技术领域technical field
本发明属于有机合成领域，涉及一种抗氧剂的合成工艺，主要涉及6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-(乙基～十二烷基)酰胺及4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]乙基～十二烷基]苯甲酰胺化合物的合成方法。The invention belongs to the field of organic synthesis, and relates to a synthesis process of an antioxidant, and mainly relates to a synthesis method of 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-(ethyl-dodecyl)amide and 4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidine)amino]ethyl-dodecyl]benzamide.
背景技术Background technique
聚酰胺作为五大通用工程塑料之一，其在多个领域具有广泛应用，如：医疗器械、电子电器、汽车、机械、纺织等。聚酰胺原料一般呈现不透明的浅白色，而在发生氧化后通常呈现黄色、橙色及严重的红褐色，这不仅会导致材料外观变差，更会引发材料性能上的急剧衰减。抗氧剂的添加可以有效延长聚酰胺材料的氧化周期，减少聚酰胺材料的性能损失。包括巴斯夫、陶氏等多家公司也对聚酰胺的抗氧剂进行了研发，并且有像1098、1010、1076等聚酰胺适用抗热氧老化剂以及445、622、770等光稳定剂面世，但对于同时具备抗热氧老化和光稳定性的抗氧剂却很少提及。As one of the five general-purpose engineering plastics, polyamide is widely used in many fields, such as: medical equipment, electronic appliances, automobiles, machinery, textiles, etc. Polyamide raw materials generally appear opaque and light white, and usually appear yellow, orange and severe reddish brown after oxidation, which will not only lead to the deterioration of the appearance of the material, but also cause a sharp decline in the performance of the material. The addition of antioxidants can effectively prolong the oxidation cycle of polyamide materials and reduce the performance loss of polyamide materials. Many companies, including BASF and Dow, have also researched and developed polyamide antioxidants, and there are polyamide anti-oxidative aging agents such as 1098, 1010, and 1076, as well as light stabilizers such as 445, 622, and 770. However, antioxidants with both thermal-oxidative aging resistance and light stability are rarely mentioned.
贺黎明，曾佳等人提供了一种由2,6-二叔丁基-苯酚为受阻酚原料合成的双酚类化合物，此法需加入多种脱水剂，并且最终效率不高于70％。其步骤较为繁琐。同时，涉及的有机溶剂等反应参与物种类较多，步骤繁琐。He Liming, Zeng Jia and others provided a bisphenol compound synthesized from 2,6-di-tert-butyl-phenol as a hindered phenol raw material. This method needs to add a variety of dehydrating agents, and the final efficiency is not higher than 70%. Its steps are more complicated. At the same time, there are many types of reaction participants such as organic solvents involved, and the steps are cumbersome.
刘俊丽，赵含江等提供了三种基于3,5-二叔丁基-4-羟基-苯丙酸的新型结构受阻酚型抗氧剂的合成方法，其通过有机溶剂和异丙醇铝合成了多种单酚、双酚、多酚类抗氧剂，并且整体方法较为简单，但该方法中有金属元素，这会引发金属离子络合体的出现，并诱发氧化反应的加剧，而该方法仅描述了抗氧剂的合成，未对其抗氧化能力进行评价对比。Liu Junli, Zhao Hanyi, etc. provided three new structures based on 3,5-two-uncle-4-hydroxyl-phenyate-resistant phenol-type antioxidants. It synthesized a variety of single-phenol, bisphenol, polyphenol antioxidants through organic solvents and isopropyl aluminum, and the overall method was relatively simple, but this method has metal elements, which will trigger the appearance of metal ion synthesis and and and and and and and that and the appearance of metal ions The oxidation reaction is intensified, and this method only describes the synthesis of antioxidants and does not evaluate its antioxidant capacity.
李克国，张会京等人提供了一种含有受阻酚结构的受阻胺光稳定剂的合成方法，其通过加入包括负载催化剂MF/γ-Al2O3、负载型四氯化锡催化剂开展反应。相较于以往合成路线具有较好的精简，但存在催化剂合成后易失效、反应温度较高、涉及多种有机试剂的问题。Li Keguo, Zhang Huijing and others provided a synthesis method of a hindered amine light stabilizer containing a hindered phenol structure, which was reacted by adding a supported catalyst MF/γ-Al2O3 and a supported tin tetrachloride catalyst. Compared with the previous synthetic route, it has a better simplification, but there are problems that the catalyst is prone to failure after synthesis, the reaction temperature is high, and a variety of organic reagents are involved.
发明内容Contents of the invention
本发明的目的是针对当前抗氧剂无同时具备抗热氧和光稳定性能力的现状，提供了一类方法简单、产率较高、反应条件温和、步骤简便的4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]乙基～十二烷基]苯甲酰胺类化合物及其合成方法。The purpose of the present invention is to provide a class of 4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4piperidine)amino]ethyl-dodecyl]benzamide compounds with simple method, high yield, mild reaction conditions and simple steps, and a synthesis method thereof, in view of the fact that current antioxidants do not have both thermal oxygen resistance and light stability.
一方面，本发明提供一种具备光稳定性和抗热氧老化能力的抗氧剂，其具有如下所示的结构：On the one hand, the present invention provides an antioxidant with photostability and thermo-oxidative aging resistance, which has the following structure:
其中n为1-11的整数，其中R独立地选自具有推电子效应的基团，如甲基、双取代甲基、异丁基、叔丁基，优选为叔丁基基团。 Where n is an integer of 1-11, wherein R is independently selected from groups having electron-pushing effects, such as methyl, disubstituted methyl, isobutyl, tert-butyl, preferably tert-butyl.
另一方面，本发明还提供了所述抗氧剂的制备方法，其合成路线包含：On the other hand, the present invention also provides the preparation method of described antioxidant, and its synthetic route comprises:
(1)酰氯化反应：(1) Acyl chloride reaction:
(2)4-氨基-2,2,6,6-四甲基哌啶的酰胺化反应：(2) Amidation reaction of 4-amino-2,2,6,6-tetramethylpiperidine:
(3)4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4-哌啶)胺基]乙基～十二烷基]苯甲酰胺化合物的合成反应：(3) Synthetic reaction of 4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidine)amino]ethyl～dodecyl]benzamide compound:
本发明中，所述制备方法包含以下步骤：(1)w-氨基酰氯和对羟基苯甲酰氯化合物的合成；(2)6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-(乙基～十二烷基)酰胺的合成；(3)抗氧剂的合成。In the present invention, the preparation method comprises the following steps: (1) synthesis of w-amino acid chloride and p-hydroxybenzoyl chloride compound; (2) synthesis of 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-(ethyl-dodecyl)amide; (3) synthesis of antioxidant.
其中：in:
w-氨基酸具有如下的结构其中n为碳原子数1-11；w-Amino acid has the following structure Wherein n is carbon atom number 1-11;
W-氨基酰氯具有以下结构：W-Amino acid chloride has the following structure:
其中n为碳原子数1-11； Wherein n is carbon atom number 1-11;
对羟基苯甲酸化合物具有以下结构：其中R独立地选自具有推电子效应的基团，如甲基、双取代甲基、异丁基、叔丁基，优选为叔丁基基团。Parabens have the following structure: Wherein R is independently selected from groups having an electron-pushing effect, such as methyl, disubstituted methyl, isobutyl, tert-butyl, preferably tert-butyl.
