WO2018035999A1 - 对苯二胺化学接枝改性的聚磷酸铵衍生物及其制备方法 - Google Patents

对苯二胺化学接枝改性的聚磷酸铵衍生物及其制备方法 Download PDF

Info

Publication number
WO2018035999A1
WO2018035999A1 PCT/CN2016/106218 CN2016106218W WO2018035999A1 WO 2018035999 A1 WO2018035999 A1 WO 2018035999A1 CN 2016106218 W CN2016106218 W CN 2016106218W WO 2018035999 A1 WO2018035999 A1 WO 2018035999A1
Authority
WO
WIPO (PCT)
Prior art keywords
ammonium polyphosphate
phenylenediamine
app
papp
derivative
Prior art date
Application number
PCT/CN2016/106218
Other languages
English (en)
French (fr)
Inventor
郑玉婴
连汉青
Original Assignee
福州大学
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 福州大学 filed Critical 福州大学
Publication of WO2018035999A1 publication Critical patent/WO2018035999A1/zh

Links

Images

Classifications

    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention belongs to the field of chemical synthesis, and particularly relates to an ammonium polyphosphate derivative modified by chemical grafting of p-phenylenediamine and a preparation method thereof.
  • ammonium polyphosphate As an efficient halogen-free flame retardant, ammonium polyphosphate (APP) has been a research hotspot at home and abroad in recent years. As a flame retardant, APP is a good way to avoid the hazards of halogens and heavy metals, and is in line with today's environmentally friendly development philosophy. APP acts as an acid source and a gas source in the flame retardant system. The combustion can decompose the high-viscosity inorganic acid and release the ammonia gas and water, which can well function as a heat insulating and oxygen barrier. In addition, it also has the advantages of being less hygroscopic, low in cost, good in dispersibility, and good in suppressing smoke. However, the disadvantages of APP in water solubility, high temperature and easy decomposition, flame retardant effect and poor compatibility with polymer matrix hinder its application in polymer flame retardant, so it is necessary to modify it.
  • the European patent states that melamine formaldehyde, water and methanol are mixed at a high temperature for microcapsule coating of APP, and the obtained product can reduce the water solubility thereof, but the compatibility with the polymer matrix and the thermal stability are not described.
  • Wuhan University of Technology, Qiang Qiang et al. used a silicone coupling agent to modify the surface of APP, which made APP have good hydrophobicity and dispersibility, but did not discuss its thermal stability. Therefore, it is necessary and urgent to prepare a material having good water resistance and thermal stability while being compatible with a polymer matrix.
  • the object of the present invention is to provide a polyphosphate ammonium derivative which is chemically graft modified with p-phenylenediamine and a preparation method thereof according to the deficiencies of the prior art.
  • the solubility of the ammonium polyphosphate derivative of the invention is reduced by 0.52 g/100 mL, the thermal decomposition weight loss at 340 ° C to 460 ° C is obviously slowed down, and the compatibility with the matrix EVA is also greatly improved ( That is, the elongation at break of the composite formed by mixing with EVA is increased by 30%), the UL-94 grade is changed from V-1 to V-0, and the oxygen index is increased from 26.1% to 28.2%.
  • the present invention adopts the following technical solutions:
  • ammonium polyphosphate derivative modified by chemical grafting of p-phenylenediamine which is obtained by chemically grafting p-phenylenediamine onto ammonium polyphosphate, and specifically comprises the following steps:
  • the invention has the beneficial effects that the invention adopts the reaction of p-phenylenediamine with ammonium polyphosphate, and utilizes the multi-carbon property of the aromatic amine to better reflect the concept of the integration of the acid source, the gas source and the carbon source.
  • the prepared ammonium polyphosphate derivative modified by p-phenylenediamine has better flame retardant effect than ammonium polyphosphate, and the UL-94 grade changes from V-1 to V-0, and the oxygen index From 26.1% to 28.2%; in addition, the obtained ammonium polyphosphate derivative has good water resistance, thermal stability and compatibility with the polymer matrix, and its solubility is reduced by 0.52g / 100mL, 340 ° C ⁇
