CN110511431A - A kind of nitrogen of the structure containing benzoguanamine-phosphorus system efficient flame-retarding agent and its synthesis and application - Google Patents

A kind of nitrogen of the structure containing benzoguanamine-phosphorus system efficient flame-retarding agent and its synthesis and application Download PDF

Info

Publication number
CN110511431A
CN110511431A CN201910828940.2A CN201910828940A CN110511431A CN 110511431 A CN110511431 A CN 110511431A CN 201910828940 A CN201910828940 A CN 201910828940A CN 110511431 A CN110511431 A CN 110511431A
Authority
CN
China
Prior art keywords
nitrogen
benzomelamine
benzoguanamine
flame retardant
phosphorus system
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910828940.2A
Other languages
Chinese (zh)
Other versions
CN110511431B (en
Inventor
周红
陈瑞
胡开贤
许明星
潘志权
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Jinshangyuan New Materials Technology Co ltd
Original Assignee
Wuhan Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Institute of Technology filed Critical Wuhan Institute of Technology
Priority to CN201910828940.2A priority Critical patent/CN110511431B/en
Publication of CN110511431A publication Critical patent/CN110511431A/en
Application granted granted Critical
Publication of CN110511431B publication Critical patent/CN110511431B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Epoxy Resins (AREA)
  • Fireproofing Substances (AREA)

Abstract

本发明提供一种含苯代三聚氰胺结构的氮‑磷系高效阻燃剂及其合成与应用，涉及阻燃剂技术领域。一种含苯代三聚氰胺结构的氮‑磷系高效阻燃剂，具有以下结构式：本发明的阻燃剂的合成，包括以下步骤：（1）在氮气保护下，将苯代三聚氰胺、水杨醛加入溶剂中，得到水杨苯代三聚氰胺溶液；（2）使9，10‑二氢‑9‑氧杂‑10‑磷杂菲‑10‑氧化物与水杨苯代三聚氰胺进行亲和取代反应，得到水杨苯代三聚氰胺磷杂菲溶液；（3）将水杨苯代三聚氰胺磷杂菲溶液冷却，得到含苯代三聚氰胺结构的氮‑磷系高效阻燃剂。利用苯代三聚氰胺结构的成碳性和热稳定性，及氮‑磷共轭协同阻燃的特点，从而获得成碳率和阻燃效果更好的阻燃剂，产率高。

The invention provides a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure and its synthesis and application, and relates to the technical field of flame retardants. A nitrogen-phosphorus high-efficiency flame retardant containing benzomelamine structure has the following structural formula: The synthesis of the flame retardant of the present invention comprises the following steps: (1) under the protection of nitrogen, adding benzomelamine and salicylaldehyde into the solvent to obtain a salicylic benzomelamine solution; (2) making 9,10-2 Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide carries out affinity substitution reaction with salicylic benzomelamine phosphaphenanthrene to obtain salicylic benzomelamine phosphaphenanthrene solution; The phenanthrene solution is cooled to obtain a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure. Utilizing the carbon formation and thermal stability of the benzomelamine structure, and the characteristics of nitrogen-phosphorus conjugate synergistic flame retardancy, a flame retardant with better carbon formation rate and flame retardancy effect is obtained, and the yield is high.

Description

一种含苯代三聚氰胺结构的氮-磷系高效阻燃剂及其合成与 应用A nitrogen-phosphorus high-efficiency flame retardant containing benzomelamine structure and its synthesis and application

技术领域technical field

本发明涉及阻燃剂技术领域，具体涉及一种含苯代三聚氰胺结构的氮-磷系高效阻燃剂及其合成与应用。The invention relates to the technical field of flame retardants, in particular to a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure and its synthesis and application.

背景技术Background technique

树脂是一类日常生活中常用的高分子材料，因其具有很好的抗氧化、抗腐蚀的特性，被应用到很多技术领域。然而树脂的易燃，安全性低。Resin is a kind of polymer material commonly used in daily life. Because of its good anti-oxidation and anti-corrosion properties, it is applied to many technical fields. However, the resin is flammable and has low safety.

环氧树脂是一类重要的热固性塑料，因其具有良好的粘结性、电绝缘性、化学稳定性，广泛应用于涂料、粘胶剂、电子电器材料、工程塑料和复合材料、土建材料等领域。但环氧树脂极限氧指数非常低，极易燃烧，失火后持续燃烧且发烟量大。其易燃性限制了它在许多领域的应用。因此，赋予EP良好的阻燃性是至关重要的。Epoxy resin is an important class of thermosetting plastics. Because of its good adhesion, electrical insulation and chemical stability, it is widely used in coatings, adhesives, electronic and electrical materials, engineering plastics and composite materials, civil engineering materials, etc. field. However, the limiting oxygen index of epoxy resin is very low, and it is extremely flammable. After a fire, it continues to burn and emits a large amount of smoke. Its flammability limits its application in many fields. Therefore, it is crucial to endow EP with good flame retardancy.

