WO2020047900A1

WO2020047900A1 - Flame retardant, compound flame retardant, and flame retardant polymer material comprising compound flame retardant

Info

Publication number: WO2020047900A1
Application number: PCT/CN2018/106152
Authority: WO
Inventors: 姚强; 曹微虹; 唐天波; 赵月英; 陈俊; 屈亚平
Original assignee: 中国科学院宁波材料技术与工程研究所; 浙江传化华洋化工有限公司
Priority date: 2018-09-07
Filing date: 2018-09-18
Publication date: 2020-03-12
Also published as: CN109265743B; CN109265743A

Abstract

Disclosed are a flame retardant, a compound flame retardant, and a flame retardant polymer material comprising the compound flame retardant. The flame retardant is a phosphoric acid-arylphosphonic acid metal salt and/or a phosphorous acid-arylphosphonic acid metal salt, the phosphoric acid-arylphosphonic acid metal salt and the phosphorous acid-arylphosphonic acid metal salt both being in a layered single phase. The flame retardant overcomes the respective disadvantages of a phosphate (phosphite) salt and a phenylphosphonate salt in the prior art, especially the issues of the prior art in which the phosphate (phosphite) salt has poor compatibility with a polymer material and easily separates therefrom, and the phenylphosphonate salt flame retardant has a low flame retardant efficiency. The flame retardant can also increase the flame retardant effect of a dialkylphosphinate salt flame retardant on a polymer material. Further provided are a compound flame retardant comprising the flame retardant, and a flame retardant polymer material comprising the compound flame retardant.

Description

阻燃剂、复合阻燃剂以及含有该复合阻燃剂的阻燃高分子材料Flame retardant, composite flame retardant and flame retardant polymer material containing the composite flame retardant

技术领域Technical field

本发明涉及一种阻燃剂、复合阻燃剂以及含有该复合阻燃剂的阻燃高分子材料，属于阻燃高分子材料领域。The invention relates to a flame retardant, a composite flame retardant and a flame retardant polymer material containing the composite flame retardant, and belongs to the field of flame retardant polymer materials.

背景技术Background technique

现今阻燃高分子材料已经被广泛运用于电子和电器领域中，例如由阻燃高分子材料制成的电器插座、连接器和继电器等小型电子元部件。现有较常用的阻燃高分子材料有玻璃纤维增强聚酰胺、聚酯PBT和高温尼龙等。现有技术中常通过在高分子材料中添加溴系阻燃剂来实现高分子材料的阻燃，但在阻燃高分子材料燃烧时，其中的溴系阻燃剂会分解产生强烈致癌的二噁英和会引起二次污染的溴化氢。因此，最近人们限制了溴系阻燃剂在高分子阻燃材料中的应用，人们转而采用无卤阻燃剂实现高分子材料的阻燃。Nowadays, flame retardant polymer materials have been widely used in the field of electronics and electrical appliances, such as electrical sockets, connectors and relays made of flame retardant polymer materials, and other small electronic components. The currently more commonly used flame retardant polymer materials are glass fiber reinforced polyamide, polyester PBT and high temperature nylon. In the prior art, the flame retardancy of polymer materials is often achieved by adding bromine flame retardants to the polymer materials. However, when the flame retardant polymer materials are burned, the bromine flame retardants therein will decompose to produce a strong carcinogenic dioxin. Yinghe will cause secondary pollution with hydrogen bromide. Therefore, recently, the application of brominated flame retardants in polymer flame retardant materials has been limited, and people have turned to halogen-free flame retardants to achieve flame retardance of polymer materials.

在无卤阻燃剂中，磷系阻燃剂以其多样化的阻燃机理引起了人们的广泛关注。但现有的有机磷系阻燃剂普遍存在热稳定性低，挥发性大以及化学稳定性差的特性，这些特性阻碍了有机磷系阻燃剂作为高分子材料阻燃剂使用。为了提高磷系阻燃剂的耐热和耐化学稳定性，磷酸盐类阻燃剂和膦酸盐类阻燃剂得到了大力发展。Among halogen-free flame retardants, phosphorus-based flame retardants have attracted widespread attention due to their diverse flame retardant mechanisms. However, the existing organic phosphorus-based flame retardants generally have the characteristics of low thermal stability, large volatility, and poor chemical stability. These characteristics prevent the use of organic phosphorus-based flame retardants as polymer material flame retardants. In order to improve the heat resistance and chemical resistance of phosphorus flame retardants, phosphate flame retardants and phosphonate flame retardants have been vigorously developed.

现有磷系阻燃剂中包括亚磷酸盐阻燃体系，亚磷酸盐多采用高温高压水热法或固-固反应制备，高温高压水热法由于反应条件苛刻，对设备要求高，生产安全性较差不利于工业化生产；固-固反应法制得的产物中残留了较多的亚磷酸，亚磷酸容易引起高分子材料的降解。另外亚磷酸盐(譬如亚磷酸镁)具有较好的水溶性，这一特性使得亚磷酸盐不仅很难通过在水中沉淀的方法来获得，也因容易被水析出而无法在工程塑料中长时间发挥阻燃剂的作用。Existing phosphorus-based flame retardants include a phosphite flame retardant system. Phosphites are mostly prepared by high temperature and high pressure hydrothermal method or solid-solid reaction. The high temperature and high pressure hydrothermal method requires severe equipment due to harsh reaction conditions and production safety. Poor performance is not conducive to industrial production; a large amount of phosphorous acid remains in the product prepared by the solid-solid reaction method, and the phosphorous acid easily causes the degradation of polymer materials. In addition, phosphite (such as magnesium phosphite) has better water solubility. This characteristic makes phosphite not only difficult to obtain by precipitation in water, but also because it is easily precipitated by water and cannot be used for a long time in engineering plastics. Play the role of flame retardant.

现有膦系阻燃剂中包括苯基膦酸盐，目前含苯基膦酸盐的阻燃体系在使用中存在阻燃效果差等问题，含苯基膦酸盐的阻燃体系不能满足工程塑料类高分子材料的加工和性能要求。Existing phosphine-based flame retardants include phenyl phosphonates. The current flame retardant systems containing phenyl phosphonates have problems such as poor flame retardancy in use, and the flame retardant systems containing phenyl phosphonates cannot meet engineering requirements. Processing and performance requirements of plastic polymer materials.

发明内容Summary of the Invention

根据本发明的一个方面，提供了一种阻燃剂，该阻燃剂选自磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐；所述磷酸-芳基膦酸金属盐和所述亚磷酸-芳基膦酸金属盐均为具有层状单一相。According to one aspect of the present invention, there is provided a flame retardant selected from the group consisting of a phosphoric acid-arylphosphonic acid metal salt and / or a phosphorous acid-arylphosphonic acid metal salt; the phosphoric acid-arylphosphonic acid; Both the metal salt and the phosphite-arylphosphonic acid metal salt have a layered single phase.

层状单一相的磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐克服了现有(亚)磷酸盐和芳基膦酸盐的各自不足，特别是克服了现有技术中(亚)磷酸盐同高分子材料相容性差、易析出以及芳基膦酸盐阻燃剂阻燃效率低的问题。The layered single-phase metal phosphate-arylphosphonic acid salt and / or phosphorous acid-arylphosphonic acid metal salt overcome the respective deficiencies of the existing (phosphite) and arylphosphonates, and in particular overcome the existing In the technology, (phosphite) phosphate has poor compatibility with high-molecular materials, is easy to precipitate, and has low flame-retardant efficiency.