对羟基苯甲酰氯化合物具有以下结构：其中R独立地选自具有推电子效应的基团，如甲基、双取代甲基、异丁基、叔丁基，优选为叔丁基基团。The p-hydroxybenzoyl chloride compound has the following structure: Wherein R is independently selected from groups having an electron-pushing effect, such as methyl, disubstituted methyl, isobutyl, tert-butyl, preferably tert-butyl.
所述步骤(1)包含以下步骤：以四氢呋喃作为溶剂，少量三乙胺作为缚酸剂，将三光气溶解后与w-氨基酸或对羟基苯甲酸化合物混合，在惰性气体流通及搅拌下，升温反应，反应完成后进行减压蒸馏，收集残留物即为w-氨基酰氯与对羟基苯甲酰氯化合物；The step (1) includes the following steps: using tetrahydrofuran as a solvent and a small amount of triethylamine as an acid-binding agent, dissolving triphosgene and mixing it with w-amino acid or p-hydroxybenzoic acid compound, heating and reacting under the circulation and stirring of an inert gas, performing vacuum distillation after the reaction is completed, and collecting the residue as w-amino acid chloride and p-hydroxybenzoyl chloride compound;
所述步骤(1)中各原料的投料比为：w-氨基酸/对羟基苯甲酸化合物：三光气：三乙胺＝30：10～15：3～6，分别将w-氨基酸/对羟基苯甲酸化合物溶于THF溶液中。The feeding ratio of each raw material in the step (1) is: w-amino acid/p-hydroxybenzoic acid compound: triphosgene: triethylamine = 30: 10-15: 3-6, respectively dissolving w-amino acid/p-hydroxybenzoic acid compound in THF solution.
本发明中，所述反应溶剂THF的浓度为99.5％(AR分析纯)，所述三光气的浓度为99％，所述升温反应温度为25～40℃，反应时间为2～3h；减压蒸馏的温度为50～60℃，负压强度为0.05～0.1MPa，产品w-氨基酰氯和对羟基苯甲酰氯化合物的产率＞92％，纯度≥94％。In the present invention, the concentration of the reaction solvent THF is 99.5% (AR analytically pure), the concentration of the triphosgene is 99%, the temperature of the heating reaction is 25-40°C, and the reaction time is 2-3h; the temperature of the vacuum distillation is 50-60°C, the negative pressure is 0.05-0.1MPa, the yield of the product w-aminoacyl chloride and p-hydroxybenzoyl chloride compound is >92%, and the purity is more than or equal to 94%.
所述步骤(2)包含以下步骤：在惰性气体保护将4-氨基-2,2,6,6-四甲基哌啶于THF中稀释得到4-氨基-2,2,6,6-四甲基哌啶溶液，并将步骤(1)制得的w-氨基酰氯滴入4-氨基-2,2,6,6-四甲基哌啶溶液中反应，持续时间在1～2h，反应时间在1～3h间，期间保持搅拌，反应完成后对溶液进行减压蒸馏，并收集残留物，残留物即为6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-(乙基～十二烷基)酰胺；The step (2) includes the following steps: diluting 4-amino-2,2,6,6-tetramethylpiperidine in THF under the protection of an inert gas to obtain a 4-amino-2,2,6,6-tetramethylpiperidine solution, and dripping the w-amino acid chloride prepared in step (1) into the 4-amino-2,2,6,6-tetramethylpiperidine solution to react for a duration of 1 to 2 hours and a reaction time of 1 to 3 hours. Collect the residue, the residue is 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-(ethyl-dodecyl)amide;
所述步骤(2)中各原料投料比为：w-氨基酰氯：4-氨基-2,2,6,6-四甲基哌啶＝0.98～1.02：1，将4-氨基-2,2,6,6-四甲基哌啶溶于THF溶液中。The feeding ratio of each raw material in the step (2) is: w-amino acid chloride: 4-amino-2,2,6,6-tetramethylpiperidine=0.98-1.02:1, and 4-amino-2,2,6,6-tetramethylpiperidine is dissolved in THF solution.
本发明中，所述滴入的时间为1～2h，反应的温度为0-5℃，反应时间为1～3h，所述减压蒸馏的温度为50～60℃，负压强度为0.05～0.1MPa，6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-(乙基～十二烷基)酰胺的合成的产率＞93％，纯度＞97％。In the present invention, the dripping time is 1-2 hours, the reaction temperature is 0-5° C., the reaction time is 1-3 hours, the vacuum distillation temperature is 50-60° C., the negative pressure strength is 0.05-0.1 MPa, and the synthesis yield of 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-(ethyl-dodecyl)amide has a yield of >93% and a purity of >97%.
所述步骤(3)包含以下步骤：将6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-(乙基～十二烷基)酰胺于THF中稀释，并在惰性气体保护下将对羟基苯甲酰氯化合物缓慢滴入反应，保持搅拌，反应完成后对溶液进行减压蒸馏，并收集残留物，残留物即为4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4-哌啶)胺基]乙基～十二烷基]苯甲酰胺化合物。The step (3) includes the following steps: dilute 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-(ethyl-dodecyl)amide in THF, slowly drop p-hydroxybenzoyl chloride compound into the reaction under the protection of an inert gas, keep stirring, after the reaction is completed, the solution is distilled under reduced pressure, and the residue is collected. The residue is 4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4- piperidine) amino] ethyl ~ dodecyl] benzamide compound.
所述滴入时间为1～2h，反应温度为0～5℃，反应时间为时间为2-4h，所述减压蒸馏的温度为50～60℃，负压强度为0.05～0.1MPa，残留物4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4-哌啶)胺基]乙基～十二烷基]苯甲酰胺化合物为浅白色固体粉末，产率≥95％，纯度＞97％，并于空气中长期放置会出现颜色加深现象。The dropping time is 1-2 hours, the reaction temperature is 0-5°C, the reaction time is 2-4h, the vacuum distillation temperature is 50-60°C, the negative pressure strength is 0.05-0.1MPa, and the residue 4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidine)amino]ethyl-dodecyl]benzamide compound is a light white solid powder with a yield of ≥95% and a purity > 97%, and the color will deepen when placed in the air for a long time.
所述步骤(3)中各原料投料比为：6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-(乙基～十二烷基)酰胺：对羟基苯甲酰氯化合物＝1：1～1.05，将6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-(乙基～十二烷基)酰胺溶解或分散于THF溶液中。The feeding ratio of each raw material in the step (3) is: 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-(ethyl-dodecyl)amide:p-hydroxybenzoyl chloride compound=1:1-1.05, and 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-(ethyl-dodecyl)amide is dissolved or dispersed in the THF solution.
本发明的具体合成路线如下：Concrete synthetic route of the present invention is as follows:
本发明合成的最终产物产率可达95％以上，产率的计算方式如下：The synthetic final product productive rate of the present invention can reach more than 95%, and the calculation method of productive rate is as follows:
其中I为产率(％)，m为制得的产物G的质量(g)，n为反应物F或D的摩尔量(mol)，M为产物G的摩尔质量(g/mol)。Wherein I is the productive rate (%), m is the quality (g) of the product G that makes, n is the molar weight (mol) of reactant F or D, M is the molar mass (g/mol) of product G.
