WO2023109737A1 - 一种膨胀阻燃功能化poss阻燃剂及其制备方法 - Google Patents

一种膨胀阻燃功能化poss阻燃剂及其制备方法 Download PDF

Info

Publication number
WO2023109737A1
WO2023109737A1 PCT/CN2022/138321 CN2022138321W WO2023109737A1 WO 2023109737 A1 WO2023109737 A1 WO 2023109737A1 CN 2022138321 W CN2022138321 W CN 2022138321W WO 2023109737 A1 WO2023109737 A1 WO 2023109737A1
Authority
WO
WIPO (PCT)
Prior art keywords
poss
flame retardant
pamam
flame
retardant
Prior art date
Application number
PCT/CN2022/138321
Other languages
English (en)
French (fr)
Inventor
黄国波
肖圣威
冯新建
陈文杰
Original Assignee
兴宇汽车零部件股份有限公司
台州学院
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 兴宇汽车零部件股份有限公司, 台州学院 filed Critical 兴宇汽车零部件股份有限公司
Publication of WO2023109737A1 publication Critical patent/WO2023109737A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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

Definitions

  • the invention relates to a flame retardant, in particular to an intumescent flame retardant functionalized POSS flame retardant and its preparation.
  • flame retardants include halogen flame retardants and phosphorus flame retardants.
  • halogenated flame retardants are one of the main flame retardants used in plastics. They have the advantages of high flame retardant efficiency, good weather resistance and high thermal stability. At the same time, they have little impact on the mechanical properties of materials.
  • halogenated flame retardants release corrosive gases and dense smoke during combustion, which increases the harm to the environment and human health. In addition, the release of dense smoke and irritating gases also poses a danger to the escape of people in the fire. come difficult.
  • Phosphorus-based flame retardants mainly promote the dehydration and carbonization of polymer materials through high-boiling oxygen-containing acids, and have the advantages of low toxicity, weak corrosion, high thermal stability and low price.
  • silicon-based flame retardants with green environmental protection properties have been rapidly developed.
  • the Si-O-Si structure in silicon-based flame retardants interacts with polymer materials.
  • Form a dense barrier carbon layer which has the functions of anti-dripping and smoke suppression.
  • Cage polyhedral oligomeric silsesquioxane (POSS) is a cage nanoframe composed of silicon-oxygen bonds, and its eight corners are active sites that can be further modified.
  • the unique cage structure has good Excellent solubility, structural stability and heat resistance have great application prospects in the field of designing new flame retardants.
  • the contribution of POSS to the flame retardancy of polymers has the following three points: (1) the cage structure of POSS will reduce the movement rate of polymer molecular chains and improve the thermal stability of polymers; (2) when the polymer compounded with POSS When the material is burned, the decomposition of the groups on the eight corners of POSS will consume part of the heat, thereby effectively slowing down the degradation rate of the polymer; (3) POSS itself will produce a layer of insulating silicon carbon layer to cover the surface of the polymer after burning, further Slows down the conduction of heat.
  • the primary technical problem to be solved by the present invention is to provide an intumescent flame retardant functionalized POSS flame retardant.
  • the intumescent flame-retardant functionalized POSS flame retardant of the present invention has a structural schematic diagram as shown in Figure 1.
  • the cage-like Si-O-Si structure part is POSS
  • the middle dendritic macromolecule is polyamide- Amine (PAMAM)
  • the capping part is phosphorus oxychloride.
  • the intumescent flame-retardant functionalized POSS flame retardant is prepared by reacting the functionalized POSS with the -NH 2 at the end of PAMAM, and then reacting the remaining -NH 2 of PAMAM with phosphorus oxychloride.
  • the intumescent flame-retardant functionalized POSS flame retardant wherein the ratio of the amounts of PAMAM, POSS, and phosphorus oxychloride is 1:1-3:3-13.
  • the algebra of the dendritic macromolecule PAMAM is the first generation, the second generation or the third generation.
  • the phosphorus oxychloride is 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane (DCCP).
  • the second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned flame retardant.
  • the preparation method of described intumescent flame retardant functionalized POSS flame retardant comprises the steps:
  • PAMAM-POSS reacts with 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane (DCCP) to obtain intumescent flame retardant Functionalized POSS flame retardant (PAMAM-POSS-DPPC).
  • DCCP 2-oxo-2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane
  • step (1) to step (2) will be described in detail below respectively.
  • the reaction described in the step (1) of the present invention can specifically be carried out as follows: dissolve PAMAM in a solvent, add a certain amount of acid-binding agent, then dropwise add a POSS suspension containing a benzyl chloride, at a temperature of 35 to 90°C Stir the reaction for 8 to 36 hours, and separate and obtain PAMAM-POSS.
  • step (1) the ratio of the amount of PAMAM to the feed material of POSS containing one benzyl chloride is 1:1-3.
  • the acid-binding agent is selected from one of the following: triethylamine and pyridine, and the ratio of the amount of the acid-binding agent to the feed material of POSS containing one benzyl chloride is 1.0 to 1.5: 1.0.
  • the solvent is selected from one of the following: alcohols, furan compounds, and amide compounds; preferably one of the following: methanol, ethanol, tetrahydrofuran, and N,N'-dimethylformamide.
  • Step (1) After the reaction is completed, conventional separation methods such as distillation can be used to separate and obtain PAMAM-POSS.
  • step (2) of the present invention can specifically be carried out as follows: in a solvent, the PAMAM-POSS and DPPC prepared in step (1) are reacted at 25-60°C for 6-24 hours in the presence of an acid-binding agent, PAMAM-POSS-DPPC was isolated.
  • step (2) the ratio of the amount of the feed material of PAMAM-POSS to DPPC is 1:3-13.
  • the acid-binding agent is selected from one of the following: sodium bicarbonate and sodium carbonate, and the ratio of the acid-binding agent to the feed material of DPPC is 1.0-1.2:1.0.
  • the solvent is selected from one of the following: halogenated hydrocarbons, ketones; preferably one of the following: chloroform, acetone.
  • Step (2) After the reaction is completed, PAMAM-POSS-DPPC can be separated by conventional separation methods such as distillation.
  • the intumescent flame-retardant functionalized POSS flame retardant prepared by the invention not only has flame retardancy, but also can reinforce the polymer matrix.
  • the dispersibility of the flame retardant in the polymer material is solved, and the flame retardant effect of the flame retardant on the polymer is improved;