为了提高环氧树脂的阻燃性能，常见的方法是添加阻燃剂。传统的阻燃剂含有卤素，燃烧时存在多烟、有毒气体放出。现有技术中的，环氧树脂的阻燃剂的制备往往是与9,10-二氢-9-氧-10-磷杂菲-10-氧化物（DOPO）复合，但是制备的阻燃剂的成碳率比较低，阻燃效果比较差。In order to improve the flame retardant performance of epoxy resin, the common method is to add flame retardants. Traditional flame retardants contain halogens, which emit smoke and toxic gases when burned. In the prior art, the preparation of epoxy resin flame retardants is often compounded with 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (DOPO), but the prepared flame retardant The carbon formation rate is relatively low, and the flame retardant effect is relatively poor.

发明内容Contents of the invention

有鉴于此，本发明提供一种含苯代三聚氰胺结构的氮-磷系高效阻燃剂及其合成与应用，利用苯代三聚氰胺结构的成碳性和热稳定性，及氮-磷共轭协同阻燃的特点，从而获得成碳率和阻燃效果更好的阻燃剂，含有该阻燃剂的环氧树脂热固材料在燃烧中更容易形成致密碳层，从而隔绝氧气与内部材料的接触，达到阻燃效果。In view of this, the present invention provides a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure and its synthesis and application, utilizing the carbon formation and thermal stability of the benzomelamine structure, and the nitrogen-phosphorus conjugate synergistic The characteristics of flame retardant, so as to obtain a flame retardant with better carbon formation rate and flame retardant effect. The epoxy resin thermosetting material containing this flame retardant is more likely to form a dense carbon layer during combustion, thereby isolating oxygen and internal materials. Contact to achieve flame retardant effect.

本发明为一种含苯代三聚氰胺结构的氮-磷系高效阻燃剂，具有以下结构式：The invention is a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure, which has the following structural formula:

一种前文所述的含苯代三聚氰胺结构的氮-磷系高效阻燃剂的合成，包括以下步骤：A kind of synthesis of nitrogen-phosphorus high-efficiency flame retardant containing benzomelamine structure described above comprises the following steps:

（1）在氮气保护下，将苯代三聚氰胺、水杨醛按照摩尔比为1:2-2.5的比例加入溶剂中，60-90℃下，反应3-4小时，进行席夫碱反应，得到水杨苯代三聚氰胺溶液，溶剂可以使用DMF，反应过程中的反应方程式如下；(1) Under the protection of nitrogen, add benzomelamine and salicylaldehyde into the solvent at a molar ratio of 1:2-2.5, react at 60-90°C for 3-4 hours, and perform Schiff base reaction to obtain Salicylbenzomelamine solution, solvent can use DMF, and the reaction equation in the reaction process is as follows;

（2）将与水杨醛的摩尔量相等的9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物加入所述水杨苯代三聚氰胺溶液，使9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物与水杨苯代三聚氰胺进行亲和取代反应，反应的时间为6-7小时，反应温度为60-90℃，得到，得到水杨苯代三聚氰胺磷杂菲溶液，反应方程式如下；(2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide equivalent to the molar amount of salicylaldehyde is added to the salicylic benzomelamine solution to make 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide undergoes affinity substitution reaction with salicylic benzomelamine, the reaction time is 6-7 hours, and the reaction temperature is 60-90°C to obtain, to obtain Salicylic benzomelamine phosphaphenanthrene solution, the reaction equation is as follows;

（3）将所述水杨苯代三聚氰胺磷杂菲溶液冷却，降温至室温，加入去离子水后，有白色固体析出，过滤以后用去离子水洗涤2-3次，再60-70℃干燥10-12h得到含苯代三聚氰胺结构的氮-磷系高效阻燃剂。(3) Cool the salicylic benzomelamine phosphaphenanthrene solution and cool it down to room temperature. After adding deionized water, a white solid precipitates out. After filtering, wash with deionized water for 2-3 times, and then dry at 60-70°C After 10-12 hours, a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure is obtained.

一种如前文所述的含苯代三聚氰胺结构的氮-磷系高效阻燃剂的应用，包括以下步骤：将环氧树脂、含苯代三聚氰胺结构的氮-磷系高效阻燃剂按照质量比为100：5-10混合，在90-100℃搅拌；抽真空以后加入质量为环氧树脂的0.15-0.2倍的固化剂，混合均匀后得到树脂混合物；将树脂混合物倒入模具，冷却后得到环氧树脂固体。An application of a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure as described above, comprising the following steps: mixing epoxy resin and a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure according to the mass ratio Mix at 100:5-10, stir at 90-100°C; add a curing agent whose mass is 0.15-0.2 times that of the epoxy resin after vacuuming, and mix well to obtain a resin mixture; pour the resin mixture into a mold and cool to obtain Epoxy solid.