所述阻燃剂为磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐；所述磷酸-芳基膦酸金属盐和所述亚磷酸-芳基膦酸金属盐均为层状单一相。The flame retardant is a phosphoric acid-arylphosphonic acid metal salt and / or a phosphorous acid-arylphosphonic acid metal salt; the phosphoric acid-arylphosphonic acid metal salt and the phosphorous acid-arylphosphonic acid metal salt are both It is a layered single phase.

以下为便于说明将(磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐)简称组分A，组分A可按高分子材料阻燃剂的加入量加入高分子材料中，例如组分A的加入量为高分子材料总质量的0.5-10wt％。In the following, for convenience of explanation, (phosphoric acid-arylphosphonic acid metal salt and / or phosphorous acid-arylphosphonic acid metal salt) is simply referred to as component A, and component A may be added to the polymer material according to the amount of the polymer material flame retardant added. In the example, the amount of component A is 0.5-10 wt% of the total mass of the polymer material.

当组分A为所述层状单一相的磷酸-芳基膦酸金属盐和亚磷酸-芳基膦酸金属盐二者的混合物时，可以按任意本领域助剂使用比例混合。When component A is a mixture of the layered single-phase phosphoric acid-arylphosphonic acid metal salt and phosphorous acid-arylphosphonic acid metal salt, it can be mixed in any proportion of auxiliary agents used in the art.

优选地，所述磷酸-芳基膦酸金属盐与所述亚磷酸-芳基膦酸金属盐按质量比为0.5～10:30～1混合。Preferably, the phosphoric acid-arylphosphonic acid metal salt and the phosphorous acid-arylphosphonic acid metal salt are mixed at a mass ratio of 0.5 to 10:30 to 1.

本发明中层状单一相磷酸-芳基膦酸金属盐、层状单一相亚磷酸-芳基膦酸金属盐均可按现有技术中公开的方法制备得到，例如US4962228和US7199172中公开的方法。The layered single-phase phosphoric acid-arylphosphonic acid metal salt and the layered single-phase phosphorous acid-arylphosphonic acid metal salt in the present invention can be prepared according to the methods disclosed in the prior art, for example, the methods disclosed in US4962228 and US7199172. .

根据现有方法可知，层状单一相磷酸-芳基膦酸金属盐、或层状单一相亚磷酸-芳基膦酸金属盐的制备方法简单，可通过形成沉淀分离得到，条件温和，无需高压高温，便于实现工业化生产，实现大规模生产后可降低该阻燃剂的生产成本。According to the existing methods, the preparation method of the layered single-phase phosphoric acid-arylphosphonic acid metal salt, or the layered single-phase phosphorous acid-arylphosphonic acid metal salt is simple, and can be obtained through precipitation and separation. The conditions are mild and no high pressure is required. The high temperature is convenient for industrialized production, and the production cost of the flame retardant can be reduced after mass production.

优选地，所述亚磷酸-芳基膦酸金属盐选自具有式I所示化学式的化合物中的至少一种：Preferably, the phosphite-arylphosphonic acid metal salt is selected from at least one of the compounds having the chemical formula represented by Formula I:

J(O ₃PH) _x1(O ₃PR ¹) _y1·z ₁H ₂O 式I J (O ₃ PH) _x1 (O ₃ PR ¹ ) _y1z ₁ H ₂ O Formula I

其中，J为至少一种二价金属阳离子，R ¹为芳香基，x ₁+y ₁＝1，0.15<x ₁<0.70，0.30<y ₁<0.85，0≤z ₁<1.2。 Wherein, J is at least one divalent metal cation, R ¹ is an aromatic group, x ₁ + y ₁ = _1, 0.15 <x ₁ <0.70, 0.30 <y ₁ <0.85, and ₀ ≦ z ₁ <1.2.

可选地，所述式I中0.32≤y ₁≤0.83；0≤z ₁≤1.1；J为碱土金属离子或锌离子。x ₁还可以为0.44、0.57、0.37、0.19、0.68、0.51、0.35、0.45；y ₁还可以为0.56、0.43、0.63、0.81、0.32、0.49、0.65、0.55。 Optionally, in the formula I, 0.32 ≦ y ₁ ≦ 0.83; 0 ≦ z ₁ ≦ 1.1; J is an alkaline earth metal ion or a zinc ion. x ₁ can also be 0.44, 0.57, 0.37, 0.19, 0.68, 0.51, 0.35, 0.45; y ₁ can also be 0.56, 0.43, 0.63, 0.81, 0.32, 0.49, 0.65, 0.55.

可选地，所述式I中0.40≤y ₁≤0.81；z ₁为0；J为Ca ²⁺、Mg ²⁺、Zn ²⁺中的至少一种；R ¹为苯基。 Optionally, in the formula I, 0.40 ≦ y ₁ ≦ 0.81; z ₁ is 0; J is at least one of Ca ²⁺ , Mg ²⁺ , and Zn ²⁺ ; and R ¹ is phenyl.

优选地，所述磷酸-芳基膦酸金属盐选自具有式II所示化学式的化合物中的至少一种：Preferably, the phosphoric acid-arylphosphonic acid metal salt is selected from at least one compound having a chemical formula represented by Formula II:

Q(O ₃POH) _x2(O ₃PR ²) _y2·z ₂H ₂O 式II Q (O ₃ POH) _x2 (O ₃ PR ² ) _y2 · z ₂ H ₂ O Formula II

其中，Q为至少一种二价金属阳离子，R ²为芳香基，x ₂+y ₂＝1，0.15<x ₂<0.70，0.30<y ₂<0.85，0≤z ₂<1.2。 Wherein, Q is at least one divalent metal cation, R ² is an aromatic group, x ₂ + y ₂ = 1, 0.15 <x ₂ <0.70, 0.30 <y ₂ <0.85, and ₀ ≦ z ₂ <1.2.

可选地，所述式II中0.32≤y ₂≤0.83；0≤z ₂≤1.1；所述Q为碱土金属离子或锌离子。 Optionally, in Formula II, 0.32 ≦ y ₂ ≦ 0.83; 0 ≦ z ₂ ≦ 1.1; and Q is an alkaline earth metal ion or a zinc ion.

可选地，所述式II中0.40≤y ₂≤0.81；z ₂为0；所述Q为Ca ²⁺、Mg ²⁺或Zn ²⁺中的至少一种；所述R ²为苯基。 Optionally, in Formula II, 0.40 ≦ y ₂ ≦ 0.81; z ₂ is 0; the Q is at least one of Ca ²⁺ , Mg ²⁺ or Zn ²⁺ ; and R ² is a phenyl group.

具有式I或者式II的层状单一相的(亚)磷酸-芳基膦酸金属盐的制备，可以通过亚磷酸-芳基膦酸或者磷酸-芳基膦酸的混合酸以及它们的碱金属跟二价金属阳离子交换而得，具体的制备过程见美国专利US4962228和US7199172。Preparation of a layered single-phase (phosphite) -arylphosphonic acid metal salt having Formula I or Formula II can be performed by a mixed acid of phosphorous-arylphosphonic acid or phosphoric acid-arylphosphonic acid and their alkali metals It is obtained by exchanging with divalent metal cations. The specific preparation process is described in US patents US4962228 and US7199172.