  • the intumescent flame retardant functionalized POSS flame retardant described in the present invention anchors phosphorus and nitrogen elements in the POSS surface, which greatly reduces its toxicity in use and harm to the environment;
  • the intumescent flame-retardant functionalized POSS flame retardant of the present invention uses POSS as a nano-reinforced filler, which has a reinforcing effect on the polymer matrix and improves Improve the mechanical properties of flame retardant materials;
  • the flame retardant of the present invention utilizes the synergistic flame retardant effect of phosphorus-nitrogen compounds and POSS to improve the flame retardant effect on polymer materials, reduce the usage of flame retardants in polymer materials, Reduce the cost of flame retardant materials.
  • the flame retardant of the invention has low addition amount, good flame retardant effect and wide application range.
  • Fig. 1 is a schematic diagram of a structural example of PAMAM-POSS-DPPC
  • Figure 2 is a schematic diagram of the PAMAM-POSS-DPPC reaction based on second-generation PAMAM
  • Fig. 3 is the infrared spectrogram of PAMAM-POSS and PAMAM-POSS-DPPC;
  • Fig. 4 is the XPS energy spectrogram of PAMAM, PAMAM-POSS and PAMAM-POSS-DPPC;
  • Fig. 5 is the SEM image and element distribution of PAMAM-POSS-DPPC.
  • the synthetic operation of PAMAM-POSS is the same as in Example 1.
  • the ratio of the amount of PAMAM to the feed material of POSS containing one benzyl chloride is 1:1, the algebra of PAMAM is one generation, the ratio of the amount of acid-binding agent pyridine to the feed material of POSS containing one benzyl chloride is 1.5:1.0, and the solvent It is tetrahydrofuran, the reaction temperature is 90°C, the reaction time is 8 hours, and the product yield is 86.2%.
  • the synthetic operation of PAMAM-POSS is the same as in Example 1.
  • the ratio of the amount of PAMAM to the feed material of POSS containing one benzyl chloride is 1:2.5
  • the algebra of PAMAM is the second generation
  • the ratio of the amount of acid-binding agent triethylamine to the feed material of POSS containing one benzyl chloride is 1.2: 1.0
  • the solvent is ethanol
  • the reaction temperature is 35° C.
  • the reaction time is 36 hours
  • the product yield is 96.7%.
  • the synthetic operation of PAMAM-POSS is the same as in Example 1.
  • the ratio of the amount of PAMAM to the feed material of POSS containing one benzyl chloride is 1:3, the algebra of PAMAM is three generations, the ratio of the amount of acid-binding agent pyridine to the feed material of POSS containing one benzyl chloride is 1.4:1.0, and the solvent It is N,N'-dimethylformamide, the reaction temperature is 45°C, the reaction time is 18 hours, and the product yield is 89.3%.
  • PAMAM-POSS The synthetic operation of PAMAM-POSS is the same as in Example 1. 4.6g of the above-prepared PAMAM-POSS were dissolved in 50ml of chloroform, and 1.2g of sodium bicarbonate was added, then the mixture of 1.55g of DPPC dissolved in 25ml of chloroform was slowly added dropwise to PAMAM-POSS with a constant pressure dropping funnel. In the POSS solution, stirred and reacted at 35° C. for 24 h, the obtained product was purified by vacuum distillation to obtain a yellow solid PAMAM-POSS-DPPC with a yield of 93.5%.
  • the synthesis operation of PAMAM-POSS is the same as in Example 2, and the synthesis operation of PAMAM-POSS-DPPC is the same as in Example 5.
  • the ratio of the amount of feed material of PAMAM-POSS to DPPC is 1:3, the ratio of the amount of feed material of acid-binding agent sodium bicarbonate to DPPC is 1.2:1.0, the solvent is dichloromethane, and the reaction temperature is 25°C. The time is 24 hours, and the product yield is 92.4%.
  • the synthesis operation of PAMAM-POSS is the same as in Example 4, and the synthesis operation of PAMAM-POSS-DPPC is the same as in Example 5.
  • the ratio of the amount of feed material of PAMAM-POSS to DPPC is 1:13
  • the ratio of the amount of feed material of acid-binding agent sodium carbonate to DPPC is 1.2:1.0
  • the solvent is acetone
  • the reaction temperature is 60°C
  • the reaction time is 6 hours
  • the product yield was 77.4%.
  • Embodiment 8 Application of intumescent flame retardant functionalized POSS flame retardant
  • thermoplastic dynamic vulcanizate (TPV) (the manufacturer is Kumho Chemical, the model is Innoprene TPV) and 50g PAMAM-POSS-DPPC into the disperser and stir for 20 minutes. After taking it out, the above mixture is passed through the screw extruder (processing temperature range TPV/PAMAM-POSS-DPPC composite material was obtained by extrusion and granulation at 170-190° C., and the results of measuring the mechanical properties and flame retardant properties of the composite material are shown below.
  • thermoplastic dynamic vulcanizate pure thermoplastic dynamic vulcanizate
  • TPV/POSS composite material POSS accounts for 5% of the mass fraction of thermoplastic dynamic vulcanizate
  • TPV/PAMAM-POSS-DPPC composite material PAMAM-POSS-DPPC
  • the preparation method is as example 5, The mass fraction of PAMAM-POSS-DPPC in thermoplastic dynamically vulcanized rubber is 5%.
  • thermoplastic dynamic vulcanizate TPV/POSS
  • 5% POSS 5% intumescent flame retardant functionalized POSS flame retardant
  • the tensile strength of the thermoplastic dynamically vulcanized rubber (TPV/PAMAM-POSS-DPPC) composite was increased by 60%, indicating that the intumescent flame-retardant functionalized POSS has a significant reinforcing effect on thermoplastic dynamically vulcanized rubber, and the strengthening effect is better than that of unfunctionalized POSS .
  • thermoplastic dynamic vulcanizate compared with pure thermoplastic dynamic vulcanizate, the peak heat release rate of thermoplastic dynamic vulcanizate (TPV/POSS) composites with 5% POSS was reduced by 26%, and the ignition time was extended by only 5 seconds, The peak heat release rate of thermoplastic dynamically vulcanized rubber (TPV/PAMAM-POSS-DPPC) composites added with 5% intumescent flame retardant functionalized POSS flame retardant was reduced by 38.6%, and the ignition time was prolonged by 12 seconds, which greatly reduced the fire risk. The total heat release and the average mass loss rate of TPV/PAMAM-POSS-DPPC composites are lower than those of TPV/POSS composites.
  • the intumescent flame retardant functionalized POSS has a significant flame retardant effect on thermoplastic dynamic vulcanizate, and the flame retardant effect is better than that of unfunctionalized POSS.
  • the intumescent flame retardant functionalized POSS flame retardant not only has a flame retardant effect on the matrix resin, but also can significantly improve the strength of the material, and its modification effect is better than that of the unfunctionalized POSS, which is a good solution
  • the current small molecule flame retardants improve the flame retardancy of polymer materials, they worsen the technical problems of the mechanical properties of the materials.