所述固化剂可以为4,4'二氨基二苯甲烷(DDM)固化剂。The curing agent may be a 4,4' diaminodiphenylmethane (DDM) curing agent.

本反应的反应过程为首先使苯代三聚氰胺、水杨醛发生席夫碱反应，生成中间产物水杨苯代三聚氰胺，然后再加入DOPO，水杨苯代三聚氰胺与DOPO发生亲核取代反应生成水杨苯代三聚氰胺磷杂菲（HDPD），即阻燃剂，经降温使水杨苯代三聚氰胺磷杂菲（HDPD）析晶，过滤、洗涤以后得到HDPD固体，即含苯代三聚氰胺结构的氮-磷系高效阻燃剂。The reaction process of this reaction is first to make benzomelamine and salicylaldehyde undergo a Schiff base reaction to generate the intermediate product salicylic benzomelamine, then add DOPO, and salicylic benzomelamine and DOPO undergo a nucleophilic substitution reaction to generate salicyl Benzomelamine phosphaphenanthrene (HDPD), that is, flame retardant, crystallize salicylic benzomelamine phosphaphenanthrene (HDPD) after cooling down, filter and wash to obtain HDPD solid, that is, nitrogen-phosphorus containing benzomelamine structure Department of high-efficiency flame retardants.

本发明的有益效果：苯代三聚氰胺中含有丰富的伯胺，与DOPO反应形成的衍生物具有氮磷的协同作用，可以促进DOPO的阻燃效果；以苯代三聚氰胺、水杨醛为原料，使得阻燃剂中具有苯代三聚氰胺结构，苯代三聚氰胺结构具有很好的成碳性和热稳定性，含有阻燃剂的环氧树脂热固材料在燃烧中更容易形成致密碳层，从而隔绝氧与内部材料的接触，达到阻燃效果，提高阻燃剂阻燃效果；氮-磷共轭协同阻燃，阻燃剂的结构中空间位阻大，有利于提高阻燃效应；此外苯代三聚氰胺还有促进固化的作用，在燃烧的时候阻碍树脂的熔融，阻燃燃烧，合成方法简单、产率高达97%，且不含有卤素，绿色环保。Beneficial effects of the present invention: benzomelamine is rich in primary amines, and the derivatives formed by reacting with DOPO have a synergistic effect of nitrogen and phosphorus, which can promote the flame-retardant effect of DOPO; using benzomelamine and salicylaldehyde as raw materials, make The flame retardant has a benzomelamine structure, and the benzomelamine structure has good carbon formation and thermal stability. The epoxy resin thermosetting material containing the flame retardant is more likely to form a dense carbon layer during combustion, thereby isolating oxygen. The contact with the internal material achieves the flame retardant effect and improves the flame retardant effect of the flame retardant; nitrogen-phosphorus conjugate synergistic flame retardant, the steric hindrance in the structure of the flame retardant is large, which is conducive to improving the flame retardant effect; in addition, benzomelamine It also has the effect of promoting solidification, hinders the melting of resin when burning, and flame-retardant combustion. The synthesis method is simple, the yield is as high as 97%, and it does not contain halogen, which is green and environmentally friendly.

附图说明Description of drawings

图1为本发明中实施例1中提供的一种含苯代三聚氰胺结构的氮-磷系高效阻燃剂的核磁氢谱谱图；Fig. 1 is the NMR spectrogram of a kind of nitrogen-phosphorus high-efficiency flame retardant containing benzomelamine structure provided in Example 1 of the present invention;

图2为本发明中实施例1中提供的一种含苯代三聚氰胺结构的氮-磷系高效阻燃剂的核磁磷谱谱图；Fig. 2 is the NMR phosphorus spectrogram of a kind of nitrogen-phosphorus high-efficiency flame retardant containing benzomelamine structure provided in Example 1 of the present invention;

图3为未添加本发明的阻燃剂的环氧树脂燃烧以后残渣的SEM图；Fig. 3 is the SEM figure of residue after the epoxy resin burning without adding flame retardant of the present invention;

图4本发明的实施例1中提供的一种含苯代三聚氰胺结构的氮-磷系高效阻燃剂的应用制备的含阻燃剂的环氧树脂固体燃烧以后残渣的SEM图。Fig. 4 is an SEM image of the residue after solid combustion of the epoxy resin containing the flame retardant prepared by using the nitrogen-phosphorus high-efficiency flame retardant containing the benzomelamine structure provided in Example 1 of the present invention.

具体实施方式Detailed ways

下面结合具体实施方式对本发明进行详细描述。The present invention will be described in detail below in conjunction with specific embodiments.