最后，本发明还提供了所述抗氧剂在聚酰胺组合物中的应用，所述的聚酰胺组合物包括PA6等聚酰胺牌号，添加质量分数约0.05％～0.55％的本发明合成的抗氧剂，并复配0.05～0.5％的S9228亚磷酸酯类抗氧剂，其中较优的组合为0.2～0.4％的本发明抗氧剂复配0.1～0.3％的S9228抗氧剂，更优的为0.25％的本发明抗氧剂复配0.2％的S9228抗氧剂。Finally, the present invention also provides the application of the antioxidant in a polyamide composition. The polyamide composition includes polyamide grades such as PA6, adding about 0.05% to 0.55% of the antioxidant synthesized by the present invention, and compounding 0.05 to 0.5% of the S9228 phosphite antioxidant. Oxygen, more preferably 0.25% of the antioxidant of the present invention compounded with 0.2% of the S9228 antioxidant.
本发明与现有抗氧剂对比具有以下优点：Compared with existing antioxidants, the present invention has the following advantages:
1)合成路线较为简便，没有显著的废液危害；1) The synthetic route is relatively simple, and there is no significant waste liquid hazard;
2)收率高，产物收集率可达95％以上；2) The yield is high, and the product collection rate can reach more than 95%;
3)实现反应溶剂的循环利用；3) realize the recycling of reaction solvent;
4)抗氧化效果显著优于现有抗氧剂，热氧老化后黄度指数有明显下降。4) The anti-oxidation effect is significantly better than that of existing antioxidants, and the yellowness index decreases significantly after thermal oxygen aging.
说明书附图Instructions attached
图1为本发明实施例5中产物G的红外谱图Fig. 1 is the infrared spectrogram of product G in the embodiment of the present invention 5
具体实施方式Detailed ways
下面通过一些具体实施例来对本发明中4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]乙基～十二烷基]苯甲酰胺类化合物的合成方法及性能表现进一步说明。以3,5-二叔丁基-4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]己基]苯甲酰胺、3,5-二叔丁基-4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]壬基]苯甲酰胺、3,5-二叔丁基-4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]十二烷基基]苯甲酰胺的合成方法为例。The synthesis method and performance of 4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidinyl)amino]ethyl-dodecyl]benzamide compounds in the present invention will be further described through some specific examples below. With 3,5-di-tert-butyl-4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidine)amino]hexyl]benzamide, 3,5-di-tert-butyl-4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidinyl)amino]nonyl]benzamide, 3,5-di-tert-butyl-4-hydroxy-α,α - The synthetic method of dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidinyl)amino]dodecyl]benzamide is an example.
应注意的是，本发明下列实施例仅以w-氨基己酸、w-氨基壬酸、w-氨基十二烷酸为例，不限制本发明的具体实施范围，此外应注意，在阅读了本发明的内容之后，本领域技术人员可以对本发明做各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。It should be noted that the following examples of the present invention only take w-aminocaproic acid, w-aminononanoic acid, and w-aminododecanoic acid as examples, and do not limit the specific implementation scope of the present invention. In addition, it should be noted that after reading the contents of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.
本发明中涉及的试剂、原料等若无特别说明，则均为市售常见原料：Reagents, raw materials, etc. involved in the present invention are commercially available common raw materials unless otherwise specified:
w-氨基己酸/w-氨基壬酸/w-氨基十二烷酸：上海阿拉丁生化科技股份有限公司，纯度＞98％；w-aminocaproic acid/w-aminononanoic acid/w-aminododecanoic acid: Shanghai Aladdin Biochemical Technology Co., Ltd., purity > 98%;
3,5-二叔丁基对羟基苯甲酸:上海阿拉丁生化科技股份有限公司，纯度＞98％；3,5-di-tert-butyl p-hydroxybenzoic acid: Shanghai Aladdin Biochemical Technology Co., Ltd., purity > 98%;
四氢呋喃：上海麦克林生化科技股份有限公司，AR分析纯，纯度＞99％；Tetrahydrofuran: Shanghai Macklin Biochemical Technology Co., Ltd., AR analytically pure, purity > 99%;
三乙胺：德国默克有限公司，AR分析纯，纯度＞99％；Triethylamine: Germany Merck Co., Ltd., AR analytical grade, purity> 99%;
三光气：上海阿拉丁生化科技股份有限公司，纯度＞99％；Triphosgene: Shanghai Aladdin Biochemical Technology Co., Ltd., purity > 99%;
4-氨基-2,2,6,6-四甲基哌啶：上海阿拉丁生化科技股份有限公司，纯度＞98％；4-Amino-2,2,6,6-tetramethylpiperidine: Shanghai Aladdin Biochemical Technology Co., Ltd., purity > 98%;
NaOH：国药集团药业股份有限公司，纯度＞96％。NaOH: Sinopharm Group Pharmaceutical Co., Ltd., purity>96%.
实施例1Example 1
(1)将w-氨基己酸(30mmol，3.93g)、3,5-二叔丁基对羟基苯甲酸(30mmol，7.5g)分别分散至THF(40mL)溶液中，加入少量三乙胺(3mmol，0.3g)，将三光气(10mmol，2.97g)溶于THF溶液(40ml)，使用恒压滴液漏斗滴入混合溶液中，期间保持惰性气体流通和搅拌，反应时间为1h，反应温度为25℃，结束后减压蒸馏得到残留液即为w-氨基己酰氯和3,5-二叔丁基对羟基苯甲酰氯，产率均＞89％，纯度＞92％，减馏温度为55℃，减馏后的液体经再次负压后收集用做后续实验溶剂。(1) Disperse w-aminocaproic acid (30mmol, 3.93g) and 3,5-di-tert-butyl-p-hydroxybenzoic acid (30mmol, 7.5g) into THF (40mL) solution respectively, add a small amount of triethylamine (3mmol, 0.3g), dissolve triphosgene (10mmol, 2.97g) in THF solution (40ml), use a constant pressure dropping funnel to drop into the mixed solution, and keep the inert gas flowing and Stirring, the reaction time is 1h, the reaction temperature is 25°C, and after the end, the residual liquid obtained by vacuum distillation is w-aminocaproyl chloride and 3,5-di-tert-butyl-p-hydroxybenzoyl chloride. The yields are both > 89%, and the purity is > 92%.
(2)将4-氨基-2,2,6,6-四甲基哌啶(25mmol，3.9g)与THF混溶，使用恒压滴液漏斗将w-氨基己酰氯(25.5mmol，3.81g)缓慢滴入混合溶液中，持续1h，反应温度为5℃，保持惰性气体流通及搅拌，反应1h，完成后减压蒸馏得到残留液，即为6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-己酰胺，减馏温度为55℃，产率＞84.2％，纯度＞89％。减馏后的液体经再次负压后收集用做后续实验溶剂。(2) Mix 4-amino-2,2,6,6-tetramethylpiperidine (25mmol, 3.9g) with THF, use a constant pressure dropping funnel to slowly drop w-aminocaproyl chloride (25.5mmol, 3.81g) into the mixed solution for 1h, the reaction temperature is 5°C, keep inert gas circulation and stirring, react for 1h, and then distill under reduced pressure to obtain the residual liquid, which is 6-amino-N-(2,2,6,6-tetramethyl -4-piperidine)-hexanamide, the reduction temperature is 55°C, the yield is >84.2%, and the purity is >89%. The liquid after reduction was collected under negative pressure again and used as a solvent for subsequent experiments.