Landscapes

  • 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)
  • Fireproofing Substances (AREA)

Abstract

一种膨胀阻燃功能化POSS阻燃剂及其制备方法，该阻燃剂是通过官能化POSS与PAMAM部分末端-NH 2反应，再通过磷酰氯对PAMAM剩余的-NH 2封端反应制得。制得的膨胀阻燃功能化POSS阻燃剂不仅具有阻燃性，而且能对聚合物基体起到补强作用。通过将阻燃元素磷、氮负载在POSS表面，从而可以在阻燃材料的制备过程中将有阻燃元素磷、氮、硅均匀分散于聚合物基体中，解决了阻燃剂在高分子材料中的分散性问题，而且将磷、氮元素锚固在POSS的表面，大大降低了其在使用中的毒性以及对环境的危害；可提高阻燃材料的力学性能和阻燃性能；所述的阻燃剂添加量低、阻燃效果好、适用范围广。

Description

一种膨胀阻燃功能化POSS阻燃剂及其制备方法 技术领域
本发明涉及一种阻燃剂，具体涉及一种膨胀阻燃功能化POSS阻燃剂及其制备。
背景技术
依据阻燃元素划分，阻燃剂包括卤系阻燃剂和磷系阻燃剂。卤系阻燃剂是塑料中主要应用的阻燃剂之一，具有阻燃效率高、耐候性好和热稳定性高等优点，同时，对材料机械性能的影响较小。但是，卤系阻燃剂在燃烧过程中会释放出腐蚀性气体和浓烟，增加了对环境和人类健康的危害，此外，释放出浓烟和刺激性气体还给处于火灾中的人员逃生带来困难。磷系阻燃剂主要是通过高沸点含氧酸来促进高分子材料脱水和炭化，具有毒性低、腐蚀性弱、热稳定性高和价格低廉等优点。近年来，随着全球环境问题的不断凸显，具有绿色环保性能的硅系阻燃得到了快速发展，硅系阻燃剂中的Si-O-Si结构与高分子材料相互作用，在燃烧过程中形成致密的阻隔炭层，具有防滴落、可抑烟的功能。笼型聚倍半硅氧烷(polyhedral oligomeric silsesquioxane，POSS)是一种由硅氧键构成的笼型纳米框架，其八个角是可以进一步予以修饰的活性位点，独特的笼型结构具有良好的溶解性、结构稳定性和耐热性，在设计新型阻燃剂领域具有巨大的应用前景。POSS对聚合物阻燃的贡献有以下三点：(1)POSS的笼状结构会降低聚合物分子链的运动速率，提高聚合物的热稳定性；(2)当混有POSS的高分子复合材料燃烧时，POSS八个角上的基团分解会消耗一部分热量，从而有效减缓聚合物的降解速率；(3)POSS本身经过燃烧后会产生一层绝热硅碳层覆盖在聚合物表面，进一步减缓了热量的传导。然而，当前POSS阻燃剂的理想阻燃效果往往需要较大的添加量，这大大增加的该类阻燃剂的使用成本。因此，如何找到能与之协同阻燃，同时降低成本的材料是开发新型POSS阻燃剂的研究重点之一。
发明内容
本发明要解决的首要技术问题在于提供一种膨胀阻燃功能化POSS阻燃剂。
本发明所述的膨胀阻燃功能化POSS阻燃剂，其一种结构示意图如图1所示，图中，笼状Si-O-Si结构部分为POSS，中间树枝状大分子为聚酰胺-胺(PAMAM)，封端部分为磷酰氯。
所述的膨胀阻燃功能化POSS阻燃剂，是通过官能化POSS与PAMAM末端-NH 2部分反应，再通过磷酰氯对PAMAM剩余的-NH 2封端反应制得。
所述的膨胀阻燃功能化POSS阻燃剂，其中PAMAM、POSS、磷酰氯的物质的量之比为1：1～3：3～13。
其中树枝状大分子PAMAM的代数为一代、二代或三代。
所述的磷酰氯为2-氧代-2-氯-5，5-二甲基-1，3，2-二氧磷杂环己烷(DCCP)。
本发明要解决的第二个技术问题在于提供一种上述阻燃剂的制备方法。
所述的膨胀阻燃功能化POSS阻燃剂的制备方法，包括如下步骤：
(1)含有一个苄氯的POSS与PAMAM末端-NH 2进行亲核加成-消除取代反应，得到PAMAM-POSS。
(2)PAMAM-POSS与2-氧代-2-氯-5，5-二甲基-1，3，2-二氧磷杂环己烷(DCCP)进行封端反应，制得膨胀阻燃功能化POSS阻燃剂(PAMAM-POSS-DPPC)。