实施例1Example 1

一种含苯代三聚氰胺结构的氮-磷系高效阻燃剂，具有以下结构式：A nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure has the following structural formula:

本实施例中所述的含苯代三聚氰胺结构的氮-磷系高效阻燃剂的合成，包括以下步骤：The synthesis of the nitrogen-phosphorus high-efficiency flame retardant containing benzomelamine structure described in this embodiment comprises the following steps:

（1）在氮气保护下，将苯代三聚氰胺、水杨醛按照摩尔比为1:2的比例加入溶剂中，60℃下，反应3小时，进行席夫碱反应，得到水杨苯代三聚氰胺溶液，溶剂可以使用DMF，反应过程中的反应方程式如下；(1) Under the protection of nitrogen, add benzomelamine and salicylaldehyde into the solvent at a molar ratio of 1:2, react at 60°C for 3 hours, and perform a Schiff base reaction to obtain salicylbenzomelamine solution , the solvent can use DMF, and the reaction equation in the reaction process is as follows;

（2）将与水杨醛的摩尔量相等的9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物加入所述水杨苯代三聚氰胺溶液，使9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物与水杨苯代三聚氰胺进行亲和取代反应，反应的时间为6小时，反应温度为60℃，得到，得到水杨苯代三聚氰胺磷杂菲溶液，反应方程式如下；(2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide equivalent to the molar amount of salicylaldehyde is added to the salicylic benzomelamine solution to make 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was subjected to affinity substitution reaction with salicylic benzomelamine, the reaction time was 6 hours, and the reaction temperature was 60°C to obtain salicylic benzo Melamine phosphaphenanthrene solution, the reaction equation is as follows;

（3）将所述水杨苯代三聚氰胺磷杂菲溶液冷却，降温至室温，加入去离子水后，有白色固体析出，过滤以后用去离子水洗涤2次，再60℃干燥10h得到含苯代三聚氰胺结构的氮-磷系高效阻燃剂。(3) Cool the salicylic benzomelamine phosphaphenanthrene solution and cool it down to room temperature. After adding deionized water, a white solid precipitates out. After filtering, it is washed twice with deionized water, and then dried at 60°C for 10 hours to obtain benzene-containing Nitrogen-phosphorus high-efficiency flame retardant with melamine structure.

一种如前文所述的含苯代三聚氰胺结构的氮-磷系高效阻燃剂的应用，包括以下步骤：将环氧树脂、含苯代三聚氰胺结构的氮-磷系高效阻燃剂按照质量比为100：5混合，在90℃搅拌；抽真空以后加入质量为环氧树脂的0.15倍的DDM固化剂，混合均匀后得到树脂混合物；将树脂混合物倒入模具，冷却后得到环氧树脂固体。An application of a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure as described above, comprising the following steps: mixing epoxy resin and a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure according to the mass ratio Mix at 100:5 and stir at 90°C; add DDM curing agent whose mass is 0.15 times that of the epoxy resin after vacuuming, and mix well to obtain a resin mixture; pour the resin mixture into a mold, and obtain a solid epoxy resin after cooling.

取本实施例中制备的阻燃剂进行核磁氢谱谱图、核磁磷谱谱图分析，结果如图1、图2所示。图1和图2分别为合成的阻燃剂HDPD的1HNMR及磷谱图。氢谱中只含三类氢，分别是苯环，CH及OH, 而该氢谱图中除溶剂峰外，只呈现这三类氢的化学位移，且积分面积与各类氢的个数之比吻合。另外，分子结构中只含一种磷，而磷谱中只呈现了一种磷的化学位移，且此位移与原料DOPO中磷元素的化学位移存在较大差异。产率为96.8%。The flame retardant prepared in this example was analyzed by proton nuclear magnetic spectrum and phosphorus nuclear magnetic spectrum, and the results are shown in Fig. 1 and Fig. 2 . Figure 1 and Figure 2 are the 1 HNMR and phosphorus spectrum of the synthesized flame retardant HDPD, respectively. There are only three types of hydrogen in the hydrogen spectrum, which are benzene ring, CH and OH. In addition to the solvent peak, the hydrogen spectrum only shows the chemical shifts of these three types of hydrogen, and the relationship between the integral area and the number of each type of hydrogen Than match. In addition, there is only one kind of phosphorus in the molecular structure, and only one kind of phosphorus chemical shift is shown in the phosphorus spectrum, and this shift is quite different from the chemical shift of phosphorus in raw material DOPO. The yield was 96.8%.

制备出的环氧树脂固体氧指数测试结果为33.0，垂直燃烧实验结果为V1 级别。The test result of the solid oxygen index of the prepared epoxy resin was 33.0, and the result of the vertical combustion test was V 1 level.

图3为未添加本发明的阻燃剂的环氧树脂燃烧以后残渣的SEM图；图4本发明的实施例1中制备的环氧树脂固体燃烧以后残渣的SEM图。可以看出实施例中的环氧树脂固体的燃烧后表层致密，能够起到很好隔绝空气的作用，进而阻燃。Fig. 3 is the SEM picture of the residue after burning of the epoxy resin without adding the flame retardant of the present invention; Fig. 4 is the SEM picture of the residue of the epoxy resin solid after burning prepared in Example 1 of the present invention. It can be seen that the surface layer of the solid epoxy resin in the embodiment is dense after burning, which can play a good role in isolating the air and thus flame retardant.