具有式I或者式II层状单一相的(亚)磷酸-芳基膦酸金属盐不是(亚)磷酸盐和芳基膦酸盐的简单物理混合物，而是整个物质的XRD(X-射线衍射谱)检测结果的结构呈现层状结构的均一相。在简单的物理混合物中，所得(亚)磷酸-芳基膦酸混合金属盐只有芳基膦酸盐是层状结构，但(亚)磷酸盐是三维结构，呈现出的最终物理性能是各自的相加。层状单一相的结构可以通过XRD来测定层间距或通过测量吸附的伯胺量来确定(具体操作步骤请参见Scott K J，Zhang Y，Wang R C，et al.Synthesis，Characterization，and Amine Intercalation Behavior of Zinc Phosphite Phenylphosphonate Mixed Derivatives[J].Chemistry of Materials，1995，7(6):1095-1102.)，我们发现它呈现出的最终物理性能跟各个组成相加的性能非常不一样。The (phospho) phosphoryl-arylphosphonic acid metal salt having a layered single phase of Formula I or Formula II is not a simple physical mixture of (phosphite) and arylphosphonate, but XRD (X-ray diffraction of the entire substance) The structure of the detection result showed a uniform phase of the layered structure. In a simple physical mixture, only the arylphosphonate is a layered structure, but the (phospho) phosphate has a three-dimensional structure, and the final physical properties exhibited are each Add up. The structure of the layered single phase can be determined by measuring the interlayer distance by XRD or by measuring the amount of primary amines adsorbed (for specific procedures, see Scott K, Zhang Y, Wang R, C, et al. Synthesis, Characterization, and Amine Intercalation Behavior of Phosphite Phenoylphosphonate Mixed Derivatives [J]. Chemistry of Materials, 1995, 7 (6): 1095-1102.), We find that the final physical properties it exhibits are very different from the performance of the addition of each component.

为了满足磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐为层状单一相结构的条件，需要有足够的芳基膦酸盐，为此式I和式II中均需满足0.30<y ₁(y ₂)<0.85，优选地，0.32≤y ₁(y ₂)≤0.83，特别优选地，0.40≤y ₁(y ₂)≤0.81。如果y ₁(y ₂)≤0.30，则无法获得具有层状单一相的(亚)磷酸-芳基膦酸金属盐，在XRD中层间距明显小于纯的芳基膦酸盐。如果y ₁(y ₂)≥0.85，则将其加入阻燃剂后，所制得的高分子材料的阻燃性能下降。由于式I和式II中x ₁+y ₁＝1，x ₂+y ₂＝1，可以方便地得出对应的x ₁(x ₂)值。具体x ₁(x ₂)的范围为0.15<x ₁(x ₂)<0.70；优选为：0.17≤x ₁(x ₂)≤0.68，更优选为：0.19≤x ₁(x ₂)≤0.6。 In order to satisfy the conditions that the phosphoric acid-arylphosphonic acid metal salt and / or phosphorous acid-arylphosphonic acid metal salt has a layered single-phase structure, sufficient arylphosphonates are required. It is required to satisfy 0.30 <y ₁ (y ₂ ) <0.85, preferably 0.32 ≦ y ₁ (y ₂ ) ≦ 0.83, and particularly preferably 0.40 ≦ y ₁ (y ₂ ) ≦ 0.81. If y ₁ (y ₂ ) ≤ 0.30, a (phospho) phosphoryl-arylphosphonic acid metal salt having a layered single phase cannot be obtained, and the interlayer distance in XRD is significantly smaller than that of a pure arylphosphonate. If y ₁ (y ₂ ) ≧ 0.85, the flame retardancy of the prepared polymer material is reduced after adding the flame retardant. Since x ₁ + y ₁ = 1 and x ₂ + y ₂ = 1 in Formula I and Formula II, corresponding values of x ₁ (x ₂ ) can be conveniently obtained. Specifically, the range of x ₁ (x ₂ ) is 0.15 <x ₁ (x ₂ ) <0.70; preferably: 0.17 ≦ x ₁ (x ₂ ) ≦ 0.68, and more preferably: 0.19 ≦ x ₁ (x ₂ ) ≦ 0.6.

式I和式II均满足0≤z ₁(z ₂)<1.2，优选地，0≤z ₁(z ₂)≤1.1，特别优选地，z ₁(z ₂)为0或非常接近于0。如果z ₁(z ₂)≥1.2，则水分含量过多，在高分子材料的加工过程中，会引起材料的降解。 Both Formula I and Formula II satisfy 0 ≦ z ₁ (z ₂ ) <1.2, preferably, 0 ≦ z ₁ (z ₂ ) ≦ 1.1, and particularly preferably, z ₁ (z ₂ ) is 0 or very close to 0. If z ₁ (z ₂ ) ≥ 1.2, the moisture content is too much, which will cause the degradation of the material during the processing of the polymer material.

式I和式II中的x ₁(x ₂)和y ₁(y ₂)的比例可以通过碱解或酸解溶解之后，用 ³¹P核磁来确定。(亚)磷酸(盐)和膦酸(盐)在 ³¹P核磁中的峰面积比例即为x ₁(x ₂)和y ₁(y ₂)之比。式I中的z ₁(z ₂)可以通过TGA热失重曲线来确定。从前述的《Characterization，and Amine Intercalation Behavior of Zinc Phosphite Phenylphosphonate Mixed Derivatives》中可知，式I的化合物中的水可以完全被等当量的伯胺取代，因此z ₁(z ₂)也可以通过被胺取代过的盐的TGA中的伯胺失重量计算得到。 The ratio of x ₁ (x ₂ ) and y ₁ (y ₂ ) in Formula I and Formula II can be determined by ³¹ P NMR after being dissolved by alkaline or acid hydrolysis. The ratio of the peak areas of (p) phosphoric acid (salt) and phosphonic acid (salt) in ³¹ P NMR is the ratio of x ₁ (x ₂ ) and y ₁ (y ₂ ). Z ₁ (z ₂ ) in Formula I can be determined by a TGA thermal weight loss curve. From the aforementioned "Characterization, and Amine Intercalation Behavior of Zinc Phosphite Phenylphosphonate Mixed Derivatives", it can be known that the water in the compound of formula I can be completely replaced by an equivalent amount of primary amine, so z ₁ (z ₂ ) can also be replaced by The weight loss of the primary amine in the TGA of the salt was calculated.

式I和式II中，所述J或Q分别独立地优选地为碱土金属离子或锌离子，特别优选地，所述J或Q分别独立地为Ca ²⁺，Mg ²⁺，Zn ²⁺。R ¹优选为芳基，特别优选地，所述R ¹为苯基。 In Formula I and Formula II, the J or Q are each independently preferably an alkaline earth metal ion or a zinc ion, and particularly preferably, the J or Q are each independently Ca ²⁺ , Mg ²⁺ , or Zn ²⁺ . R ¹ is preferably an aryl group, and particularly preferably, R ¹ is a phenyl group.

本发明的又一方面还提供了一种复合阻燃剂，所述复合阻燃剂包括组分A和组分B；Another aspect of the present invention also provides a composite flame retardant, which includes a component A and a component B;

其中，所述组分A选自上述的阻燃剂；Wherein, the component A is selected from the aforementioned flame retardants;

所述组分B选自二烷基次膦酸盐中的至少一种。The component B is selected from at least one of dialkylphosphinates.