下面分别对上述步骤(1)～步骤(2)进行详细说明。
本发明步骤(1)所述的反应具体可按照如下进行：将PAMAM溶于溶剂中，加入一定量的缚酸剂，再滴加含有一个苄氯的POSS悬浮液，在35～90℃温度下搅拌反应8～36小时，分离制得PAMAM-POSS。
步骤(1)中，所述的PAMAM与含有一个苄氯的POSS的投料物质的量之比为1：1～3。
步骤(1)中，所述的缚酸剂选自下述之一：三乙胺、吡啶，所述的缚酸剂与含有一个苄氯的POSS的投料物质的量之比为1.0～1.5：1.0。
步骤(1)中，所述的溶剂选自下述之一：醇类、呋喃类化合物、酰胺类化合物；优选下列之一：甲醇、乙醇、四氢呋喃、N,N'-二甲基甲酰胺。
步骤(1)在反应结束后，可采用蒸馏等常规分离方法分离得到PAMAM-POSS。
本发明步骤(2)所述的反应具体可按照如下进行：在溶剂中，步骤(1)制得的PAMAM-POSS与DPPC在缚酸剂存在下，于25～60℃反应6～24小时，分离得PAMAM-POSS-DPPC。
步骤(2)中，所述的PAMAM-POSS与DPPC的投料物质的量之比为1：3～13。
步骤(2)中，所述的缚酸剂选自下述之一：碳酸氢钠、碳酸钠，所述的缚酸剂与DPPC的投料物质的量之比为1.0～1.2：1.0。
步骤(2)中，所述的溶剂选自下述之一：卤代烃、酮类化合物；优选下列之一：三氯甲烷、丙酮。
步骤(2)在反应结束后，可采用蒸馏等常规分离方法分离得到PAMAM-POSS-DPPC。
与现有技术相比，本发明的有益效果体现在如下几方面：
本发明制得的膨胀阻燃功能化POSS阻燃剂不仅具有阻燃性，而且能对聚合物基体起到 补强作用。利用接枝反应等对POSS进行化学改性，将阻燃元素磷、氮负载在POSS表面，并通过阻燃材料的制备将有阻燃元素磷、氮、硅均匀分散于聚合物基体中，解决了阻燃剂在高分子材料中的分散性问题，提高了阻燃剂对聚合物的阻燃效果；本发明所述的膨胀阻燃功能化POSS阻燃剂，将磷、氮元素锚固在POSS的表面，大大降低了其在使用中的毒性以及对环境的危害；本发明所述的膨胀阻燃功能化POSS阻燃剂，是以POSS为纳米增强填料，对聚合物基体具有增强作用，提高了阻燃材料的力学性能；本发明所述的阻燃剂利用磷氮系化合物与POSS协同阻燃作用，提高对高分子材料的阻燃效果，减少阻燃剂在高分子材料的使用量，降低阻燃材料的成本。本发明所述的阻燃剂添加量低、阻燃效果好、适用范围广。
附图说明
图1是PAMAM-POSS-DPPC的一种结构实例示意图；
图2是基于二代PAMAM的PAMAM-POSS-DPPC反应原理图；
图3是PAMAM-POSS以及PAMAM-POSS-DPPC的红外光谱图；
图4是PAMAM、PAMAM-POSS以及PAMAM-POSS-DPPC的XPS能谱图；
图5是PAMAM-POSS-DPPC的SEM图及元素分布。
具体实施方式
以下以具体实施例来说明本发明的技术方案，但本发明的保护范围不限于此：
实施例1
将二代PAMAM加热至50℃，用20ml甲醇充分溶解3.56g二代PAMAM并加入至三口烧瓶中，向三口烧瓶中加入2ml三乙胺；随后用25ml甲醇溶解4.4g含有一个苄氯的POSS，用恒压滴液漏斗缓慢滴加至三口烧瓶中，并在50℃下继续搅拌反应24h，经减压蒸馏处理后得到淡黄色固体PAMAM-POSS，收率为94.8％。
实施例2
PAMAM-POSS的合成操作同实施例1。PAMAM与含有一个苄氯的POSS的投料物质的量之比为1：1，PAMAM的代数为一代，缚酸剂吡啶与含有一个苄氯的POSS的投料物质的量之比为1.5：1.0，溶剂为四氢呋喃，反应温度为90℃，反应时间8小时，产物收率为86.2％。
实施例3
PAMAM-POSS的合成操作同实施例1。PAMAM与含有一个苄氯的POSS的投料物质的量之比为1：2.5，PAMAM的代数为二代，缚酸剂三乙胺与含有一个苄氯的POSS的投料物质的量之比为1.2：1.0，溶剂为乙醇，反应温度为35℃，反应时间36小时，产物收率为96.7％。
实施例4