实施例2Example 2

一种含苯代三聚氰胺结构的氮-磷系高效阻燃剂，具有以下结构式：A nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure has the following structural formula:

本实施例中所述的含苯代三聚氰胺结构的氮-磷系高效阻燃剂的合成，包括以下步骤：The synthesis of the nitrogen-phosphorus high-efficiency flame retardant containing benzomelamine structure described in this embodiment comprises the following steps:

（1）在氮气保护下，将苯代三聚氰胺、水杨醛按照摩尔比为1:2-2.5的比例(1) Under the protection of nitrogen, mix benzomelamine and salicylaldehyde in a molar ratio of 1:2-2.5

加入DMF中，90℃下，反应4小时，进行席夫碱反应，得到水杨苯代三聚氰胺溶液；Adding it to DMF, reacting at 90°C for 4 hours, performing Schiff base reaction to obtain salicylbenzomelamine solution;

（2）将与水杨醛的摩尔量相等的9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物加入所述水杨苯代三聚氰胺溶液，使9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物与水杨苯代三聚氰胺进行亲和取代反应，反应的时间为7小时，反应温度为90℃，得到，得到水杨苯代三聚氰胺磷杂菲溶液；(2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide equivalent to the molar amount of salicylaldehyde is added to the salicylic benzomelamine solution to make 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was subjected to affinity substitution reaction with salicylic benzomelamine, the reaction time was 7 hours, and the reaction temperature was 90°C to obtain salicylic benzo Melamine phosphaphenanthrene solution;

（3）将所述水杨苯代三聚氰胺磷杂菲溶液冷却，降温至室温，加入去离子水后，有白色固体析出，过滤以后用去离子水洗涤3次，再70℃干燥12h得到含苯代三聚氰胺结构的氮-磷系高效阻燃剂。(3) Cool the salicylic benzomelamine phosphaphenanthrene solution and cool it down to room temperature. After adding deionized water, a white solid precipitates out. After filtering, it is washed with deionized water for 3 times, and then dried at 70°C for 12 hours to obtain benzene-containing Nitrogen-phosphorus high-efficiency flame retardant with melamine structure.

一种如前文所述的含苯代三聚氰胺结构的氮-磷系高效阻燃剂的应用，包括以下步骤：将环氧树脂、含苯代三聚氰胺结构的氮-磷系高效阻燃剂按照质量比为100：10混合，在100℃搅拌；抽真空以后加入质量为环氧树脂的0.2倍的DDM固化剂，混合均匀后得到树脂混合物；将树脂混合物倒入模具，冷却后得到环氧树脂固体。An application of a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure as described above, comprising the following steps: mixing epoxy resin and a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure according to the mass ratio Mix at 100:10 and stir at 100°C; add DDM curing agent whose mass is 0.2 times that of the epoxy resin after vacuuming, and mix well to obtain a resin mixture; pour the resin mixture into a mold and cool to obtain a solid epoxy resin.

阻燃剂的产率为97.2%，制备的环氧树脂固体氧指数测试结果为35.5，垂直燃烧实验结果为V0 级别。The yield of the flame retardant was 97.2%. The test result of the solid oxygen index of the prepared epoxy resin was 35.5, and the result of the vertical combustion test was V 0 level.

实施例3Example 3

一种含苯代三聚氰胺结构的氮-磷系高效阻燃剂，具有以下结构式：A nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure has the following structural formula:

本实施例中所述的含苯代三聚氰胺结构的氮-磷系高效阻燃剂的合成，包括以下步骤：The synthesis of the nitrogen-phosphorus high-efficiency flame retardant containing benzomelamine structure described in this embodiment comprises the following steps:

（1）在氮气保护下，将苯代三聚氰胺、水杨醛按照摩尔比为1:2.1的比例加入DMF溶剂中，70℃下，反应3.5小时，进行席夫碱反应，得到水杨苯代三聚氰胺溶液；(1) Under nitrogen protection, add benzomelamine and salicylaldehyde into the DMF solvent at a molar ratio of 1:2.1, react at 70°C for 3.5 hours, and perform a Schiff base reaction to obtain salicylbenzomelamine solution;

（2）将与水杨醛的摩尔量相等的9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物加入所述水杨苯代三聚氰胺溶液，使9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物与水杨苯代三聚氰胺进行亲和取代反应，反应的时间为6.5小时，反应温度为80℃，得到，得到水杨苯代三聚氰胺磷杂菲溶液；(2) 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide equivalent to the molar amount of salicylaldehyde is added to the salicylic benzomelamine solution to make 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was subjected to affinity substitution reaction with salicylbenzomelamine, the reaction time was 6.5 hours, and the reaction temperature was 80°C to obtain salicylbenzo Melamine phosphaphenanthrene solution;

（3）将所述水杨苯代三聚氰胺磷杂菲溶液冷却，降温至室温，加入去离子水后，有白色固体析出，过滤以后用去离子水洗涤3次，再65℃干燥11h得到含苯代三聚氰胺结构的氮-磷系高效阻燃剂。(3) Cool the salicylic benzomelamine phosphaphenanthrene solution and cool it down to room temperature. After adding deionized water, a white solid precipitates out. After filtering, it is washed with deionized water for 3 times, and then dried at 65°C for 11 hours to obtain benzene-containing Nitrogen-phosphorus high-efficiency flame retardant with melamine structure.