(3)将3,5-二叔丁基对羟基苯甲酰氯(25.5mmol，6.375g)溶于THF(40mL)中，随后使用恒压滴液漏斗缓慢滴入6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-己酰胺(25mmol，6.725g)的THF(40mL)溶液，持续1h，期间保持惰性气体流通和搅拌，反应时间为2h，反应温度为5℃，结束后减压蒸馏得到残留液即为3,5-二叔丁基-4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]己基]苯甲酰胺，最终产物产率＞90.4％，纯度＞93％。(3) Dissolve 3,5-di-tert-butyl-p-hydroxybenzoyl chloride (25.5mmol, 6.375g) in THF (40mL), and then use a constant-pressure dropping funnel to slowly drop into a solution of 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-hexanamide (25mmol, 6.725g) in THF (40mL) for 1h, while maintaining inert gas circulation and stirring, the reaction time is 2 h, the reaction temperature is 5°C, and after the end, the residual liquid obtained by distillation under reduced pressure is 3,5-di-tert-butyl-4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidine)amino]hexyl]benzamide, the yield of the final product is >90.4%, and the purity is >93%.
实施例2Example 2
(1)将w-氨基十二烷基酸(30mmol，6.45g)、3,5-二叔丁基对羟基苯甲酸(30mmol，7.5g)分别分散至THF(40mL)溶液中，加入少量三乙胺(4mmol，0.404g)，将三光气(12mmol，3.56g)溶于THF溶液(40ml)，使用恒压滴液漏斗滴入混合溶液中，期间保持惰性气体流通和搅拌，反应时间为2.5h，反应温度为30℃，结束后减压蒸馏得到残留液即为w-氨基十二烷基酰氯和3,5-二叔丁基对羟基苯甲酰氯，产率均＞95％，纯度＞97％，减馏温度为55℃，减馏后的液体经负压蒸馏后收取用做后续实验溶剂。(1) Disperse w-aminododecanoic acid (30mmol, 6.45g) and 3,5-di-tert-butyl-p-hydroxybenzoic acid (30mmol, 7.5g) into THF (40mL) solution respectively, add a small amount of triethylamine (4mmol, 0.404g), dissolve triphosgene (12mmol, 3.56g) in THF solution (40ml), use a constant pressure dropping funnel to drop into the mixed solution, and keep inert Gas circulation and stirring, the reaction time is 2.5 hours, the reaction temperature is 30°C, after the vacuum distillation, the residual liquid is w-aminododecyl chloride and 3,5-di-tert-butyl-p-hydroxybenzoyl chloride, the yields are both > 95%, the purity is > 97%, the reduction temperature is 55°C, and the liquid after reduction is subjected to negative pressure distillation and collected as a solvent for subsequent experiments.
(2)将4-氨基-2,2,6,6-四甲基哌啶(25mmol，3.9g)与THF混溶，使用恒压滴液漏斗将w-氨基十二烷基酰氯(25.5mmol，6.43g)缓慢滴入混合溶液中，持续1.5h，反应温度为5℃，保持惰性气体流通及搅拌，反应1h，完成后减压蒸馏得到残留液，即为6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-十二烷基酰胺，减馏温度为55℃，最终产率＞95％，纯度＞97.5％。减馏后的液体经再次负压后收集用做后续实验溶剂。(2) Mix 4-amino-2,2,6,6-tetramethylpiperidine (25mmol, 3.9g) with THF, slowly drop w-aminododecanoyl chloride (25.5mmol, 6.43g) into the mixed solution using a constant pressure dropping funnel for 1.5h, the reaction temperature is 5°C, keep the inert gas flowing and stirring, react for 1h, and then distill under reduced pressure to obtain the residual liquid, which is 6-amino-N-(2,2,6,6 -Tetramethyl-4-piperidine)-dodecylamide, the reducing distillation temperature is 55°C, the final yield>95%, and the purity>97.5%. The liquid after reduction was collected under negative pressure again and used as a solvent for subsequent experiments.
(3)将3,5-二叔丁基对羟基苯甲酰氯(25.5mmol，6.375g)溶于THF(40mL)中，随后使用恒压滴液漏斗缓慢滴入6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-十二烷基酰胺(25mmol，8.85g)的THF(40mL)溶液，持续1h，期间保持惰性气体流通和搅拌，反应时间为4h，反应温度为3℃，结束后减压蒸馏得到残留液即为3,5-二叔丁基-4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]十二烷基]苯甲酰胺，最终产物产率＞96％，纯度＞98％。(3) Dissolve 3,5-di-tert-butyl-p-hydroxybenzoyl chloride (25.5mmol, 6.375g) in THF (40mL), and then use a constant-pressure dropping funnel to slowly drop into a THF (40mL) solution of 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-dodecylamide (25mmol, 8.85g) for 1h, during which the inert gas circulation and stirring were maintained, and the reaction time was 4 h, the reaction temperature is 3°C, and after the end, the residual liquid obtained by distillation under reduced pressure is 3,5-di-tert-butyl-4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidine)amino]dodecyl]benzamide, the yield of the final product is >96%, and the purity is >98%.
实施例3Example 3
(1)将w-氨基壬酸(30mmol，5.19g)、3,5-二叔丁基对羟基苯甲酸(30mmol，7.5g)分别分散至THF(40mL)溶液中，加入少量三乙胺(6mmol，0.6g)，将三光气(10mmol，2.97g)溶于THF溶液(40ml)，使用恒压滴液漏斗滴入混合溶液中，期间保持惰性气体流通和搅拌，反应时间为3h，反应温度为40℃，结束后减压蒸馏得到残留液即为w-氨基壬酰氯和3,5-二叔丁基对羟基苯甲酰氯，产率均＞78％，纯度＞81％，减馏温度为55℃，减馏后的液体经再次负压后收集用做后续实验溶剂。(1) Disperse w-aminononanoic acid (30mmol, 5.19g) and 3,5-di-tert-butyl p-hydroxybenzoic acid (30mmol, 7.5g) into THF (40mL) solution respectively, add a small amount of triethylamine (6mmol, 0.6g), dissolve triphosgene (10mmol, 2.97g) in THF solution (40ml), use a constant pressure dropping funnel to drop into the mixed solution, and keep the inert gas flowing and Stirring, the reaction time is 3 hours, the reaction temperature is 40°C, and after the end, the residual liquid obtained by vacuum distillation is w-aminononanoyl chloride and 3,5-di-tert-butyl-p-hydroxybenzoyl chloride. The yields are both >78%, and the purity is >81%.