PAMAM-POSS的合成操作同实施例1。PAMAM与含有一个苄氯的POSS的投料物质的量之比为1：3，PAMAM的代数为三代，缚酸剂吡啶与含有一个苄氯的POSS的投料物质的量之比为1.4：1.0，溶剂为N,N'-二甲基甲酰胺，反应温度为45℃，反应时间18小时，产物收率为89.3％。
实施例5
PAMAM-POSS的合成操作同实施例1。将4.6g上述制备的PAMAM-POSS溶解于50ml三氯甲烷中，加入1.2g碳酸氢钠，然后用恒压滴液漏斗将25ml三氯甲烷中溶有1.55g DPPC的混合液缓慢滴加入PAMAM-POSS溶液中，35℃下搅拌反应24h，所得产物经减压蒸馏提纯得到黄色固体PAMAM-POSS-DPPC，收率为93.5％。
实施例6
PAMAM-POSS的合成操作同实施例2，PAMAM-POSS-DPPC合成操作同实施例5。PAMAM-POSS与DPPC的投料物质的量之比为1：3，缚酸剂碳酸氢钠与DPPC的投料物质的量之比为1.2：1.0，溶剂为二氯甲烷，反应温度为25℃，反应时间24小时，产物收率为92.4％。
实施例7
PAMAM-POSS的合成操作同实施例4，PAMAM-POSS-DPPC合成操作同实施例5。PAMAM-POSS与DPPC的投料物质的量之比为1：13，缚酸剂碳酸钠与DPPC的投料物质的量之比为1.2：1.0，溶剂为丙酮，反应温度为60℃，反应时间6小时，产物收率为77.4％。
实施例8：膨胀阻燃功能化POSS阻燃剂的应用
膨胀阻燃功能化POSS阻燃剂PAMAM-POSS-DPPC的制备操作同实施例5。将950g热塑性动态硫化橡胶(TPV)(厂家为锦湖化学，型号为Innoprene TPV)和50g PAMAM-POSS-DPPC放入分散机搅拌20分钟，取出后将上述混合物，经过螺杆挤出机(加工温度范围为170～190℃)挤出造粒，得到TPV/PAMAM-POSS-DPPC复合材料，测量该复合材料力学性能、阻燃性能的结果如下所示。
表1
Figure PCTCN2022138321-appb-000001
Figure PCTCN2022138321-appb-000002
注——TPV：纯的热塑性动态硫化橡胶；TPV/POSS复合材料：POSS占热塑性动态硫化橡胶的质量分数为5％；TPV/PAMAM-POSS-DPPC复合材料：PAMAM-POSS-DPPC制备方法如实例5，PAMAM-POSS-DPPC占热塑性动态硫化橡胶的质量分数为5％。
通过表1可知，与纯的热塑性动态硫化橡胶相比，添加5％POSS的热塑性动态硫化橡胶(TPV/POSS)复合材料的拉伸强度提高了35％，添加5％膨胀阻燃功能化POSS阻燃剂的热塑性动态硫化橡胶(TPV/PAMAM-POSS-DPPC)复合材料的拉伸强度提高了60％，表明膨胀阻燃功能化POSS对热塑性动态硫化橡胶有显著的增强作用，且增强效果优于未功能化POSS。此外，在阻燃性能提高方面，与纯热塑性动态硫化橡胶相比，添加5％POSS的热塑性动态硫化橡胶(TPV/POSS)复合材料的热释放速率峰值降低了26％，点燃时间延长了仅5秒，添加5％膨胀阻燃功能化POSS阻燃剂的热塑性动态硫化橡胶(TPV/PAMAM-POSS-DPPC)复合材料热释放速率峰值降低了38.6％，点燃时间延长了12秒，这样就大大降低了材料的火灾风险。TPV/PAMAM-POSS-DPPC复合材料的热释放总量、质量损失平均速率的值均低于TPV/POSS复合材料。这些表明膨胀阻燃功能化POSS对热塑性动态硫化橡胶有显著的阻燃作用，且阻燃效果优于未功能化POSS。总而言之，膨胀阻燃功能化POSS阻燃剂作为一种阻燃剂，不仅对基体树脂具有阻燃作用，而且能显著提高材料的强度，其改性效果优于未功能化POSS，很好解决了当前小分子阻燃剂在提高高分子材料阻燃性时，恶化了材料力学性能的技术难题。
以上所述的实施例只是本发明的一种较佳的方案，并非对本发明作任何形式上的限制，在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。