二烷基次膦酸盐可以为现有方法制备得到的各类二烷基次膦酸盐或商业途径购得。Dialkylphosphinates can be obtained from various types of dialkylphosphinates prepared by existing methods or purchased commercially.

所述组分A与所述组分B的质量比为0.5～10：30～1。The mass ratio of the component A to the component B is 0.5 to 10: 30 to 1.

优选地，所述二烷基次膦酸盐选自具有式III所示化学式的化合物或式IV所示化学式的化合物中的至少一种：Preferably, the dialkylphosphinate is selected from at least one of a compound having a chemical formula represented by Formula III or a compound having a chemical formula represented by Formula IV:

其中，R ₅和R ₆分别独立地选自C ₁～C ₈的烷基；G ^m+表示价态为m的金属G离子，m为金属G的价态；A选自C ₁～C ₁₆的亚烃基；R ₇和R ₈分别独立地选自C ₁～C ₈的烷基；L ^p+表示价态为p的金属L离子，p为金属L的价态。 Among them, R ₅ and R ₆ are each independently selected from C ₁ to C ₈ alkyl groups; G ^{m +} represents a metal G ion having a valence state of m, and m is a valence state of a metal G; A is selected from C ₁ to C ₁₆ R ₇ and R ₈ are each independently selected from C ₁ to C ₈ alkyl groups; L ^{p +} represents a metal L ion having a valence state of p, and p is a valence state of a metal L.

可选地，R ₅、R ₆分别独立地选自C ₁～C ₄的直链烷基或支链烷基。 Optionally, R ₅ and R ₆ are each independently selected from a linear alkyl group or a branched alkyl group of C ₁ to C ₄ .

可选地，R ₇、R ₈分别独立地选自C ₁～C ₄的直链烷基或支链烷基。 Optionally, R ₇ and R ₈ are each independently selected from a linear alkyl group or a branched alkyl group of C ₁ to C ₄ .

优选地，所述A独立地选自C ₁～C ₅的亚烷基、C ₆～C ₁₀的亚芳香基、烷基取代亚芳香基或芳基取代亚烷基。 Preferably, A is independently selected from C ₁ to C ₅ alkylene, C ₆ to C ₁₀ arylene, alkyl-substituted arylene or aryl-substituted alkylene.

优选地，所述亚芳香基中取代基为烷基或烯烃基。Preferably, the substituent in the arylene group is an alkyl group or an olefin group.

优选地，式III中，所述金属离子G ^m+独立地选自二价金属阳离子、三价金属阳离子中的至少一种。 Preferably, in Formula III, the metal ion G ^{m + is} independently selected from at least one of a divalent metal cation and a trivalent metal cation.

优选地，所述金属离子G ^m+和所述金属离子L ^p+分别独立地选自二价金属阳离子、三价金属阳离子中的至少一种； Preferably, the metal ion G ^{m +} and the metal ion L ^{p +} are each independently selected from at least one of a divalent metal cation and a trivalent metal cation;

优选地，所述金属离子G ^m+和所述金属离子L ^p+分别独立地选自Mg ²⁺、Ca ²⁺、Ba ²⁺、Fe ²⁺、Fe ³⁺、Al ³⁺、Zn ²⁺中的至少一种。 Preferably, the metal ion G ^{m +} and the metal ion L ^{p +} are independently selected from the group consisting of Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Fe ²⁺ , Fe ³⁺ , Al ³⁺ , and Zn ²⁺ . At least one.

进一步优选地，所述组分B选自二乙基次膦酸铝、二乙基次膦酸锌中的至少一种。Further preferably, the component B is selected from at least one of aluminum diethylphosphinate and zinc diethylphosphinate.

更优选地，本发明提供的上述复合阻燃剂，能有效提高玻璃纤维增强聚酰胺高分子材料和聚酯高分子材料的阻燃性能。More preferably, the composite flame retardant provided by the present invention can effectively improve the flame retardancy of glass fiber reinforced polyamide polymer materials and polyester polymer materials.

本发明的又一方面还提供了一种阻燃高分子材料，所述阻燃高分子材料包含如上述复合阻燃剂和高分子材料。具体地，含有如上述所述的具有层状单一相的磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐。Another aspect of the present invention also provides a flame-retardant polymer material, which includes the composite flame retardant and the polymer material as described above. Specifically, it contains a phosphoric acid-arylphosphonic acid metal salt and / or a phosphorous acid-arylphosphonic acid metal salt having a layered single phase as described above.

优选地，所述阻燃高分子材料包含含有组分A以及组分B的复合阻燃剂。Preferably, the flame-retardant polymer material includes a composite flame retardant containing component A and component B.

所述组分A为磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐；所述磷酸-芳基膦酸金属盐和所述亚磷酸-芳基膦酸金属盐均为层状单一相。组分A可按本领域惯用助剂加入量添加，优选地，所述复合阻燃剂中的组分A在所述阻燃高分子材料中的质量百分含量为0.5-10wt％。更优选地，所述复合阻燃剂中的组分A在所述阻燃高分子材料中的质量百分含量为0.75-8wt％。进一步优选地，所述复合阻燃剂中的组分A在所述阻燃高分子材料中的质量百分含量为1-5wt％。The component A is a phosphoric acid-arylphosphonic acid metal salt and / or a phosphorous acid-arylphosphonic acid metal salt; the phosphoric acid-arylphosphonic acid metal salt and the phosphorous acid-arylphosphonic acid metal salt are both It is a layered single phase. Component A can be added according to the amount of additives commonly used in the art. Preferably, the mass percentage content of component A in the composite flame retardant in the flame retardant polymer material is 0.5-10 wt%. More preferably, the mass percentage content of component A in the composite flame retardant in the flame retardant polymer material is 0.75-8 wt%. Further preferably, the mass percentage content of component A in the composite flame retardant in the flame retardant polymer material is 1 to 5 wt%.

可选地，所述组分A的加入质量占所述阻燃高分子材料总质量的4wt％、3wt％、1wt％。Optionally, the added mass of the component A accounts for 4 wt%, 3 wt%, and 1 wt% of the total mass of the flame-retardant polymer material.

优选地，所述组分B加入质量占所述阻燃高分子材料总质量的1～30％。更优选地，所述复合阻燃剂中的组分B在所述阻燃高分子材料中的质量百分含量为10～20wt％。Preferably, the added mass of the component B accounts for 1-30% of the total mass of the flame-retardant polymer material. More preferably, the mass percentage content of component B in the composite flame retardant in the flame-retardant polymer material is 10-20 wt%.

当按上述比列添加组分A和组分B时，高分子材料的阻燃效果大幅提升。并且组分A的层状单一相结构克服了现有技术中(亚)磷酸盐同高分子材料相容性差、易析出以及芳基膦酸盐阻燃效果差的问题。When component A and component B are added according to the above-mentioned ratio, the flame retardant effect of the polymer material is greatly improved. And the layered single-phase structure of component A overcomes the problems of poor compatibility of the (phosphite) phosphate with the polymer material, easy precipitation, and poor arylphosphonate flame retardancy in the prior art.

可选地，所述组分B加入质量占所述阻燃高分子材料总质量的上限选自30wt％、28wt％、26wt％、24wt％、22wt％、20wt％、18wt％，下限选自15wt％、13wt％、11wt％、9wt％、7wt％、5wt％、3wt％、1wt％。Optionally, the upper limit of the mass of the component B added to the total mass of the flame-retardant polymer material is selected from 30wt%, 28wt%, 26wt%, 24wt%, 22wt%, 20wt%, 18wt%, and the lower limit is selected from 15wt %, 13 wt%, 11 wt%, 9 wt%, 7 wt%, 5 wt%, 3 wt%, 1 wt%.