(2)将4-氨基-2,2,6,6-四甲基哌啶(25mmol，3.9g)与THF混溶，使用恒压滴液漏斗将w-氨基壬酰氯(25.5mmol，4.88g)缓慢滴入混合溶液中，持续2h，反应温度为0℃，保持惰性气体流通及搅拌，反应2h，完成后减压蒸馏得到残留液，即为6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-壬酰胺，减馏温度为55℃，最终产率＞91％，纯度＞89％。减馏后的液体经再次负压后收集用做后续实验溶剂。(2) Mix 4-amino-2,2,6,6-tetramethylpiperidine (25mmol, 3.9g) with THF. Use a constant pressure dropping funnel to slowly drop w-aminononanoyl chloride (25.5mmol, 4.88g) into the mixed solution for 2 hours. The reaction temperature is 0°C. Keep the inert gas flowing and stirring, react for 2 hours, and then distill under reduced pressure to obtain the residual liquid, which is 6-amino-N-(2,2,6,6-tetramethyl -4-piperidine)-nonanamide, the reducing distillation temperature is 55°C, the final yield is >91%, and the purity is >89%. The liquid after reduction was collected under negative pressure again and used as a solvent for subsequent experiments.
(3)将3,5-二叔丁基对羟基苯甲酰氯(25.5mmol，6.375g)溶于THF(40mL)中，随后使用恒压滴液漏斗缓慢滴入6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-壬酰胺(25mmol，6.725g)的THF(40mL)溶液，持续2h，期间保持惰性气体流通和搅拌，反应时间3h，反应温度为0℃，结束后减压蒸馏得到残留液即为3,5-二叔丁基-4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]壬基]苯甲酰胺，最终产物产率＞96.7％，纯度＞98.1％。(3) Dissolve 3,5-di-tert-butyl-p-hydroxybenzoyl chloride (25.5mmol, 6.375g) in THF (40mL), then use a constant pressure dropping funnel to slowly drop into a solution of 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-nonanamide (25mmol, 6.725g) in THF (40mL) for 2h, during which the inert gas circulation and stirring were maintained, and the reaction time was 3h , the reaction temperature is 0°C. After the end, the residual liquid obtained by distillation under reduced pressure is 3,5-di-tert-butyl-4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidinyl)amino]nonyl]benzamide. The yield of the final product is >96.7%, and the purity is >98.1%.
实施例4Example 4
(1)将w-氨基己酸(30mmol，3.93g)、3,5-二叔丁基对羟基苯甲酸(30mmol，7.5g)分别分散至THF(40mL)溶液中，加入少量三乙胺(3mmol，0.3g)，将三光气(15mmol，4.45g)溶于THF溶液(40ml)，使用恒压滴液漏斗滴入混合溶液中，期间保持惰性气体流通和搅拌，反应时间为2h，反应温度为30℃，结束后减压蒸馏得到残留液即为w-氨基己酰氯和3,5-二叔丁基对羟基苯甲酰氯，产率均＞96％，纯度＞98％，减馏温度为55℃，减馏后的液体经再次负压后收集用做后续实验溶剂。(1) Disperse w-aminocaproic acid (30mmol, 3.93g) and 3,5-di-tert-butyl p-hydroxybenzoic acid (30mmol, 7.5g) into THF (40mL) solution respectively, add a small amount of triethylamine (3mmol, 0.3g), dissolve triphosgene (15mmol, 4.45g) in THF solution (40ml), use a constant pressure dropping funnel to drop into the mixed solution, and keep the inert gas flowing and Stirring, the reaction time is 2 hours, the reaction temperature is 30°C, and after the end, the residual liquid obtained by vacuum distillation is w-aminocaproyl chloride and 3,5-di-tert-butyl-p-hydroxybenzoyl chloride. The yields are both >96%, and the purity is >98%.
(2)将4-氨基-2,2,6,6-四甲基哌啶(25mmol，3.9g)与THF混溶，使用恒压滴液漏斗将w-氨基己酰氯(25.5mmol，3.81g)缓慢滴入混合溶液中，持续1.5h，反应温度为0℃，保持惰性气体流通及搅拌，反应3h，完成后减压蒸馏得到残留液，即为6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-己酰胺，减馏温度为55℃，最终产率＞95％，纯度＞97％。减馏后的液体经再次负压后收集用做后续实验溶剂。(2) Mix 4-amino-2,2,6,6-tetramethylpiperidine (25mmol, 3.9g) with THF, use a constant pressure dropping funnel to slowly drop w-aminocaproyl chloride (25.5mmol, 3.81g) into the mixed solution for 1.5h, the reaction temperature is 0°C, keep the inert gas flowing and stirring, react for 3h, and then distill under reduced pressure to obtain the residual liquid, which is 6-amino-N-(2,2,6,6- Tetramethyl-4-piperidine)-hexanamide, the reducing distillation temperature is 55°C, the final yield is >95%, and the purity is >97%. The liquid after reduction was collected under negative pressure again and used as a solvent for subsequent experiments.
(3)将3,5-二叔丁基对羟基苯甲酰氯(25.5mmol，6.375g)溶于THF(40mL)中，随后使用恒压滴液漏斗缓慢滴入6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-己酰胺(25mmol，6.725g)的THF(40mL)溶液，持续1h，期间保持惰性气体流通和搅拌，反应时间为2h，反应温度为3℃，结束后减压蒸馏得到残留液即为3,5-二叔丁基-4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]己基]苯甲酰胺，最终产物产率＞97％，纯度＞97％。(3) Dissolve 3,5-di-tert-butyl-p-hydroxybenzoyl chloride (25.5mmol, 6.375g) in THF (40mL), and then use a constant-pressure dropping funnel to slowly drop into a solution of 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-hexanamide (25mmol, 6.725g) in THF (40mL) for 1h, while maintaining inert gas circulation and stirring, the reaction time is 2 h, the reaction temperature is 3°C, and after the end, the residual liquid obtained by distillation under reduced pressure is 3,5-di-tert-butyl-4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidine)amino]hexyl]benzamide, the yield of the final product is >97%, and the purity is >97%.
实施例5Example 5
(1)将w-氨基己酸(30mmol，3.93g)、3,5-二叔丁基对羟基苯甲酸(30mmol，7.5g)分别分散至THF(40mL)溶液中，加入少量三乙胺(3mmol，0.3g)，将三光气(12mmol，3.56g)溶于THF溶液(40ml)，使用恒压滴液漏斗滴入混合溶液中，期间保持惰性气体流通和搅拌，反应时间为2h，反应温度为30℃，结束后减压蒸馏得到残留液即为w-氨基己酰氯和3,5-二叔丁基对羟基苯甲酰氯，产率均＞98％，纯度＞98％，减馏温度为55℃，减馏后的液体经再次负压后收集用做后续实验溶剂。(1) Disperse w-aminocaproic acid (30mmol, 3.93g) and 3,5-di-tert-butyl-p-hydroxybenzoic acid (30mmol, 7.5g) into THF (40mL) solution respectively, add a small amount of triethylamine (3mmol, 0.3g), dissolve triphosgene (12mmol, 3.56g) in THF solution (40ml), use a constant pressure dropping funnel to drop into the mixed solution, and keep the inert gas flowing and Stirring, the reaction time is 2 hours, the reaction temperature is 30°C, and after the end of the vacuum distillation, the residual liquid is w-aminocaproyl chloride and 3,5-di-tert-butyl-p-hydroxybenzoyl chloride. The yields are both >98%, and the purity is >98%.