Claims (10)

  1. 一种膨胀阻燃功能化POSS阻燃剂，其特征在于，是通过官能化POSS与PAMAM部分末端-NH 2反应，再通过磷酰氯对PAMAM剩余的-NH 2封端反应制得。
  2. 如权利要求1所述的膨胀阻燃功能化POSS阻燃剂，其特征在于，所述PAMAM的代数为一代、二代或三代；所述的磷酰氯为2-氧代-2-氯-5，5-二甲基-1，3，2-二氧磷杂环己烷(DCCP)。
  3. 如权利要求1所述的膨胀阻燃功能化POSS阻燃剂，其特征在于，所述的PAMAM、POSS、磷酰氯的物质的量之比为1：1～3：3～13。
  4. 制备如权利要求1所述的膨胀阻燃功能化POSS阻燃剂的方法，其特征在于，包括如下步骤：
    (1)将含有一个苄氯的POSS与PAMAM的部分末端-NH 2进行亲核加成-消除取代反应，得到PAMAM-POSS；
    (2)将PAMAM-POSS与2-氧代-2-氯-5，5-二甲基-1，3，2-二氧磷杂环己烷(DCCP)进行封端反应，制得膨胀阻燃功能化POSS阻燃剂(PAMAM-POSS-DPPC)。
  5. 如权利要求4所述的膨胀阻燃功能化POSS阻燃剂的制备方法，其特征在于，所述步骤(1)具体为：将PAMAM溶于溶剂中，加入一定量的缚酸剂，再滴加含有一个苄氯的POSS悬浮液，在35～90℃温度下搅拌反应8～36小时，分离制得PAMAM-POSS；所述的PAMAM与含有一个苄氯的POSS的投料物质的量之比为1：1～3，所述的缚酸剂与含有一个苄氯的POSS的投料物质的量之比为1.0～1.5：1.0。
  6. 根据权利要求5所述的膨胀阻燃功能化POSS阻燃剂的制备方法，其特征在于，所述的缚酸剂选自三乙胺、吡啶。
  7. 根据权利要求5所述的膨胀阻燃功能化POSS阻燃剂的制备方法，其特征在于，步骤(1)中，所述的溶剂选自下述之一：醇类、呋喃类化合物、酰胺类化合物；优选下列之一：甲醇、乙醇、四氢呋喃、N,N'-二甲基甲酰胺。
  8. 如权利要求4所述的膨胀阻燃功能化POSS阻燃剂的制备方法，其特征在于，所述步骤(2)具体为：在溶剂中，将步骤(1)制得的PAMAM-POSS与DPPC在缚酸剂存在下，于25～60℃反应6～24小时，分离得PAMAM-POSS-DPPC；所述的PAMAM-POSS与DPPC的投料物质的量之比为1：3～13，该步骤中所述缚酸剂与DPPC的投料物质的量之比为1.0～1.2：1.0。
  9. 如权利要求8所述的膨胀阻燃功能化POSS阻燃剂的制备方法，其特征在于，步骤(2)中，所述的缚酸剂选自碳酸氢钠、碳酸钠。
  10. 如权利要求8所述的膨胀阻燃功能化POSS阻燃剂的制备方法，其特征在于，步骤(2) 中，所述的溶剂选自下述之一：卤代烃、酮类化合物；优选下列之一：三氯甲烷、丙酮。
PCT/CN2022/138321 2021-12-15 2022-12-12 一种膨胀阻燃功能化poss阻燃剂及其制备方法 WO2023109737A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111533776.6A CN114044907B (zh) 2021-12-15 2021-12-15 一种膨胀阻燃功能化poss阻燃剂及其制备方法
CN202111533776.6 2021-12-15

Publications (1)

Publication Number Publication Date
WO2023109737A1 true WO2023109737A1 (zh) 2023-06-22

Family

ID=80212877

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/138321 WO2023109737A1 (zh) 2021-12-15 2022-12-12 一种膨胀阻燃功能化poss阻燃剂及其制备方法

Country Status (2)

Country Link
CN (1) CN114044907B (zh)
WO (1) WO2023109737A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114044907B (zh) * 2021-12-15 2022-11-11 兴宇汽车零部件股份有限公司 一种膨胀阻燃功能化poss阻燃剂及其制备方法
CN115521543B (zh) * 2022-09-30 2024-03-22 天津金发新材料有限公司 一种低烟气毒性、低热释放速率、高氧指数阻燃pp材料及其制备方法与应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5902863A (en) * 1997-07-21 1999-05-11 Dow Corning Corporation Dendrimer-based networks containing lyophilic organosilicon and hydrophilic polyamidoamine nanoscopic domains
CN102964632A (zh) * 2012-10-23 2013-03-13 台州学院 一种树枝状磷氮系阻燃剂的制备及应用
CN105504352A (zh) * 2016-01-25 2016-04-20 黄国波 一种磷氮系树枝状大分子功能化石墨烯阻燃剂及其应用