优选地，所述阻燃高分子材料中还包括功能添加剂，所述功能添加剂包括抗氧剂、增强剂、抗滴落剂、稳定剂、颜料、染料、成炭催化剂、分散剂、成核剂或无机填料中的至少一种。Preferably, the flame retardant polymer material further includes a functional additive, and the functional additive includes an antioxidant, a reinforcing agent, an anti-dripping agent, a stabilizer, a pigment, a dye, a carbon-forming catalyst, a dispersant, and a nucleating agent. Or at least one of inorganic fillers.

优选地，所述增强剂为玻璃纤维。Preferably, the reinforcing agent is glass fiber.

优选地，所述无机填料为云母石、碳酸钙、氧化钙和硅石中的至少一种。Preferably, the inorganic filler is at least one of mica, calcium carbonate, calcium oxide, and silica.

优选地，所述阻燃高分子材料包括玻璃纤维。Preferably, the flame-retardant polymer material includes glass fiber.

本领域技术人员可以根据实际需要，选择功能添加剂、高分子材料的种类和加入量。可选的，所述功能添加剂在所述阻燃高分子材料中的质量百分含量为10～40％。Those skilled in the art may select the types and addition amounts of functional additives, polymer materials according to actual needs. Optionally, the mass percentage content of the functional additive in the flame-retardant polymer material is 10-40%.

需注意本发明中阻燃高分子材料中所有组分的重量百分比之和为100wt％。It should be noted that the sum of the weight percentages of all components in the flame-retardant polymer material in the present invention is 100% by weight.

高分子材料可以为各类高分子材料如热塑性高分子材料或热固性高分子材料。优选地，所述高分子材料选自热塑性高分子材料中的至少一种。更优选为热塑性高分子材料，热塑性高分子是指具有加热软化、冷却硬化特性的塑料。The polymer material can be various types of polymer materials such as thermoplastic polymer materials or thermosetting polymer materials. Preferably, the polymer material is selected from at least one of thermoplastic polymer materials. More preferably, it is a thermoplastic polymer material, and a thermoplastic polymer is a plastic which has the characteristics of heat softening and cooling hardening.

本发明中高分子是指由众多原子或原子团主要以共价键结合而成的分子量在一万以上的化合物。其包括聚乙烯、聚丙烯、聚苯乙烯、高抗冲聚苯乙烯、丙烯腈-丁二烯-苯乙烯共聚物、聚酰胺塑料、聚酰胺纤维、聚酯塑料、聚酯纤维、聚碳酸酯等。优选地，所述高分子材料为聚酰胺、聚酯中的至少一种。The polymer in the present invention refers to a compound having a molecular weight of more than 10,000, which is formed by a plurality of atoms or atom groups mainly covalently bonded. It includes polyethylene, polypropylene, polystyrene, high impact polystyrene, acrylonitrile-butadiene-styrene copolymer, polyamide plastic, polyamide fiber, polyester plastic, polyester fiber, polycarbonate Wait. Preferably, the polymer material is at least one of polyamide and polyester.

本发明中聚酰胺，是指结构单元主链中含极性酰胺基团-NH-C(O)-的高分子材料，该聚酰胺由a、b、c中的至少一组原料反应得到；The polyamide in the present invention refers to a polymer material containing a polar amide group -NH-C (O)-in a main chain of a structural unit, and the polyamide is obtained by reacting at least one group of raw materials in a, b, and c;

a、至少一种二元羧酸与至少一种二元胺。a. At least one dicarboxylic acid and at least one diamine.

b、至少一种氨基酸。b. at least one amino acid.

c、至少一种内酰胺。c. At least one lactam.

本发明中聚酯，是其结构单元主链中含酯基团-O-C(O)-的高分子材料，通过二元羧酸和二元醇缩合反应合成。The polyester in the present invention is a polymer material containing an ester group -O-C (O)-in the main chain of its structural unit, and is synthesized through a condensation reaction of a dicarboxylic acid and a glycol.

优选地，所述阻燃高分子材料中的高分子材料为聚酰胺、聚酯中的至少一种。Preferably, the polymer material in the flame-retardant polymer material is at least one of polyamide and polyester.

优选地，所述高分子材料选自聚酰胺6、聚酰胺66、聚对苯二甲酸乙二酯、聚对苯二甲酸丙二酯、聚对苯二甲酸丁二酯中的至少一种。Preferably, the polymer material is selected from at least one of polyamide 6, polyamide 66, polyethylene terephthalate, polytrimethylene terephthalate, and polybutylene terephthalate.

本发明中，C ₁～C ₈、C ₁～C ₁₆等均指基团所包含的碳原子数。 In the present invention, C ₁ to C ₈ , C ₁ to C ₁₆ and the like all refer to the number of carbon atoms contained in the group.

本发明中，“烃类化合物”是碳氢化合物的统称，是由碳与氢原子所构成的化合物，烃类化合物包括烷烃化合物、烯烃化合物、炔烃化合物和芳烃化合物。In the present invention, "hydrocarbon compounds" are collectively referred to as hydrocarbon compounds, and are compounds composed of carbon and hydrogen atoms. The hydrocarbon compounds include alkane compounds, olefin compounds, alkyne compounds, and aromatic compounds.

本发明中，“亚烃基”是指由烃类化合物分子上失去任意两个氢原子所形成的基团，包括亚烷基、亚芳基、亚芳烷基、亚烷芳基、烷基-芳基亚基等。In the present invention, "alkylene" refers to a group formed by the loss of any two hydrogen atoms on a hydrocarbon compound molecule, and includes alkylene, arylene, aralkylene, alkylenearyl, and alkyl- Aryl subunits, etc.

本发明中，“烷基”是由烷烃化合物分子上失去任意一个氢原子所形成的基团。烷烃化合物包括直链烷烃、支链烷烃和环烷烃。In the present invention, an "alkyl group" is a group formed by the loss of any hydrogen atom in the molecule of an alkane compound. Alkanes include linear, branched, and cycloalkanes.

本发明中，“芳基”是芳香族化合物分子上失去芳香环上一个氢原子所形成的基团；如甲苯失去苯环上甲基对位的氢原子所形成的对甲苯基。In the present invention, an "aryl group" is a group formed by the loss of a hydrogen atom on an aromatic ring on an aromatic compound molecule; for example, toluene is a p-tolyl group formed by the loss of a methyl para-position hydrogen atom on a benzene ring.

本发明中，“烷基取代亚芳香基”是指含有烷基取代基的芳香化合物，失去任意两个芳香环上的氢原子所形成的基团。In the present invention, the "alkyl-substituted arylene group" refers to a group formed by the loss of a hydrogen atom on any two aromatic rings of an aromatic compound containing an alkyl substituent.

本发明中，“芳基取代亚烷基”是指含有烷基取代基的芳香化合物，失去任意两个非芳香环上的氢原子所形成的基团。In the present invention, the "aryl-substituted alkylene group" refers to a group formed by the loss of hydrogen atoms on any two non-aromatic rings of an aromatic compound containing an alkyl substituent.