  • the weight loss of thermal decomposition at 460 °C is obviously slowed down, and the compatibility with the matrix EVA is also greatly improved (ie, the elongation at break of the composite formed by mixing with EVA is increased by 30%), which will be beneficial to its use as a flame retardant.
  • polymers it has broad market prospects and social benefits.
  • Figure 1 is an infrared absorption spectrum of PAPP and APP
  • Figure 3 shows the TG and DTG curves of PAPP and APP
  • Figure 4 is a graph showing the elongation at break of APP/EVA and PAPP/EVA composites.
  • Table 1 shows the water solubility data of PAPP and APP. It can be seen from Table 1 that the water solubility coefficient of APP is about 1.78 g/100 mL; after chemical modification, the water solubility coefficient of PAPP is 1.26 g/100 mL, which is 0.52 g/100 mL lower than that before modification.
  • Table 2 shows the flame retardant data of PAPP and APP.
  • APP and PAPP were separately added to the EVA matrix to form foam APP/EVA and PAPP/EVA.
  • the flame retardant performance of the APP after modification was significantly improved, and the UL-94 grade changed from V-1.
  • the oxygen index increased from 26.1% to 28.2%.
  • Figure 1 is an infrared absorption spectrum of PAPP and APP. It can be seen from the figure that both APP and PAPP have broad peaks around 3400-3030 cm -1 , which is the stretching vibration absorption peak of NH 4 + on NH 4 + . Comparative APP visible spectrum, of PAPP curve appears in the vicinity of the absorption peak of 3050cm -1, a peak of stretching vibration of CH bond on the benzene ring; at 1635cm -1 and 1580cm -1 as a peak C is a benzene ring skeleton characteristic peaks; the The peak of the bending vibration characteristic near the 840 cm -1 is the bending vibration characteristic of the benzene ring instead of the CH bond. Since the characteristic peak of the benzene ring CH bond appeared in the PAPP line, it was shown that PPDA and APP were successfully attached to the surface by bonding.
  • FIG. 2 is a schematic diagram of the nuclear magnetic resonance spectrum and structure of PAPP and APP. It can be seen from the figure that both PAPP and APP have characteristic peaks at 2.5 ppm, which is a characteristic peak of the solvent dimethyl sulfoxide. At the same time, the PAPP line showed a new characteristic peak at 6.45 ppm, which is the peak of hydrogen on the benzene ring. In addition, no new peaks appeared on the PAPP line, indicating that -NH 2 was completely removed and p-phenylenediamine was successfully grafted onto APP.
  • Figure 3 (a) is the TG curve of PAPP and APP
  • Figure 3 (b) is the DTG curve of PAPP and APP.
  • APP has two thermal decomposition stages, starting at 300 ° C and 600 ° C, respectively, while PAPP has a strong thermal decomposition stage only around 480 ° C.
  • Two spikes of APP and one spike of PAPP can be observed on the DTG map, respectively, corresponding to the information embodied in the TG curve.
  • the thermal decomposition of PAPP is more complicated, not only the decomposition of APP but also the thermal decomposition of p-phenylenediamine salt.
  • PAPP is thermally decomposed at 100 °C ⁇ 450 °C to release NH 3 and H 2 O, wherein NH 3 is not only provided by APP, but also -NH 3 + on p-phenylenediamine salt can also release NH 3 , which is also PAPP before 340 ° C
  • the quality loss is slightly larger.
  • the residual quality of PAPP between 340 °C and 470 °C is significantly higher than APP. This is because PAPP decomposes a structure containing ⁇ PN-Ph, which has been shown to have higher thermal stability. It can be explained from the TG and DTG curves that the thermal stability of PAPP is stronger than that of APP.
  • Figure 4 is a graph showing the elongation at break of APP/EVA and PAPP/EVA composites.
  • APP and PAPP were separately added to the EVA matrix to form composite APP/EVA and PAPP/EVA. It can be seen from the figure that as the addition amount of APP and PAPP increases, the elongation at break shows a downward trend. However, PAPP has a significantly lower elongation at break than APP. This is because PPDA is grafted. The active H on PPDA forms a hydrogen bond with the O atom of the EVA matrix, which improves the compatibility.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

提供了一种对苯二胺化学接枝改性的聚磷酸铵衍生物及其制备方法，采用无水乙醇为溶剂，对苯二胺（PPDA）和聚磷酸铵（APP）溶解在其中，在氮气气氛下油浴加热经过后续处理制得对苯二胺化学接枝改性的聚磷酸铵衍生物（PAPP）。所提供的聚磷酸铵衍生物溶解度降低了0.52g/100mL，340℃-460℃热分解失重明显减缓，与基体EVA的相容性也有很大提高，与EVA混合形成的复合材料断裂伸长率提高了30%，UL-94等级从V-1变到V-0，氧指数从26.1%提升到28.2%。