CN107868255A (zh) * 2017-11-17 2018-04-03 厦门大学 具有自组装增强作用的poss‑dopo‑三嗪衍生物阻燃剂的制备方法及其应用
CN112961359A (zh) * 2021-02-24 2021-06-15 北华大学 NH2-POSS-bisDOPO阻燃剂及其制备方法与应用
CN114044907A (zh) * 2021-12-15 2022-02-15 兴宇汽车零部件股份有限公司 一种膨胀阻燃功能化poss阻燃剂及其制备方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000129109A (ja) * 1998-10-21 2000-05-09 Kanegafuchi Chem Ind Co Ltd 難燃性熱可塑性樹脂組成物
WO2003064490A2 (en) * 2001-06-27 2003-08-07 Hybrid Plastics Llp Process for the functionalization of polyhedral oligomeric silsesquioxanes
WO2006115547A2 (en) * 2005-04-20 2006-11-02 Dendritic Nanotechnologies, Inc. Dendritic polymers with enhanced amplification and interior functionality
JPWO2009031593A1 (ja) * 2007-09-03 2010-12-16 国立大学法人京都大学 シルセスキオキサンを含む造影剤
CN103804693B (zh) * 2014-01-24 2016-03-09 中国科学院化学研究所 树枝状聚缩酮及其制备方法和应用
WO2016092569A1 (en) * 2014-12-10 2016-06-16 Council Of Scientific & Industrial Research A discontinuous reverse micellar composition in cubic fd3m phase for sustained release of therapeutic drugs
CN105153467B (zh) * 2015-10-11 2018-06-05 台州学院 一种膨胀型阻燃剂功能化水滑石阻燃剂及其制备方法
CN106220854B (zh) * 2016-07-26 2019-03-19 上海工程技术大学 一种超支化poss阻燃剂及其制备方法和应用
CN106750185B (zh) * 2017-03-06 2018-02-09 山东清硕环境科技有限公司 一种端氨基有机硅树枝状大分子固化剂及基于该固化剂制备的烟囱防腐专用纳米杂化聚合物
CN112321823A (zh) * 2020-11-22 2021-02-05 同济大学 低生物毒性的树枝状大分子光引发剂及其制备和应用
CN112724404B (zh) * 2021-01-18 2023-10-10 东华大学 超支化磷氮系poss-ep阻燃剂及其制备、应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5902863A (en) * 1997-07-21 1999-05-11 Dow Corning Corporation Dendrimer-based networks containing lyophilic organosilicon and hydrophilic polyamidoamine nanoscopic domains
CN102964632A (zh) * 2012-10-23 2013-03-13 台州学院 一种树枝状磷氮系阻燃剂的制备及应用
CN105504352A (zh) * 2016-01-25 2016-04-20 黄国波 一种磷氮系树枝状大分子功能化石墨烯阻燃剂及其应用
CN107868255A (zh) * 2017-11-17 2018-04-03 厦门大学 具有自组装增强作用的poss‑dopo‑三嗪衍生物阻燃剂的制备方法及其应用
CN112961359A (zh) * 2021-02-24 2021-06-15 北华大学 NH2-POSS-bisDOPO阻燃剂及其制备方法与应用
CN114044907A (zh) * 2021-12-15 2022-02-15 兴宇汽车零部件股份有限公司 一种膨胀阻燃功能化poss阻燃剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HE ZHICAI, ZHAO ZHENGPING, XIAO SHENGWEI, YANG JINTAO, ZHONG MINGQIANG: "Preparation of carbon-based hybrid particles and their application in microcellular foaming and flame-retardant materials", RSC ADVANCES, vol. 8, no. 47, 1 January 2018 (2018-01-01), pages 26563 - 26570, XP093071415, DOI: 10.1039/C8RA03007C *

