时。将本生灯火焰对准试样下端中心，并使本生灯管顶面中心与试样下端面距离保持为10±1mm，保持此距离10±0.5S：必要时可随试样长度位置变化来移动本生灯。对试样施加火焰10±0.5S后，立即将本生灯以约300mm/s的进度撤离到离试样至少150mm处。同时用计时装置测定试样的有焰燃烧时间T1(单位为s)。试样有焰燃烧停止后，即使本生灯没有撤离试样足够 150mm，立即在移本生口至试样下端面保持距离为10±1mm，再次施焰10±0.5S，必要时移开本生灯以清除滴落物，施焰后立即撤离本生灯远离试样至少150mm,同时启动记时装置测定试样的有焰时间T2,和无焰燃烧时间T3,记录T2的T3.如果5根样条均T1+T2+T3＜10s，且无滴落引燃下方棉花，则认为满足V-0条件。
表1：实施例1-6聚酰胺树脂各单体配比及测试结果
Figure PCTCN2022118963-appb-000001
由实施例1-6可知，1,4-环己烷二甲酸含量越高，熔点越高、吸水率和收缩率越低。
续表1：对比例1-8聚酰胺树脂各单体配比及测试结果
Figure PCTCN2022118963-appb-000002
对比例1/2呋喃二酸基聚酰胺树脂的熔点超过了分解温度，因此没有使用价值。
由对比例3可知，2,5-呋喃二甲酸含量越高，吸水率、收缩率越高、熔点越低，使用价值不高。
由对比例6可知，用己二酸代替环己烷二酸，即使酰胺键密度降低，但是吸水率反而升高了，并且收缩率较差，同时熔点过低。
由对比例7可知，采用相似结构的对苯二甲酸代替环己烷二酸，吸水率也过高，并且收缩率较差。
由对比例8可知，呋喃二甲酸/环己烷二酸/戊二胺链段体系的聚酰胺收缩率较差。
表3：实施例9-16和对比例9-16聚酰胺组合物各组分配比(重量份)及各项性能测试结果
Figure PCTCN2022118963-appb-000003
由实施例7-12可知，本发明的呋喃二酸基聚酰胺组合物具有良好的阻燃性。
续表3：
Figure PCTCN2022118963-appb-000004
由对比例9-11可知，熔点过高或过低都会导致无法改性加工成型。
由对比例12/13/15/16可知，采用其他二酸/二胺代替1,4-环己烷二甲酸或1,5-戊二胺，呋喃二酸基聚酰胺组合物或其他聚酰胺组合物的阻燃性较差，并且横纵向收缩率较高。

Claims (10)

  1. 一种呋喃二酸基聚酰胺树脂，其特征在于，呋喃二酸基聚酰胺树脂衍生自包括以下重复单元：(A)2,5-呋喃二甲酸，(B)1,4-环己烷二甲酸，(C)1,10-癸二胺；按二酸单元总摩尔百分比计，(A)占二酸单元5-45mol％。
  2. 根据权利要求1所述的呋喃二酸基聚酰胺树脂，其特征在于，按二酸单元总摩尔百分比计，(A)占二酸单元5-25mol％。
  3. 根据权利要求2所述的呋喃二酸基聚酰胺树脂，其特征在于，按二酸单元总摩尔百分比计，(A)占二酸单元5-15mol％。
  4. 根据权利要求1所述的呋喃二酸基聚酰胺树脂，其特征在于，所述呋喃二酸基聚酰胺树脂的相对粘度为1.8-2.4。
  5. 根据权利要求1所述的呋喃二酸基聚酰胺树脂，其特征在于，所述呋喃二酸基聚酰胺树脂的熔点290-336℃。
  6. 根据权利要求1所述的呋喃二酸基聚酰胺树脂，其特征在于，所述呋喃二酸基聚酰胺树脂的吸水率小于等于1.5％；所述呋喃二酸基聚酰胺树脂的横/纵向收缩率小于等于0.2％/0.5％。
  7. 权利要求1-6任一项所述呋喃二酸基聚酰胺树脂的制备方法，其特征在于，包括以下步骤：在压力釜中按比例加入反应原料；再加入苯甲酸、次磷酸钠和去离子水；苯甲酸物质的量为二胺、二酸总物质的量的2-3％，次磷酸钠重量为除去离子水外其他投料重量的0.05-0.15％，去离子水重量为总投料重量的25-35％；抽真空充入高纯氮气作为保护气，在搅拌下2小时内升温到210-230℃，将反应混合物在210-230℃搅拌0.5-2小时。然后在搅拌下使反应物的温度升高到220-240℃，反应在220-240℃的恒温和2.1-2.3MPa的恒压下继续进行1-3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70-90℃下真空干燥，得到预聚产物，所述预聚产物在240-260℃、40-60Pa真空条件下固相增粘8-12小时，得到呋喃二酸基聚酰胺树脂。
  8. 一种聚酰胺模塑组合物，其特征在于，按重量份计，包括以下组分：
    权利要求1-6任一项所述的呋喃二酸基聚酰胺树脂40-70份；
    无卤阻燃剂                  10-30份；
    增强材料                   0-50份。
  9. 根据权利要求8所述的聚酰胺模塑组合物，其特征在于，所述无卤阻燃剂选自膦阻燃剂、次亚磷酸酯阻燃剂、次亚磷酸盐阻燃剂、亚膦酸酯阻燃剂、亚膦酸盐阻燃剂、亚磷酸酯阻燃剂、亚磷酸盐阻燃剂、氧化膦阻燃剂、次磷酸酯阻燃剂、次磷酸盐阻燃剂、膦酸酯阻燃剂、 膦酸盐阻燃剂、磷酸酯阻燃剂或聚磷酸盐阻燃剂中的至少一种；所述的次磷酸盐阻燃剂选自次磷酸铝、次磷酸钙、二甲基次磷酸铝、二乙基次磷酸铝或甲基乙基次磷酸铝中的至少一种；所述的磷酸酯阻燃剂选自双酚A双(磷酸二苯酯)、苯氧基膦腈、间苯二酚(二苯基磷酸酯)、磷酸三苯酯、三聚氰胺聚磷酸酯或三聚氰胺氰尿酸酯中的至少一种；所述的聚磷酸盐阻燃剂选自聚磷酸铵、三聚氰胺磷酸盐、三聚氰胺焦磷酸盐或三聚氰胺聚磷酸盐的至少一种。
  10. 根据权利要求8所述的聚酰胺模塑组合物，其特征在于，所述的增强材料选自纤维状填充剂、非纤维状填充剂中的至少一种；所述纤维状填充剂选自玻璃纤维、碳纤维、玄武岩纤维、竹纤维、麻纤维、纤维素纤维或芳纶纤维中的至少一种；所述非纤维状填充剂选自氧化铝、炭黑、粘土、磷酸锆、高岭土、碳酸钙、铜粉、硅藻土、石墨、云母、硅石、二氧化钛、沸石、滑石、硅灰石、玻璃珠或玻璃粉末中的至少一种。
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