一种如前文所述的含苯代三聚氰胺结构的氮-磷系高效阻燃剂的应用，包括以下步骤：将环氧树脂、含苯代三聚氰胺结构的氮-磷系高效阻燃剂按照质量比为100：8混合，在95℃搅拌；抽真空以后加入质量为环氧树脂的0.17倍的DDM固化剂，混合均匀后得到树脂混合物；将树脂混合物倒入模具，冷却后得到环氧树脂固体。An application of a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure as described above, comprising the following steps: mixing epoxy resin and a nitrogen-phosphorus high-efficiency flame retardant containing a benzomelamine structure according to the mass ratio Mix at 100:8 and stir at 95°C; add DDM curing agent whose mass is 0.17 times that of the epoxy resin after vacuuming, and mix well to obtain a resin mixture; pour the resin mixture into a mold, and obtain a solid epoxy resin after cooling.

阻燃剂的产率为97.5%，制备的环氧树脂固体氧指数测试结果为34.6，垂直燃烧实验结果为V0 级别。The yield of the flame retardant was 97.5%. The test result of the solid oxygen index of the prepared epoxy resin was 34.6, and the result of the vertical combustion test was V 0 level.

本发明的有益效果：苯代三聚氰胺中含有丰富的伯胺，与DOPO反应形成的衍生物具有氮磷的协同作用，可以促进DOPO的阻燃效果；以苯代三聚氰胺、水杨醛为原料，使得阻燃剂中具有苯代三聚氰胺结构，苯代三聚氰胺结构具有很好的成碳性和热稳定性，含有阻燃剂的环氧树脂热固材料在燃烧中更容易形成致密碳层，从而隔绝氧与内部材料的接触，达到阻燃效果，提高阻燃剂阻燃效果；氮-磷共轭协同阻燃，阻燃剂的结构中空间位阻大，有利于提高阻燃效应；此外苯代三聚氰胺还有促进固化的作用，在燃烧的时候阻碍树脂的熔融，阻燃燃烧，合成方法简单、产率高达97%，且不含有卤素，绿色环保。Beneficial effects of the present invention: benzomelamine is rich in primary amines, and the derivatives formed by reacting with DOPO have a synergistic effect of nitrogen and phosphorus, which can promote the flame-retardant effect of DOPO; using benzomelamine and salicylaldehyde as raw materials, make The flame retardant has a benzomelamine structure, and the benzomelamine structure has good carbon formation and thermal stability. The epoxy resin thermosetting material containing the flame retardant is more likely to form a dense carbon layer during combustion, thereby isolating oxygen. The contact with the internal material achieves the flame retardant effect and improves the flame retardant effect of the flame retardant; nitrogen-phosphorus conjugate synergistic flame retardant, the steric hindrance in the structure of the flame retardant is large, which is conducive to improving the flame retardant effect; in addition, benzomelamine It also has the effect of promoting solidification, hinders the melting of resin when burning, and flame-retardant combustion. The synthesis method is simple, the yield is as high as 97%, and it does not contain halogen, which is green and environmentally friendly.

本发明不局限于上述具体的实施方式，本发明可以有各种更改和变化。凡是依据本发明的技术实质对以上实施方式所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围。The present invention is not limited to the specific embodiments described above, and various modifications and changes are possible in the present invention. Any modifications, equivalent replacements, improvements, etc. made to the above implementation methods based on the technical essence of the present invention shall be included in the protection scope of the present invention.

Claims (9)