Description

对苯二胺化学接枝改性的聚磷酸铵衍生物及其制备方法 技术领域
本发明属于化学合成领域，具体涉及一种对苯二胺化学接枝改性的聚磷酸铵衍生物及其制备方法。
背景技术
聚磷酸铵(APP)作为一种高效的无卤阻燃剂，近年来一直是国内外的研究热点。APP作为阻燃剂很好的避开了卤素和重金属等带来的危害，符合当今环境友好型的发展理念。APP在阻燃体系中起到了酸源和气源的作用，燃烧可分解出高粘度的无机酸并释放出氨气和水，能够很好的起到隔热隔氧的作用。此外其还具有不易吸湿、成本低廉、分散性好及抑烟效果好等优点。但APP在水中溶解性较大、高温易分解、阻燃效果不能持久及与聚合物基体相容性差等缺点阻碍了其在聚合物阻燃中的应用，因此有必要对其进行改性处理。
欧洲专利指出采用蜜胺甲醛、水、甲醇高温搅拌混合，用于微胶囊包覆APP，所得产物能够降低其水溶性，但未说明其与高分子基体的相容性以及热稳定性。武汉工程大学奚强等人采用有机硅偶联剂对APP进行表面改性，使得APP具有良好的疏水性和分散性，但未讨论其热稳定性等问题。因此，制备一种具有良好的耐水性、热稳定性同时与聚合物基体相容性好的材料是必要而且迫切的。
发明内容
本发明的目的在于针对现有技术的不足，提供一种一种对苯二胺化学接枝改性的聚磷酸铵衍生物及其制备方法。较未改性的聚磷酸铵，本发明的聚磷酸铵衍生物的溶解度降低了0.52g/100mL，340℃～460℃热分解失重明显减缓，与基体EVA的相容性也有很大的提高(即与EVA混合形成的复合材料断裂伸长率提高了30％)，UL-94等级从V-1变到V-0，氧指数从26.1％提升到28.2％。
为实现上述目的，本发明采用如下技术方案：
一种对苯二胺化学接枝改性的聚磷酸铵衍生物，由对苯二胺化学接枝到聚磷酸铵上制得，具体包括以下步骤：
(1)称量45g-55g的聚磷酸铵(APP)分散于无水乙醇中，磁力搅拌30min后得到APP悬浊液；
(2)称量1g-5g的对苯二胺(PPDA)分散于无水乙醇中，80W的超声波清洗器中超声分散30min得到PPDA溶液，将分散良好的PPDA溶液缓慢导入装有APP悬浊液的圆底烧瓶中；
(3)在氮气气氛下油浴加热至120℃，搅拌反应3h-7h，至反应结束后自然冷却到室温。
(4)用无水乙醇离心、反复洗涤3～5次，65℃下真空干燥48h制得对苯二胺化学接枝改性的聚磷酸铵衍生物(PAPP)。
本发明的有益效果在于：本发明采用对苯二胺与聚磷酸铵反应，利用芳香类胺的具有多碳的特性，能更好的体现(酸源、气源和炭源)一体的概念，所制得的对苯二胺化学接枝改性的聚磷酸铵衍生物与聚磷酸铵相比，具有更好的阻燃效果，UL-94等级从V-1变到V-0，氧指数从26.1％提升到28.2％；此外，制得的聚磷酸铵衍生物还具有良好的耐水性、热稳定性及与高分子基体的相容性，其溶解度降低了0.52g/100mL，340℃～460℃热分解失重明显减缓，与基体EVA的相容性也有很大的提高(即与EVA混合形成的复合材料断裂伸长率提高了30％)，这将有益于其作为阻燃剂运用在聚合物中，具有广泛的市场前景和社会效益。
附图说明
图1为PAPP、APP的红外吸收谱图；
图2为PAPP、APP的红外核磁氢谱；
图3为PAPP、APP的TG和DTG曲线；
图4为APP/EVA、PAPP/EVA复合材料的断裂伸长率曲线图。
具体实施方式
以下结合具体实施例对本发明做进一步说明，但本发明不仅仅限于这些实施例。
实施例1
(1)称量45g的APP分散于无水乙醇中，磁力搅拌30min后得到APP悬浊液；
(2)称量1g的PPDA分散于无水乙醇中，80W的超声波清洗器中超声分散30min得到PPDA溶液，将分散良好的PPDA溶液缓慢导入装有APP悬浊液的圆底烧瓶中；
(3)在氮气气氛下油浴加热至120℃，搅拌反应7h，至反应结束后自然冷却到室温；
(4)用无水乙醇离心、反复洗涤4次，65℃下真空干燥48h制得PAPP。
实施例2
(1)称量50g的APP分散于无水乙醇中，磁力搅拌30min后得到APP悬浊液；
(2)称量1g的PPDA分散于无水乙醇中，80W的超声波清洗器中超声分散30min得到PPDA溶液，将分散良好的PPDA溶液缓慢导入装有APP悬浊液的圆底烧瓶中；
(3)在氮气气氛下油浴加热至120℃，搅拌反应3h，至反应结束后自然冷却到室温；
(4)用无水乙醇离心、反复洗涤5次，65℃下真空干燥48h制得PAPP。
实施例3
(1)称量55g的APP分散于无水乙醇中，磁力搅拌30min后得到APP悬浊液；
(2)称量2g的PPDA分散于无水乙醇中，80W的超声波清洗器中超声分散30min得到PPDA溶液，将分散良好的PPDA溶液缓慢导入装有APP悬浊液的圆底烧瓶中；
(3)在氮气气氛下油浴加热至120℃，搅拌反应4h，至反应结束后自然冷却到室温；