(2)将4-氨基-2,2,6,6-四甲基哌啶(25mmol，3.9g)与THF混溶，使用恒压滴液漏斗将w-氨基己酰氯(25.5mmol，3.81g)缓慢滴入混合溶液中，持续1.5h，反应温度为3℃，保持惰性气体流通及搅拌，反应3h，完成后减压蒸馏得到残留液，即为6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-己酰胺，减馏温度为55℃，最终产率＞98.4％，纯度＞98.5％。减馏后的液体经再次负压后收集用做后续实验溶剂。(2) Mix 4-amino-2,2,6,6-tetramethylpiperidine (25mmol, 3.9g) with THF, slowly drop w-aminocaproyl chloride (25.5mmol, 3.81g) into the mixed solution using a constant-pressure dropping funnel for 1.5h, the reaction temperature is 3°C, keep inert gas circulation and stirring, react for 3h, and then distill under reduced pressure to obtain the residual liquid, which is 6-amino-N-(2,2,6,6- Tetramethyl-4-piperidine)-hexanamide, the distillation temperature is 55°C, the final yield is >98.4%, and the purity is >98.5%. The liquid after reduction was collected under negative pressure again and used as a solvent for subsequent experiments.
(3)将3,5-二叔丁基对羟基苯甲酰氯(25.5mmol，6.375g)溶于THF(40mL)中，随后使用恒压滴液漏斗缓慢滴入6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-己酰胺(25mmol，6.725g)的THF(40mL)溶液，持续1.5h，期间保持惰性气体流通和搅拌，反应时间为4h，反应温度为3℃，结束后减压蒸馏得到残留液即为3,5-二叔丁基-4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]己基]苯甲酰胺，最终产物产率＞97.8％，纯度＞98.6％。(3) Dissolve 3,5-di-tert-butyl-p-hydroxybenzoyl chloride (25.5mmol, 6.375g) in THF (40mL), and then use a constant pressure dropping funnel to slowly drop into a solution of 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-hexanamide (25mmol, 6.725g) in THF (40mL) for 1.5h, during which the inert gas circulation and stirring were maintained. The reaction time was 4 hours, and the reaction temperature was 3°C. After the end, the residual liquid was distilled under reduced pressure to obtain 3,5-di-tert-butyl-4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidinyl)amino]hexyl]benzamide. The yield of the final product was >97.8%, and the purity was >98.6%.
实施例6Example 6
(1)将w-氨基己酸(30mmol，3.93g)、3,5-二叔丁基对羟基苯甲酸(30mmol，7.5g)分别分散至THF(40mL)溶液中，加入少量三乙胺(6mmol，0.6g)，将三光气(15mmol，4.45g)溶于THF溶液(40ml)，使用恒压滴液漏斗滴入混合溶液中，期间保持惰性气体流通和搅拌，反应时间为3h，反应温度为40℃，结束后减压蒸馏得到残留液即为w-氨基己酰氯和3,5-二叔丁基对羟基苯甲酰氯，产率均＞78.5％，纯度＞76.8％，减馏温度为55℃，减馏后的液体经再次负压后收集用做后续实验溶剂。(1) Disperse w-aminocaproic acid (30mmol, 3.93g) and 3,5-di-tert-butyl p-hydroxybenzoic acid (30mmol, 7.5g) into THF (40mL) solution respectively, add a small amount of triethylamine (6mmol, 0.6g), dissolve triphosgene (15mmol, 4.45g) in THF solution (40ml), use a constant pressure dropping funnel to drop into the mixed solution, and keep the inert gas flowing and Stirring, the reaction time is 3 hours, the reaction temperature is 40°C, and after the end, the residual liquid obtained by vacuum distillation is w-aminocaproyl chloride and 3,5-di-tert-butyl-p-hydroxybenzoyl chloride. The yields are both >78.5%, and the purity is >76.8%.
(2)将4-氨基-2,2,6,6-四甲基哌啶(25mmol，3.9g)与THF混溶，使用恒压滴液漏斗将w-氨基己酰氯(25.5mmol，3.81g)缓慢滴入混合溶液中，持续2h，反应温度为0℃，保持惰性气体流通及搅拌，反应3h，完成后减压蒸馏得到残留液，即为6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-己酰胺，减馏温度为55℃，最终产率＞93.2％，纯度＞96.4％。减馏后的液体经再次负压后收集用做后续实验溶剂。(2) Mix 4-amino-2,2,6,6-tetramethylpiperidine (25mmol, 3.9g) with THF. Use a constant pressure dropping funnel to slowly drop w-aminocaproyl chloride (25.5mmol, 3.81g) into the mixed solution for 2 hours. The reaction temperature is 0°C. Keep the inert gas flowing and stirring. The reaction is 3 hours. -4-piperidine)-hexanamide, the reducing distillation temperature is 55°C, the final yield>93.2%, and the purity>96.4%. The liquid after reduction was collected under negative pressure again and used as a solvent for subsequent experiments.
(3)将3,5-二叔丁基对羟基苯甲酰氯(25.5mmol，6.375g)溶于THF(40mL)中，随后使用恒压滴液漏斗缓慢滴入6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-己酰胺(25mmol，6.725g)的THF(40mL)溶液，持续2h，期间保持惰性气体流通和搅拌，反应时间为4h，反应温度为0℃，结束后减压蒸馏得到残留液即为3,5-二叔丁基-4-羟基-α,α-二甲基-N-[6-[(2,2,6,6-四甲基-4哌啶)胺基]己基]苯甲酰胺，最终产物产率＞85.9％，纯度＞91％。(3) Dissolve 3,5-di-tert-butyl-p-hydroxybenzoyl chloride (25.5mmol, 6.375g) in THF (40mL), and then use a constant pressure dropping funnel to slowly drop into a THF (40mL) solution of 6-amino-N-(2,2,6,6-tetramethyl-4-piperidine)-hexanamide (25mmol, 6.725g) for 2h, during which the inert gas circulation and stirring were maintained, and the reaction time was 4 h, the reaction temperature is 0°C, and after the end, the residual liquid obtained by distillation under reduced pressure is 3,5-di-tert-butyl-4-hydroxy-α,α-dimethyl-N-[6-[(2,2,6,6-tetramethyl-4-piperidinyl)amino]hexyl]benzamide, the yield of the final product is >85.9%, and the purity is >91%.
对比例1Comparative example 1
将w-氨基己酸(30mmol，3.93g)分散至THF(40mL)溶液中，将三光气(15mmol，4.45g)溶于THF溶液(40ml)，使用恒压滴液漏斗滴入混合溶液中，期间保持惰性气体流通和搅拌，反应时间为3h，反应温度为40℃，结束后减压蒸馏得到残留液即为w-氨基己酰氯，产率均＞78.5％，纯度＞76.8％，减馏温度为55℃。Disperse w-aminocaproic acid (30mmol, 3.93g) into THF (40mL) solution, dissolve triphosgene (15mmol, 4.45g) in THF solution (40ml), use a constant pressure dropping funnel to drop into the mixed solution, keep the inert gas circulation and stir during the period, the reaction time is 3h, the reaction temperature is 40 ℃, after the end of vacuum distillation, the residual liquid is w-aminocaproyl chloride, the yield is >78.5%, and the purity is > 76.8%, the reduction temperature is 55°C.