1. a kind of nitrogen of structure containing benzoguanamine-phosphorus system efficient flame-retarding agent, which is characterized in that have following structure formula:
。
2. a kind of nitrogen-phosphorus system efficient flame-retarding agent synthesis of the structure containing benzoguanamine as described in power 1, which is characterized in that The following steps are included:
(1) under nitrogen protection, benzoguanamine, salicylide are added in solvent, at 60-90 DEG C, are reacted 3-4 hours, into Row schiff base reaction obtains bigcatkin willow benzoguanamine solution；
(2) the bigcatkin willow benzoguanamine solution is added in 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, made 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and bigcatkin willow benzoguanamine carry out nucleophilic substitution reaction, reaction Time is to obtain for 6-7 hours, obtains bigcatkin willow benzoguanamine phospho hetero phenanthrene solution；
(3) the bigcatkin willow benzoguanamine phospho hetero phenanthrene solution is cooling, add water, is filtered, is dried to obtain containing benzene for melamine The nitrogen of amine structure-phosphorus system efficient flame-retarding agent.
3. a kind of synthesis of the nitrogen of structure containing benzoguanamine according to claim 1-phosphorus system efficient flame-retarding agent, special Sign is that the benzoguanamine, salicylide molar ratio are 1:2-2.5.
4. a kind of synthesis of the nitrogen of structure containing benzoguanamine according to claim 2-phosphorus system efficient flame-retarding agent, special Sign is that the mole of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is equal to mole of the salicylide Amount.
5. a kind of synthesis of the nitrogen of structure containing benzoguanamine according to claim 1-phosphorus system efficient flame-retarding agent, special Sign is that the reaction temperature of nucleophilic substitution reaction described in step (2) is 60-90 DEG C.
6. a kind of synthesis of the nitrogen of structure containing benzoguanamine according to claim 1-phosphorus system efficient flame-retarding agent, special Sign is that the temperature of step (3) described drying is 60-70 DEG C, and the dry time is 10-12h.
7. a kind of nitrogen of the structure containing benzoguanamine as described in claim 1 to 6 any one-phosphorus system efficient flame-retarding agent Using, which comprises the following steps: by epoxy resin, nitrogen-phosphorus system efficient flame-retarding agent of the structure containing benzoguanamine It is 100:5-10 mixing according to mass ratio, is stirred at 90-100 DEG C；Curing agent is added after vacuumizing, is set after mixing Lipoprotein mixture；Resin compound is poured into mold, obtains epoxy resin solids after cooling.
8. the application of the nitrogen of the structure according to claim 7 containing benzoguanamine-phosphorus system efficient flame-retarding agent, feature exist In the curing agent is 4,4' diaminodiphenylmethane.
9. the application of the nitrogen of the structure according to claim 8 containing benzoguanamine-phosphorus system efficient flame-retarding agent, feature exist In the additive amount of the curing agent is 0.15-0.2 times of epoxy resin.
CN201910828940.2A 2019-09-03 2019-09-03 Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure Active CN110511431B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910828940.2A CN110511431B (en) 2019-09-03 2019-09-03 Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910828940.2A CN110511431B (en) 2019-09-03 2019-09-03 Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure

Publications (2)

Publication Number Publication Date
CN110511431A true CN110511431A (en) 2019-11-29
CN110511431B CN110511431B (en) 2021-08-27

Family

ID=68630608

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910828940.2A Active CN110511431B (en) 2019-09-03 2019-09-03 Application of nitrogen-phosphorus efficient flame retardant containing benzoguanamine structure

Country Status (1)

Country Link
CN (1) CN110511431B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111040293A (en) * 2019-12-17 2020-04-21 广东省石油与精细化工研究院 Intumescent flame-retardant polypropylene and preparation method thereof
CN112961314A (en) * 2021-03-15 2021-06-15 四川大学 Preparation method of flame-retardant water-based polyurethane for impregnation of microfiber base cloth
CN113461734A (en) * 2021-04-19 2021-10-01 衡阳师范学院 Novel Schiff base DOPO phosphorus nitrogen-containing flame retardant and synthesis method and application thereof
CN116082535A (en) * 2023-02-13 2023-05-09 皖西学院 Flame retardant containing polyglucosamine-2-amino structure, synthesis method and application
WO2023096576A3 (en) * 2021-11-23 2023-08-31 Agency For Science, Technology And Research Polymeric flame retardant synergist and the method of producing it and its formulation for polyamides
CN120192650A (en) * 2025-05-27 2025-06-24 岳阳经源塑胶制品有限公司 A high-strength flame-retardant polycarbonate plastic and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059339A (en) * 2012-12-21 2013-04-24 清华大学深圳研究生院 9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide (DOPO) group phosphorus-nitrogen flame retardant and preparation method and application thereof
CN107501526A (en) * 2017-08-04 2017-12-22 武汉工程大学 A kind of new DOPO types epoxy curing agent and preparation method thereof
CN107739453A (en) * 2017-11-14 2018-02-27 贵州省材料产业技术研究院 DOPO derivative flame retardants and its preparation method and application
CN108484879A (en) * 2018-04-24 2018-09-04 深圳华力兴新材料股份有限公司 A kind of phosphor-containing flame-proof type epoxy prepolymer and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059339A (en) * 2012-12-21 2013-04-24 清华大学深圳研究生院 9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide (DOPO) group phosphorus-nitrogen flame retardant and preparation method and application thereof
CN107501526A (en) * 2017-08-04 2017-12-22 武汉工程大学 A kind of new DOPO types epoxy curing agent and preparation method thereof
CN107739453A (en) * 2017-11-14 2018-02-27 贵州省材料产业技术研究院 DOPO derivative flame retardants and its preparation method and application
CN108484879A (en) * 2018-04-24 2018-09-04 深圳华力兴新材料股份有限公司 A kind of phosphor-containing flame-proof type epoxy prepolymer and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111040293A (en) * 2019-12-17 2020-04-21 广东省石油与精细化工研究院 Intumescent flame-retardant polypropylene and preparation method thereof
CN111040293B (en) * 2019-12-17 2022-03-08 广东省石油与精细化工研究院 Intumescent flame-retardant polypropylene and preparation method thereof
CN112961314A (en) * 2021-03-15 2021-06-15 四川大学 Preparation method of flame-retardant water-based polyurethane for impregnation of microfiber base cloth
CN113461734A (en) * 2021-04-19 2021-10-01 衡阳师范学院 Novel Schiff base DOPO phosphorus nitrogen-containing flame retardant and synthesis method and application thereof
WO2023096576A3 (en) * 2021-11-23 2023-08-31 Agency For Science, Technology And Research Polymeric flame retardant synergist and the method of producing it and its formulation for polyamides
CN116082535A (en) * 2023-02-13 2023-05-09 皖西学院 Flame retardant containing polyglucosamine-2-amino structure, synthesis method and application
CN120192650A (en) * 2025-05-27 2025-06-24 岳阳经源塑胶制品有限公司 A high-strength flame-retardant polycarbonate plastic and preparation method thereof