(4)用无水乙醇离心、反复洗涤3次，65℃下真空干燥48h制得PAPP。
实施例4
(1)称量50g的APP分散于无水乙醇中，磁力搅拌30min后得到APP悬浊液；
(2)称量3g的PPDA分散于无水乙醇中，80W的超声波清洗器中超声分散30min得到PPDA溶液，将分散良好的PPDA溶液缓慢导入装有APP悬浊液的圆底烧瓶中；
(3)在氮气气氛下油浴加热至120℃，搅拌反应6h，至反应结束后自然冷却到室温；
(4)用无水乙醇离心、反复洗涤5次，65℃下真空干燥48h制得PAPP。
实施例5
(1)称量50g的APP分散于无水乙醇中，磁力搅拌30min后得到APP悬浊液；
(2)称量4g的PPDA分散于无水乙醇中，80W的超声波清洗器中超声分散30min得到PPDA溶液，将分散良好的PPDA溶液缓慢导入装有APP悬浊液的圆底烧瓶中；
(3)在氮气气氛下油浴加热至120℃，搅拌反应5h，至反应结束后自然冷却到室温；
(4)用无水乙醇离心、反复洗涤4次，65℃下真空干燥48h制得PAPP。
实施例6
(1)称量50g的APP分散于无水乙醇中，磁力搅拌30min后得到APP悬浊液；
(2)称量5g的PPDA分散于无水乙醇中，80W的超声波清洗器中超声分散30min得到PPDA溶液，将分散良好的PPDA溶液缓慢导入装有APP悬浊液的圆底烧瓶中；
(3)在氮气气氛下油浴加热至120℃，搅拌反应7h，至反应结束后自然冷却到室温；
(4)用无水乙醇离心、反复洗涤数次，65℃下真空干燥48h制得PAPP。
性能测试与表征
表1为PAPP、APP的水溶性数据。从表1中可以看出，APP的水溶解系数大约为1.78g/100mL；经过化学改性后的PAPP，其水溶解系数为1.26g/100mL，较改性前降低了0.52g/100mL。
表1 PAPP、APP的水溶性数据
Figure PCTCN2016106218-appb-000001
表2为PAPP、APP的阻燃数据。将APP和PAPP分别添加于EVA基体中形成泡沫材料APP/EVA和PAPP/EVA，从表2中可以看出，APP经过改性处理之后阻燃性能明显提升，UL-94等级从V-1变到V-0；氧指数从26.1％提升到28.2％。
表2 PAPP、APP的阻燃数据
Figure PCTCN2016106218-appb-000002
图1为PAPP、APP的红外吸收谱图。从图中可见APP和PAPP在3400～3030cm-1附近均出现了宽峰，为NH4 +上N-H的伸缩振动吸收峰。对比APP谱线可见，PAPP曲线在3050cm-1附近出现吸收峰，为苯环上C-H键的伸缩振动峰；在1635cm-1和1580cm-1所出的峰为苯环C骨架的特征峰；在840cm-1附近出现吸收峰为苯环对位取代C-H键的弯曲振动特征峰。由于PAPP谱线出现了苯环C-H键的特征峰，说明PPDA与APP通过键合作用成功附着在其表面。
图2为PAPP、APP的核磁氢谱及结构简图。由图可见，PAPP、APP均在2.5ppm处出现特征峰，此峰为溶剂二甲基亚砜的特征峰。同时，PAPP谱线在6.45ppm处出现了新的特征峰，该峰为苯环上氢所出的峰。除此之外，在PAPP谱线上没有新的峰出现，说明-NH2已完全清除，对苯二胺成功的接枝在APP上。
图3(a)为PAPP和APP的TG曲线，图3(b)为PAPP和APP的DTG曲线。由TG曲线可得，APP有两个热分解阶段，分别始于300℃和600℃，而PAPP仅在480℃附近有一个较强的热分解阶段。在DTG图上能够分别观察到APP的两个尖峰和PAPP的一个尖峰，与TG曲线所体现的信息相对应。与APP相比，PAPP的热分解较复杂，不仅有APP的分解还有对苯二胺盐的热分解。PAPP在100℃～450℃热分解释放出NH3和H2O，其中NH3不仅由APP提供，对苯二胺盐上的-NH3 +也能释放出NH3，这也是340℃之前PAPP的质量损失略微大些的原因。PAPP在340℃～470℃之间的剩余质量要明显高于APP。这是因为PAPP分解出含～P-N-Ph的结构，该结构被证明有较高的热稳定性。由TG和DTG曲线可以说明，PAPP的热稳定性比APP来得强。
图4为APP/EVA、PAPP/EVA复合材料的断裂伸长率曲线图。将APP和PAPP分别添加于EVA基体中形成复合材料APP/EVA和PAPP/EVA，从图中可以看出，随着APP、PAPP的添加量上升，断裂伸长率呈下降的趋势。但PAPP较APP断裂伸长率下降明显较小，这是因为接枝了PPDA，PPDA上活泼H与EVA基体的O原子形成氢键的作用，改善了相容性。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (4)