本发明中，“亚芳香基”是不含取代基的芳环化合物失去芳香环上任意两个氢原子所形成的基团，如：In the present invention, an "arylene" is a group formed by an aromatic ring compound without a substituent, losing any two hydrogen atoms on the aromatic ring, such as:

等。

Wait.

本发明中，“聚酰胺”是指包含酰胺基团的高分子聚合物，其中“酰胺基团”是指具有-NH-C(O)-结构的基团。可通过一种或多种二元羧酸和一种或多种二元胺，和/或者一种或多种氨基酸，和/或者一种或多种内酰胺缩合或开环反应合成。In the present invention, "polyamide" refers to a polymer containing an amide group, and "amide group" refers to a group having a -NH-C (O)-structure. It can be synthesized by condensation or ring-opening reaction of one or more dicarboxylic acids and one or more diamines, and / or one or more amino acids, and / or one or more lactams.

本发明的有益效果包括但不限于：The beneficial effects of the present invention include, but are not limited to:

(1)本发明所提供的阻燃剂，以具有层状单一相的磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐作为阻燃剂，不同于已有的(亚)磷酸盐，已有的(亚)磷酸盐与高分子材料相容性差，容易析出。本发明提供的磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐作为阻燃剂时，由于(亚)磷酸盐和芳香基膦酸盐形成层状单一相，提高了与高分子材料的相容性，极大地避免了(亚)磷酸盐成分在阻燃高分子材料中的析出。(1) The flame retardant provided by the present invention uses a phosphoric acid-arylphosphonic acid metal salt and / or a phosphorous acid-arylphosphonic acid metal salt having a layered single phase as a flame retardant, which is different from the existing ( Phosphite, the existing (phosphite) has poor compatibility with polymer materials and is easy to precipitate. When the phosphoric acid-arylphosphonic acid metal salt and / or phosphorous acid-arylphosphonic acid metal salt provided by the present invention is used as a flame retardant, the (phosphite) and the aromatic phosphonate form a layered single phase, which improves the Compatibility with polymer materials has greatly prevented the precipitation of (phosphite) components in flame-retardant polymer materials.

(2)本发明所提供的阻燃剂，其中具有层状单一相的磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐，制备容易。按现有方法制备时，由于芳香基膦酸盐的疏水性容易析出沉淀，从而得到同时含亚磷酸根离子和芳香基膦酸根离子的沉淀化合物，制备方法条件温和，利于实现工业化生产。(2) The flame retardant provided by the present invention, wherein the phosphoric acid-arylphosphonic acid metal salt and / or phosphorous acid-arylphosphonic acid metal salt having a layered single phase is easy to prepare. When prepared by the existing method, due to the hydrophobicity of the aryl phosphonate, a precipitate is easily precipitated, so that a precipitate compound containing both a phosphite ion and an aryl phosphonate ion is obtained. The preparation method has mild conditions, which is conducive to the realization of industrial production.

(3)本发明所提供的阻燃剂，其中具有层状单一相的磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐，仅需在常温常压下即可制备得到。无需高温高压的水热法，在低于或等于100℃和常压下即能得到含有(亚)磷酸根离子并具有高度热稳定性和低水溶性的产物。(3) The flame retardant provided by the present invention, wherein the phosphoric acid-arylphosphonic acid metal salt and / or phosphorous acid-arylphosphonic acid metal salt having a layered single phase can be prepared only at normal temperature and pressure get. Without the high temperature and high pressure hydrothermal method, a product containing (phosphite) ions and having high thermal stability and low water solubility can be obtained at a temperature lower than or equal to 100 ° C and normal pressure.

(4)本发明所提供的复合阻燃剂，包含组分A和组分B的复合阻燃剂，可作为高分子材料阻燃剂使用。尤其作为玻璃纤维增强聚酰胺和玻璃纤维增强聚酯的阻燃剂使用时，能使所得高分子材料具有较优异的阻燃性能。(4) The composite flame retardant provided by the present invention includes a composite flame retardant containing component A and component B, and can be used as a polymer material flame retardant. In particular, when used as a flame retardant for glass fiber reinforced polyamide and glass fiber reinforced polyester, the obtained polymer material can have excellent flame retardancy.

(5)本发明所提供的阻燃高分子材料，其中所用阻燃剂为包含组分A和组分B的复合阻燃剂，克服了组分B单独用于高分子材料时阻燃效率低下的问题。(5) The flame retardant polymer material provided by the present invention, wherein the flame retardant used is a composite flame retardant containing component A and component B, which overcomes the low flame retardant efficiency when component B is used alone in the polymer material. The problem.

具体实施方式detailed description

本发明提到的上述特征，或实施例提到的特征可以任意组合。本案说明书所揭示的所有特征可与任何组合形式并用，说明书中所揭示的各个特征，可以被任何能提供相同、均等或相似目的的替代性特征取代。因此除有特别说明，所揭示的特征仅为均等或相似特征的一般性例子。The above-mentioned features mentioned in the present invention or the features mentioned in the embodiments can be arbitrarily combined. All features disclosed in the specification of this case can be used in combination with any combination, and each feature disclosed in the specification can be replaced by any alternative feature that can provide the same, equal, or similar purpose. Unless otherwise stated, the disclosed features are only general examples of equal or similar features.

下面结合实施例详述本发明，应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。The present invention is described in detail below with reference to examples. It should be understood that these examples are only used to illustrate the present invention and not to limit the scope of the present invention.

下列实施例中如无特别说明，原料均通过商业途径购买，其中：Unless otherwise specified in the following examples, raw materials are purchased through commercial channels, where:

PA66(又称聚酰胺66或尼龙66)：购于美国杜邦，型号：Zytel 70G35L NC010，其中玻璃纤维含量为35wt％。PA66 (also known as polyamide 66 or nylon 66): purchased from DuPont, USA, model: Zytel 70G35L NC010, where the glass fiber content is 35 wt%.

PA6(又称聚酰胺6或尼龙6)：购于美国杜邦，型号：Zytel 73G30L NC010，其中玻璃纤维含量为30wt％。PA6 (also known as polyamide 6 or nylon 6): purchased from DuPont, USA, model: Zytel 73G30L NC010, where the glass fiber content is 30% by weight.

PBT(又称聚对苯二甲酸丁二酯)：购于美国杜邦，型号：Crastin SK605NC010，玻璃纤维含量为30wt％。PBT (also known as polybutylene terephthalate): purchased from DuPont, USA, model: Crastin SK605NC010, glass fiber content is 30wt%.

DePAl：二乙基次膦酸铝，购于浙江传化华洋股份有限公司。DePAl: aluminum diethylphosphinate, purchased from Zhejiang Chuanhua Huayang Co., Ltd.

抗氧剂1010：四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯，购于萨恩化学技术(上海)有限公司。Antioxidant 1010: Tetra [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propanoic acid] pentaerythritol ester, purchased from Saen Chemical Technology (Shanghai) Co., Ltd.

抗氧剂168：三[2，4-二叔丁基苯基]亚磷酸酯，购于美国Strem化学公司。Antioxidant 168: tris [2,4-di-tert-butylphenyl] phosphite, purchased from Strem Chemical Company, USA.

复配抗氧剂：抗氧剂1010(四[β-(3，5-二叔丁基-4-羟基苯基丙酸]季戊四醇酯)与抗氧剂168(三[2，4-二叔丁基苯基]亚磷酸酯)按重量比1:1混合得到。Compound antioxidants: antioxidant 1010 (tetra [β- (3,5-di-tert-butyl-4-hydroxyphenylpropanoic acid] pentaerythritol ester) and antioxidant 168 (tri [2,4-ditert Butylphenyl] phosphite) is obtained by mixing at a weight ratio of 1: 1.