对比例2Comparative example 2
将4-氨基-2,2,6,6-四甲基哌啶(25mmol，3.9g)与THF混溶，使用恒压滴液漏斗将w-氨基己酰氯(25.5mmol，3.81g)与上述THF溶液混合反应，持续1.5h，反应温度为3℃，保持惰性气体流通及搅拌，反应3h，完成后减压蒸馏得到残留液，即为6-胺基-N-(2,2,6,6-四甲基-4-哌啶)-己酰胺，减馏温度为55℃，最终产率＞48.4％，纯度＞39.3％。Mix 4-amino-2,2,6,6-tetramethylpiperidine (25mmol, 3.9g) with THF, use a constant pressure dropping funnel to mix w-aminocaproyl chloride (25.5mmol, 3.81g) with the above THF solution, continue for 1.5h, the reaction temperature is 3°C, keep inert gas circulation and stirring, react for 3h, and then distill under reduced pressure to obtain the residual liquid, which is 6-amino-N-(2,2,6,6-tetra Methyl-4-piperidine)-hexanamide, the distillation temperature is 55°C, the final yield is >48.4%, and the purity is >39.3%.
通过比对，可以看出实施例中的合成路线及条件可以得到最好的产品合成产率及纯度。By comparison, it can be seen that the synthesis route and conditions in the examples can obtain the best product synthesis yield and purity.
为更好阐述本发明抗氧剂对聚酰胺材料的抗老化能力，进行以下应用例描述，应注意的是本发明涉及的抗氧剂1098、光稳定剂770、辅助抗氧剂S9228均为市面常见型号，热氧老化程序在高温烘箱中进行，型号为ESPEC-PH(H)-202，黄度指数测试设备为积分球色差仪，型号为Hunterlab-VIS。In order to better illustrate the anti-aging ability of the antioxidant of the present invention on polyamide materials, the following application examples are described. It should be noted that the antioxidant 1098, light stabilizer 770, and auxiliary antioxidant S9228 involved in the present invention are all common models in the market. The thermal oxygen aging process is carried out in a high-temperature oven. The model is ESPEC-PH(H)-202.
应用例1Application example 1
将实施例2中合成抗氧剂加入PA6合成单体原料-己内酰胺中，其质量分数为0.5％，加入质量比1.5：1的蒸馏水作为催化剂及压力供给剂，反应步骤为：升高温度至230℃，在该温度下持续3h，随后升高温度至260℃，保持6h，并在此温度下保持压力在1.8MPa，温度降低至室温后结束反应。制得PA6聚合物，并注塑成样件经160℃热氧老化4h后进行光学测试。The antioxidant synthesized in Example 2 was added to the PA6 synthetic monomer raw material - caprolactam, with a mass fraction of 0.5%, and distilled water with a mass ratio of 1.5:1 was added as a catalyst and a pressure supply agent. The reaction steps were: raise the temperature to 230°C, keep it at this temperature for 3 hours, then raise the temperature to 260°C, keep it for 6 hours, and keep the pressure at 1.8MPa at this temperature, and stop the reaction after the temperature drops to room temperature. The PA6 polymer was prepared and injected into a sample for optical testing after thermal oxygen aging at 160°C for 4 hours.
应用例2Application example 2
将实施例3中合成抗氧剂加入PA6合成单体原料-己内酰胺中，其质量分数为0.05％，加入质量比1.5：1的蒸馏水作为催化剂及压力供给剂，反应步骤为：升高温度至230℃，在该温度下持续3h，随后升高温度至260℃，保持6h，并在此温度下保持压力在1.8MPa，温度降低至室温后结束反应。制得PA6聚合物，并注塑成样件经160℃热氧老化4h后进行光学测试。The antioxidant synthesized in Example 3 was added to the PA6 synthetic monomer raw material - caprolactam, with a mass fraction of 0.05%, and distilled water with a mass ratio of 1.5:1 was added as a catalyst and a pressure supply agent. The reaction steps were: raise the temperature to 230°C, keep at this temperature for 3h, then raise the temperature to 260°C, keep it for 6h, and keep the pressure at 1.8MPa at this temperature, and end the reaction after the temperature drops to room temperature. The PA6 polymer was prepared and injected into a sample for optical testing after thermal oxygen aging at 160°C for 4 hours.
应用例3Application example 3
将实施例5中合成抗氧剂加入PA6合成单体原料-己内酰胺中，其质量分数为0.25％，加入质量比1.5：1的蒸馏水作为催化剂及压力供给剂，反应步骤为：升高温度至230℃，在该温度下持续3h，随后升高温度至260℃，保持6h，并在此温度下保持压力在1.8MPa，温度降低至室温后结束反应。制得PA6聚合物，并注塑成样件经160℃热氧老化4h后进行光学测试。The antioxidant synthesized in Example 5 was added to the PA6 synthesis monomer raw material - caprolactam, with a mass fraction of 0.25%, and distilled water with a mass ratio of 1.5:1 was added as a catalyst and a pressure supply agent. The reaction steps were: raise the temperature to 230°C, keep at this temperature for 3h, then raise the temperature to 260°C, keep it for 6h, and keep the pressure at 1.8MPa at this temperature, and end the reaction after the temperature is lowered to room temperature. The PA6 polymer was prepared and injected into a sample for optical testing after thermal oxygen aging at 160°C for 4 hours.
应用例4Application example 4
将实施例5中合成抗氧剂加入PA6合成单体原料-己内酰胺中，其质量分数为0.25％，加入0.2％质量分数的辅助抗氧剂S9228，加入质量比1.5：1的蒸馏水作为催化剂及压力供给剂，反应步骤为：升高温度至230℃，在该温度下持续3h，随后升高温度至260℃，保持6h，并在此温度下保持压力在1.8MPa，温度降低至室温后结束反应。制得PA6聚合物，并注塑成样件经160℃热氧老化4h后进行光学测试。Add the synthetic antioxidants in the Example 5 to the PA6 synthetic monomer-of-ingredients-己 己 将, its mass score is 0.25 %, add 0.2 % of the auxiliary antioxidant S9228, add distilled water with a mass ratio of 1.5: 1 as a catalyst and a pressure supply agent. The response step is: increase temperature to 230 ° C. H, then increase the temperature to 260 ° C, keep it 6h, and keep the pressure at 1.8MPa at this temperature, and the temperature will be reduced to the end of the temperature after the temperature. The PA6 polymer was prepared and injected into a sample for optical testing after thermal oxygen aging at 160°C for 4 hours.