  1. 一种对苯二胺化学接枝改性的聚磷酸铵衍生物，其特征在于：所述的聚磷酸铵衍生物由对苯二胺化学接枝到聚磷酸铵上制得。
  2. 一种制备如权利要求1所述的对苯二胺化学接枝改性的聚磷酸铵衍生物的方法，其特征在于：具体包括以下步骤：
    (1)称量45g-55g的聚磷酸铵分散于无水乙醇中，磁力搅拌30min后得到聚磷酸铵悬浊液；
    (2)称量1g-5g的对苯二胺分散于无水乙醇中，超声分散得到对苯二胺溶液，将分散良好的对苯二胺溶液缓慢导入装有聚磷酸铵悬浊液的圆底烧瓶中；
    (3)在氮气气氛下油浴加热至120℃，搅拌反应3h-7h，至反应结束后自然冷却到室温；
    (4)用无水乙醇离心、反复洗涤3～5次，真空干燥制得对苯二胺化学接枝改性的聚磷酸铵衍生物。
  3. 根据权利要求2所述的对苯二胺化学接枝改性的聚磷酸铵衍生物的制备方法，其特征在于：步骤(2)中超声处理条件为：超声功率为80W，时间30min。
  4. 根据权利要求2所述的方法，其特征在于：步骤(4)中真空干燥的温度为65℃，时间为48h。
PCT/CN2016/106218 2016-08-23 2016-11-17 对苯二胺化学接枝改性的聚磷酸铵衍生物及其制备方法 WO2018035999A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610704066.8A CN106279768A (zh) 2016-08-23 2016-08-23 对苯二胺化学接枝改性的聚磷酸铵衍生物及其制备方法
CN201610704066.8 2016-08-23

Publications (1)

Publication Number Publication Date
WO2018035999A1 true WO2018035999A1 (zh) 2018-03-01

Family

ID=57662244

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/106218 WO2018035999A1 (zh) 2016-08-23 2016-11-17 对苯二胺化学接枝改性的聚磷酸铵衍生物及其制备方法

Country Status (2)