核磁共振(NMR)测试：所用仪器型号AVANCE III 400MHz，购自德国Bruker公司。Nuclear magnetic resonance (NMR) test: The instrument model used was AVANCE III 400MHz, purchased from Bruker, Germany.

核磁共振测试方法：以85％磷酸的化学位移为0，扫描32次，并以峰面积之比作为亚磷酸根离子和苯膦酸根离子之比。Nuclear magnetic resonance test method: The chemical shift of 85% phosphoric acid is 0, scanning is performed 32 times, and the ratio of peak area is used as the ratio of phosphite ion and phenylphosphonate ion.

X射线衍射(XRD)测试所用仪器型号：D8ADVANCE DAVINCI，购自德国Bruker公司。X-ray diffraction (XRD) test instrument model: D8ADVANCE DAVINCI, purchased from Bruker, Germany.

X射线荧光光谱分析(XRF)测试所用仪器型号：S8TIGER，购自德国Bruker公司。X-ray fluorescence spectrometry (XRF) test instrument model: S8TIGER, purchased from Bruker, Germany.

TGA热失重处理所用仪器型号：Q500，购自美国TA公司。The instrument model used for TGA thermal weight loss treatment: Q500, purchased from American TA company.

实施例1 Zn(O ₃PH) _0.44(O ₃PPh) _0.56的制备 Example 1 Preparation of Zn (O ₃ PH) _0.44 (O ₃ PPh) _0.56

取31.60克(0.20摩尔)苯膦酸和16.40克(0.20摩尔)亚磷酸溶解在480g水中，用5％的氢氧化钠水溶液调至pH＝11，得到混合酸溶液。另取54.50克(0.40摩尔)氯化锌溶解于545克水中，得到氯化锌溶液。31.60 g (0.20 mol) of phenylphosphonic acid and 16.40 g (0.20 mol) of phosphorous acid were dissolved in 480 g of water, and adjusted to pH = 11 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 54.50 g (0.40 mol) of zinc chloride was dissolved in 545 g of water to obtain a zinc chloride solution.

在常温搅拌下，将氯化锌溶液慢慢滴加到混合酸溶液中，得到大量白色沉淀。经抽滤去除溶剂，得到滤饼用乙醇洗涤之后得到白色固体。Under normal temperature stirring, the zinc chloride solution was slowly added dropwise to the mixed acid solution to obtain a large amount of white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid.

对所得的白色固体进行 ³¹P NMR测试：将部分白色固体完全溶解于浓盐酸中，按前述核磁共振测试方法进行测试，由所得 ³¹P NMR结果可知亚磷酸和苯膦酸的比例为0.44:0.56。 The ³¹ P NMR test was performed on the obtained white solid: a part of the white solid was completely dissolved in concentrated hydrochloric acid, and the test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR result, the ratio of phosphorous acid and phenylphosphonic acid was 0.44: 0.56 .

测试所得到的白色固体产品的TGA热失重曲线：将部分白色固体分置于真空烘箱中，在120℃下干燥24小时，取出，将样品淹没于正丙胺中，在室温下搅拌3天，过滤，空气干燥样品后进行TGA热失重处理。所得TGA热失重曲线第一阶段由正丙胺引起的失重为22.4％。由于白色固体中结晶水和正丙胺的摩尔比为1：1，按下式计算出样品中带有水的摩尔比为：TGA thermal weight loss curve of the white solid product obtained by testing: Put a part of the white solid in a vacuum oven, dry it at 120 ° C for 24 hours, remove it, submerge the sample in n-propylamine, stir at room temperature for 3 days, and filter After the samples were air-dried, TGA thermal weight loss treatment was performed. The weight loss caused by n-propylamine in the first stage of the obtained TGA thermal weight loss curve was 22.4%. Since the molar ratio of crystal water and n-propylamine in the white solid is 1: 1, the molar ratio of water in the sample is calculated as follows:

0.224*187.94/(1-0.224)*59＝0.920.224 * 187.94 / (1-0.224) * 59 = 0.92

其中，187.94为Zn(O ₃PH) _0.44(O ₃PPh) _0.56的分子量，59为正丙胺的分子量。 Among them, 187.94 is a molecular weight of Zn (O ₃ PH) _0.44 (O ₃ PPh) _0.56 , and 59 is a molecular weight of n-propylamine.

因而含结晶水的固体样品具有分子式Zn(O ₃PH) _0.44(O ₃PPh) _0.56·0.92H ₂O。将含结晶水的该样品置于120℃下干燥即得失去结晶水的样品Zn(O ₃PH) _0.44(O ₃PPh) _0.56。 Therefore, a solid sample containing crystal water has a molecular formula of Zn (O ₃ PH) _0.44 (O ₃ PPh) _0.56 .0.92H ₂ O. The sample containing crystal water was dried at 120 ° C. to obtain a sample Zn (O ₃ PH) _0.44 (O ₃ PPh) _{0.56 without} crystal water.

对干燥后的样品进行XRD测试，所得X-射线衍射(XRD)结果如下表1，从表1中相对强度最高的特征峰可知，所得产物中所形成层状结构，且各层状结构之间的层间距主要为

说明所得产物中层间距较大。以下各实施例中XRD所得结果仅示出相对强度最高的特征峰对应的层间距数值。 The XRD test was performed on the dried samples. The X-ray diffraction (XRD) results obtained are shown in Table 1 below. From the characteristic peaks with the highest relative intensity in Table 1, it can be seen that the layered structure formed in the obtained product, The layer spacing is mainly

This shows that the interlayer spacing in the obtained product is large. The results obtained by XRD in the following examples only show the interlayer distance values corresponding to the characteristic peaks with the highest relative intensity.

表1Table 1

以下各实施例中，如未说明组分A中含有结晶水，则组分A中z值＝0。组分A中的结晶水已经过干燥处理去除。In the following examples, if it is not stated that component A contains crystal water, the value of z in component A = 0. The water of crystallization in component A has been removed by drying.

实施例2 Zn(O ₃PH) _0.57(O ₃PPh) _0.43的制备 Example 2 Preparation of Zn (O ₃ PH) _0.57 (O ₃ PPh) _0.43

取15.80克(0.10摩尔)苯膦酸和12.30克(0.15摩尔)亚磷酸溶解于281克水中，用5％的氢氧化钠水溶液调至pH＝11，得到混合酸溶液。另取34.08克(0.25摩尔)氯化锌溶于340克水中，得到氯化锌溶液。15.80 g (0.10 mol) of phenylphosphonic acid and 12.30 g (0.15 mol) of phosphorous acid were dissolved in 281 g of water, and adjusted to pH = 11 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 34.08 g (0.25 mol) of zinc chloride was dissolved in 340 g of water to obtain a zinc chloride solution.

在常温搅拌下，将氯化锌水溶液慢慢滴加到混合酸溶液中，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120℃下真空烘干，得到产品Zn(O ₃PH) _0.57(O ₃PPh) _0.43。 Under normal temperature stirring, a zinc chloride aqueous solution was slowly added dropwise to the mixed acid solution to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and vacuum-dried at 120 ° C. to obtain the product Zn (O ₃ PH) _0.57 (O ₃ PPh) _0.43 .