Also Published As

Publication number Publication date
CN110511431B (en) 2021-08-27

Similar Documents

Publication Publication Date Title
CN110511431A (en) A kind of nitrogen of the structure containing benzoguanamine-phosphorus system efficient flame-retarding agent and its synthesis and application
CN110041370B (en) A kind of preparation method and application of high-efficiency flame retardant containing DOPO and aminopyrazine structure
TWI585099B (en) A cyclic triphosphazene halogen-free flame retardant with an imide structure, preparation method and use thereof
CN111303483A (en) Nitrogen-phosphorus efficient flame retardant containing p-hydroxybenzaldehyde and tryptamine structures, preparation method and application
CN102391545B (en) Nitrogen and phosphorus containing flame retardant agent and preparation method thereof as well as application thereof
CN106009040B (en) It is a kind of for phosphorus-nitrogen containing sulphur fire retardant of epoxy resin and preparation method thereof
CN104774343B (en) A kind of phenyl phosphate fire retardant containing DOPO, preparation method and applications
CN107501329B (en) A kind of phosphorus nitrogen silicon ternary synergistic flame retardant and its preparation method and purposes
CN102838778A (en) Preparation method of nitrogen and phosphorus fire retardant, nitrogen and phosphorus fire retardant and application thereof
CN102924749B (en) A kind of ionic liquid type phosphate flame retardant and preparation method thereof
CN104403128A (en) Phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, preparation method of phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant, and flame-retardant epoxy resin prepared from phosphorus-containing nitrile/DOPO double-base structure phosphorus-containing fire retardant
CN110734462A (en) Synthesis and application of a nitrogen-phosphorus high-efficiency flame retardant containing benzimidazole structure
CN110643066B (en) Phosphorus-nitrogen flame retardant and preparation method thereof
CN114426701A (en) Preparation of P-N compound and graphene oxide synergistic flame retardant and application of P-N compound and graphene oxide synergistic flame retardant in epoxy resin
CN110387042A (en) DOPO structure-containing polymeric flame retardant for epoxy resin and preparation method thereof
CN109096471B (en) A kind of P-N-Si synergistic flame retardant epoxy resin curing agent and preparation method thereof
CN113234228A (en) Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof
CN118852264B (en) A DOPO-based cyclotriphosphazene halogen-free flame retardant and its preparation method and application
CN105153228B (en) A kind of organic phosphor nitrogen combustion inhibitor and the preparation method and application thereof
CN115651025A (en) DOPO derivative containing phosphorus amide, preparation method and application thereof
CN115894564A (en) Phosphorus nitrogen synergistic flame retardant DOPO-based tetrazole compound, preparation and application method
CN102634017B (en) Organosilicone-containing nitrogen phosphorus flame retardant and preparation method thereof
CN107652324B (en) Three-source-in-one expansion type fire retardant and its synthetic method and application
CN109503884B (en) A kind of tryptamine flame retardant and its synthesis and application
CN111233923B (en) Quaternary phosphonium salt flame retardant and synthetic method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20260118

Address after: 528000 Guangdong Province Foshan City Nanhai District Dalin Town Taiping Jiutan East Comprehensive Building B Building 4th Floor Room 413

Patentee after: Guangdong Jinshangyuan New Materials Technology Co.,Ltd.

Country or region after: China

Address before: 430000 No.206 Guanggu 1st Road, Donghu New Technology Development Zone, Wuhan, Hubei Province

Patentee before: WUHAN INSTITUTE OF TECHNOLOGY

Country or region before: China