Country Link
CN (1) CN106279768A (zh)
WO (1) WO2018035999A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109824984A (zh) * 2019-03-15 2019-05-31 湖北瀚氏汽车零部件有限公司 用于汽车内饰件的阻燃pp材料及其制备方法
CN111533950B (zh) * 2020-04-13 2022-04-08 浙江工业大学 一种三源一体型生物质改性膨胀阻燃剂及其制备方法、应用
CN112210156B (zh) * 2020-08-19 2023-03-17 宁夏师范学院 一种可陶瓷化无卤阻燃高分子复合材料及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101643651A (zh) * 2009-08-25 2010-02-10 四川大学 支化与交联结构大分子膨胀阻燃成炭剂及其制备方法和应用
CN103382267A (zh) * 2013-07-01 2013-11-06 四川大学 有机胺改性聚磷酸铵及其制备方法和应用
CN103756013A (zh) * 2013-12-25 2014-04-30 四川大学 阻燃改性聚磷酸铵及其制备方法和应用
CN105037689A (zh) * 2015-07-27 2015-11-11 四川大学 无卤本征阻燃环氧树脂及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100540595C (zh) * 2005-03-20 2009-09-16 杭州捷尔思阻燃化工有限公司 膨胀型无卤阻燃剂的制备方法及其产品
JP6165111B2 (ja) * 2014-07-29 2017-07-19 大日精化工業株式会社 非ハロゲン難燃性ポリウレタン樹脂組成物及び該非ハロゲン難燃性ポリウレタン樹脂組成物の製造方法
CN105602078B (zh) * 2016-02-06 2017-11-17 福州大学 一种膨胀型阻燃eva泡沫复合材料及其制备方法和应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101643651A (zh) * 2009-08-25 2010-02-10 四川大学 支化与交联结构大分子膨胀阻燃成炭剂及其制备方法和应用
CN103382267A (zh) * 2013-07-01 2013-11-06 四川大学 有机胺改性聚磷酸铵及其制备方法和应用
CN103756013A (zh) * 2013-12-25 2014-04-30 四川大学 阻燃改性聚磷酸铵及其制备方法和应用
CN105037689A (zh) * 2015-07-27 2015-11-11 四川大学 无卤本征阻燃环氧树脂及其制备方法

Also Published As

Publication number Publication date
CN106279768A (zh) 2017-01-04

Similar Documents

Publication Publication Date Title
WO2018035999A1 (zh) 对苯二胺化学接枝改性的聚磷酸铵衍生物及其制备方法
CN103382267B (zh) 有机胺改性聚磷酸铵及其制备方法和应用
CN103333370B (zh) 一种有机无机微胶囊包覆可膨胀石墨的制备方法
CN112920604B (zh) 一种基于大片径氧化石墨烯制备散热膜的方法
WO2018095357A1 (zh) 一种含氟硅聚磷酸酯及其制备方法和应用
TW200844132A (en) Fullerene film using fullerene derivative as raw material, fullerene polymer and their production methods
CN107501493B (zh) 磷氮膨胀型阻燃剂及其制备方法和用途
WO2020024766A1 (zh) 一种杂原子掺杂的聚合物纳米微球/炭纳米微球及其制备方法
CN114874534B (zh) 一种耐久型抗氧化阻燃聚合物复合材料及其制备方法
CN107337809A (zh) 一种具有防老效果的功能性介孔二氧化硅纳米粒子及其制备方法与应用
JP2009091466A (ja) 球状コア／シェル型複合微粒子およびその製造方法
CN103073889B (zh) 一种阻燃热固性树脂及其制备方法
CN114456338B (zh) 一种苯并咪唑基共价有机框架材料的光催化合成方法
CN108912445B (zh) 一种无卤阻燃聚乙烯材料及其制备方法
CN106118065A (zh) 一种膨胀阻燃硅橡胶及其制备方法
CN107501492B (zh) 席夫碱式磷氮膨胀型阻燃剂及其制备方法和用途
Zhao et al. Use of lignin-based crude carbon dots as effective antioxidant for natural rubber
CN103951829A (zh) 一种超支化聚硅氧烷液晶改性热固性树脂及其制备方法
CN116462825B (zh) 一种抑烟阻燃聚氨酯软泡及其制备方法
CN110628170B (zh) 一种基于硅烷改性的氧化石墨烯-酚醛气凝胶材料及其制备方法
CN117264561A (zh) 超临界改性氮化硼纳米管导热填料及胶黏剂的制备方法
CN115286871A (zh) 一种无卤阻燃导电聚丙烯材料
CN114874443A (zh) 一种低固化收缩率的硅橡胶及其制备方法
CN113462154A (zh) 一种高耐热氰酸酯树脂及其制备方法
CN114685937A (zh) 阻燃环氧树脂复合材料及其制备方法

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: 16914019

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16914019

Country of ref document: EP

Kind code of ref document: A1