Also Published As

Publication number Publication date
CN114044907B (zh) 2022-11-11
CN114044907A (zh) 2022-02-15

Similar Documents

Publication Publication Date Title
WO2023109737A1 (zh) 一种膨胀阻燃功能化poss阻燃剂及其制备方法
Rao et al. High strength, low flammability, and smoke suppression for epoxy thermoset enabled by a low-loading phosphorus-nitrogen-silicon compound
Wang et al. Recent advances in construction of hybrid nano-structures for flame retardant polymers application
CN112662184B (zh) 一种阻燃硅橡胶材料以及制备方法
Liu et al. A multi-element flame retardant on the basis of silicon-phosphorus-nitrogen for combustibility suppressing of epoxy
KR102180931B1 (ko) 아민화된 난연제로 개질된 그래핀 옥사이드 충전제 및 이를 이용한 폴리프로필렌 나노복합재료조성물
CN107652468A (zh) 含dopo的咪唑磺酸盐离子液体阻燃剂、制法和应用
CN109337161A (zh) 一种由核壳结构改善分散的石墨烯阻燃母料及制备方法
CN108912445B (zh) 一种无卤阻燃聚乙烯材料及其制备方法
CN115746481A (zh) 一种抗冲击阻燃耐火电缆及其生产工艺
US11084961B2 (en) Highly flame-retardant adhesive for high polymer materials
CN115232417A (zh) 一种低烟阻燃的塑料制品半导电pvc护套料
CN114989493A (zh) 一种具有抗氧化功能的微胶囊化阻燃剂及其制备方法
WO2021037273A1 (zh) 一种香草醛基含席夫碱的共价有机框架阻燃剂及其制备方法
Kong et al. Hybrid POSS Nanocomposites: An Overview of Material Toughening and Fire Retardancy
CN115948002A (zh) 一种阻燃橡胶材料及其制备方法和密封条
CN109021239A (zh) 一种同时具有含磷和双键基团的笼形低聚硅倍半氧烷及其制备方法和应用
JP2004155802A (ja) 難燃性樹脂組成物
CN102827421B (zh) 一种聚丙烯材料及其制备方法
CN113736265A (zh) 一种陶瓷化阻燃硅橡胶材料及其制备方法
CN114685937A (zh) 阻燃环氧树脂复合材料及其制备方法
Yuan et al. Synthesis of a silicon-containing flame retardant and its synergistic effect with potassium-4-(phenylsulfonyl) benzenesulfonate (KSS) in polycarbonate (PC)
CN113214656B (zh) 一种以八环糊精poss为炭源的膨胀型阻燃剂及其应用
CN113773416B (zh) 一种本征阻燃的改性天然橡胶及其制备方法
CN116675985B (zh) 一种含笼状低聚倍半硅氧烷阻燃硅橡胶及其制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22906482

Country of ref document: EP

Kind code of ref document: A1