应用例5Application example 5
将抗氧剂1098加入PA6合成单体原料-己内酰胺中，其质量分数为0.25％，加入质量比1.5：1的蒸馏水作为催化剂及压力供给剂，反应步骤为：升高温度至230℃，在该温度下持续3h，随后升高温度至260℃，保持6h，并在此温度下保持压力在1.8MPa，温度降低至室温后结束反应。制得PA6聚合物，并注塑成样件经160℃热氧老化4h后进行光学测试。Add antioxidant 1098 to PA6 synthesis monomer raw material - caprolactam, its mass fraction is 0.25%, add distilled water with a mass ratio of 1.5:1 as catalyst and pressure supply agent, the reaction steps are: raise the temperature to 230°C, keep at this temperature for 3h, then raise the temperature to 260°C, keep it for 6h, and keep the pressure at 1.8MPa at this temperature, and end the reaction after the temperature drops to room temperature. The PA6 polymer was prepared and injected into a sample for optical testing after thermal oxygen aging at 160°C for 4 hours.
应用例6Application example 6
将光稳定剂770加入PA6合成单体原料-己内酰胺中，其质量分数为0.25％，加入质量比1.5：1的蒸馏水作为催化剂及压力供给剂，反应步骤为：升高温度至230℃，在该温度下持续3h，随后升高温度至260℃，保持6h，并在此温度下保持压力在1.8MPa，温度降低至室温后结束反应。制得PA6聚合物，并注塑成样件经160℃热氧老化4h后进行光学测试。Add light stabilizer 770 to caprolactam, the raw material for PA6 synthesis monomer, with a mass fraction of 0.25%, and add distilled water with a mass ratio of 1.5:1 as a catalyst and a pressure supply agent. The reaction steps are: raise the temperature to 230°C, keep it at this temperature for 3 hours, then raise the temperature to 260°C, keep it for 6 hours, and keep the pressure at 1.8MPa at this temperature, and stop the reaction after the temperature drops to room temperature. The PA6 polymer was prepared and injected into a sample for optical testing after thermal oxygen aging at 160°C for 4 hours.
应用例7Application example 7
将抗氧剂1098、光稳定剂770加入PA6合成单体原料-己内酰胺中，其质量分数均为0.25％，加入质量比1.5：1的蒸馏水作为催化剂及压力供给剂，反应步骤为：升高温度至230℃，在该温度下持续3h，随后升高温度至260℃，保持6h，并在此温度下保持压力在1.8MPa，温度降低至室温后结束反应。制得PA6聚合物，并注塑成样件经160℃热氧老化4h后进行光学测试。Add antioxidant 1098 and light stabilizer 770 to caprolactam, the monomer raw material for PA6 synthesis, with a mass fraction of 0.25%. Distilled water with a mass ratio of 1.5:1 is added as a catalyst and a pressure supply agent. The reaction steps are as follows: raise the temperature to 230°C, keep at this temperature for 3 hours, then raise the temperature to 260°C, keep it for 6 hours, and keep the pressure at 1.8MPa at this temperature, and end the reaction after the temperature drops to room temperature. The PA6 polymer was prepared and injected into a sample for optical testing after thermal oxygen aging at 160°C for 4 hours.
应用例8Application example 8
将抗氧剂1098、光稳定剂770加入PA6合成单体原料-己内酰胺中，其质量分数均为0.25％，加入0.2％质量分数的辅助抗氧剂S9228，加入质量比1.5：1的蒸馏水作为催化剂及压力供给剂，反应步骤为：升高温度至230℃，在该温度下持续3h，随后升高温度至260℃，保持6h，并在此温度下保持压力在1.8MPa，温度降低至室温后结束反应。制得PA6聚合物，并注塑成样件经160℃热氧老化4h后进行光学测试。Add antioxidant 1098 and light stabilizer 770 to PA6 synthesis monomer raw material-caprolactam, the mass fraction is 0.25%, add 0.2% mass fraction of auxiliary antioxidant S9228, add distilled water with a mass ratio of 1.5:1 as catalyst and pressure supply agent, the reaction steps are: raise the temperature to 230°C, continue at this temperature for 3h, then raise the temperature to 260°C, keep it for 6h, and keep the pressure at 1.8MPa at this temperature, and the temperature drops After reaching room temperature, the reaction was terminated. The PA6 polymer was prepared and injected into a sample for optical testing after thermal oxygen aging at 160°C for 4 hours.
应用例9Application example 9
将聚酰胺合成单体原料及质量比1.5：1的蒸馏水(作为催化剂及压力供给剂)，加入反应容器中，反应步骤为：升高温度至230℃，在该温度下持续3h，随后升高温度至260℃，保持6h，并在此温度下保持压力在1.8MPa，温度降低至室温后结束反应。制得PA6聚合物，并注塑成样件经160℃热氧老化4h后进行光学测试。The polyamide synthesis monomer raw material and distilled water with a mass ratio of 1.5:1 (as a catalyst and a pressure supply agent) were added to the reaction vessel. The reaction steps were: raise the temperature to 230°C, keep at this temperature for 3h, then raise the temperature to 260°C, keep it for 6h, and keep the pressure at 1.8MPa at this temperature, and stop the reaction after the temperature drops to room temperature. The PA6 polymer was prepared and injected into a sample for optical testing after thermal oxygen aging at 160°C for 4 hours.
下表为不同应用例中抗氧剂成分添加量及性能测试结果比对：The following table is a comparison of the amount of antioxidant components added and performance test results in different application examples:
可以看出同等添加质量百分数下本发明提供的抗氧剂效果优于1098，并且与1098和光稳定剂770协同作用下的效果几乎等同，并且在复配S9228后的效果更优。It can be seen that the effect of the antioxidant provided by the present invention is better than that of 1098 at the same weight percentage added, and the effect is almost the same as that of 1098 and light stabilizer 770 under the synergistic effect, and the effect after compounding S9228 is even better.
以上所述实施例仅为本实验涉及到的部分具体实施例，本发明内容并不限制于以上实施例，本发明的路线可以有各种更改和变化，但应注意，对于合成步骤有所改动、拆解、替换、组合等的修改应依旧包含于本发明应包含的范围内。The above-described embodiments are only some of the specific embodiments involved in this experiment. The content of the present invention is not limited to the above embodiments. The route of the present invention can have various changes and changes, but it should be noted that modifications such as changes, disassembly, replacement, and combination of synthesis steps should still be included in the scope of the present invention.
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| CN202310302338.1ACN116478451A (en) | 2023-03-27 | 2023-03-27 | A kind of antioxidant with photostability and heat-oxidative aging resistance and preparation method thereof |
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| CN102516157A (en)* | 2011-12-07 | 2012-06-27 | 浙江大学 | Synthetic method of hindered phenol/hindered amine intramolecular compound anti-oxidant |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
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| TA01 | Transfer of patent application right | Effective date of registration:20240208 Address after:264006 No. 59, Chongqing Street, Yantai Economic and Technological Development Zone, Shandong Province Applicant after:Wanhua Chemical Group Co.,Ltd. Country or region after:China Applicant after:Wanhua chemical (Ningbo) Co.,Ltd. Address before:315812 Wanhua Industrial Park, 39 Huandao North Road, Daxie Development Zone, Ningbo City, Zhejiang Province Applicant before:Wanhua chemical (Ningbo) Co.,Ltd. Country or region before:China |