对样品进行 ³¹P NMR测试：将部分所得白色固体溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR结果可知亚磷酸和苯膦酸的比例为0.57:0.43。 The sample was subjected to ³¹ P NMR test: a part of the obtained white solid was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR result, it was found that the ratio of phosphorous acid and phenylphosphonic acid was 0.57: 0.43.

对样品进行XRD测试，所得XRD测定的层间距为

The XRD test was performed on the sample, and the interlayer distance measured by the obtained XRD was

实施例3 Zn(O ₃PH) _0.37(O ₃PPh) _0.63的制备 Example 3 Preparation of Zn (O ₃ PH) _0.37 (O ₃ PPh) _0.63

取23.71克(摩尔)苯膦酸和8.20克(0.10摩尔)亚磷酸溶解于310克水中，用5％的氢氧化钠水溶液调至pH＝11，得到混合酸溶液。另取34.08克(0.25摩尔)氯化锌溶于340克水中，得到氯化锌溶液。Take 23.71 g (mol) of phenylphosphonic acid and 8.20 g (0.10 mol) of phosphorous acid and dissolve it in 310 g of water, and adjust the pH to 11 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 34.08 g (0.25 mol) of zinc chloride was dissolved in 340 g of water to obtain a zinc chloride solution.

在常温搅拌下，将氯化锌水溶液慢慢滴加到混合酸溶液中，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120℃下真空烘干，得到产品Zn(O ₃PH) _0.37(O ₃PPh) _0.63。 Under normal temperature stirring, a zinc chloride aqueous solution was slowly added dropwise to the mixed acid solution to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and dried under vacuum at 120 ° C to obtain the product Zn (O ₃ PH) _0.37 (O ₃ PPh) _0.63 .

对样品进行 ³¹P NMR测试：将固体样品溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR表明亚磷酸和苯膦酸的比例为0.37:0.63。 The sample was subjected to ³¹ P NMR test: the solid sample was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR, the ratio of phosphorous acid and phenylphosphonic acid was 0.37: 0.63.

对样品进行XRD测试，所得XRD测定的层间距为

实施例4 Zn(O ₃PH) _0.19(O ₃PPh) _0.81的制备 Example 4 Preparation of Zn (O ₃ PH) _0.19 (O ₃ PPh) _0.81

取33.20克(0.21摩尔)苯膦酸和5.74克(0.070摩尔)亚磷酸溶解于443克水中，用5％的氢氧化钠水溶液调至pH＝11，得到混合酸溶液。另取38.16克(0.28摩尔)氯化锌溶于380克水中，得到氯化锌溶液。33.20 g (0.21 mol) of phenylphosphonic acid and 5.74 g (0.070 mol) of phosphorous acid were dissolved in 443 g of water, and adjusted to pH = 11 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 38.16 g (0.28 mol) of zinc chloride was dissolved in 380 g of water to obtain a zinc chloride solution.

在常温搅拌下，将氯化锌水溶液慢慢滴加到混合酸溶液中，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120度下真空烘干，得到产品Zn(O ₃PH) _0.19(O ₃PPh) _0.81。 Under normal temperature stirring, a zinc chloride aqueous solution was slowly added dropwise to the mixed acid solution to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and vacuum-dried at 120 degrees to obtain the product Zn (O ₃ PH) _0.19 (O ₃ PPh) _0.81 .

对样品进行 ³¹P NMR测试：将固体样品溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR表明亚磷酸和苯膦酸的比例为0.19:0.81。 The sample was subjected to ³¹ P NMR test: the solid sample was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR, the ratio of phosphorous acid and phenylphosphonic acid was 0.19: 0.81.

对样品进行XRD测试，所得XRD测定的层间距为

实施例5 Zn(O ₃PH) _0.68(O ₃PPh) _0.32的制备 Example 5 Preparation of Zn (O ₃ PH) _0.68 (O ₃ PPh) _0.32

取15.80克(0.10摩尔)苯膦酸和20.50克(0.25摩尔)亚磷酸溶解于350克水中，用5％的氢氧化钠水溶液调至pH＝11，得到混合酸溶液。另取47.71克(0.35摩尔)氯化锌溶于477克水中，得到氯化锌溶液。15.80 g (0.10 mole) of phenylphosphonic acid and 20.50 g (0.25 mole) of phosphorous acid were dissolved in 350 g of water, and adjusted to pH = 11 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 47.71 g (0.35 mol) of zinc chloride was dissolved in 477 g of water to obtain a zinc chloride solution.

在常温搅拌下，将氯化锌水溶液慢慢滴加到混合酸溶液中，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120℃下真空烘干，得到产品Zn(O ₃PH) _0.68(O ₃PPh) _0.32。 Under normal temperature stirring, a zinc chloride aqueous solution was slowly added dropwise to the mixed acid solution to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. The product was then dried in a vacuum oven at 120 ° C. to obtain Zn (O ₃ PH) _0.68 (O ₃ PPh) _0.32 .

对样品进行 ³¹P NMR测试：将固体样品溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR表明亚磷酸和苯膦酸的比例为0.68:0.32。 The sample was subjected to ³¹ P NMR test: the solid sample was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR, the ratio of phosphorous acid and phenylphosphonic acid was 0.68: 0.32.

对样品进行XRD测试，所得XRD测定的层间距为

实施例6 Ca(O ₃PH) _0.51(O ₃PPh) _0.49的制备 Example 6 Preparation of Ca (O ₃ PH) _0.51 (O ₃ PPh) _0.49

取22.13克(0.14摩尔)苯膦酸和11.48克(0.14摩尔)亚磷酸溶解于330克水中，用5％的氢氧化钠水溶液调至pH＝11，得到混合酸溶液。另取31.08克(0.28摩尔)氯化钙溶于310克水中，得到氯化锌溶液。22.13 g (0.14 mol) of phenylphosphonic acid and 11.48 g (0.14 mol) of phosphorous acid were dissolved in 330 g of water, and adjusted to pH = 11 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 31.08 g (0.28 mol) of calcium chloride was dissolved in 310 g of water to obtain a zinc chloride solution.

在常温搅拌下，将氯化钙水溶液慢慢滴加到混合酸溶液中，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120℃下真空烘干，得到产品Ca(O ₃PH) _0.51(O ₃PPh) _0.49。 Under normal temperature stirring, an aqueous calcium chloride solution was slowly added dropwise to the mixed acid solution to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and dried under vacuum at 120 ° C to obtain Ca (O ₃ PH) _0.51 (O ₃ PPh) _0.49 .

对样品进行 ³¹P NMR测试：将固体样品溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR表明亚磷酸和苯膦酸的比例为0.51:0.49。 The sample was subjected to ³¹ P NMR test: the solid sample was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR, the ratio of phosphorous acid and phenylphosphonic acid was 0.51: 0.49.

对样品进行XRD测试，所得XRD测定的层间距为

实施例7 Mg(O ₃PH) _0.35(O ₃PPh) _0.65的制备 Example 7 Preparation of Mg (O ₃ PH) _0.35 (O ₃ PPh) _0.65

取15.81克(0.10摩尔)苯膦酸和8.20克(0.10摩尔)亚磷酸溶解于350克水中，用5％的氢氧化钠水溶液调至pH＝8.5，得到混合酸溶液。另取24.07克(0.20摩尔)硫酸镁溶于240克水中，得到硫酸镁溶液。15.81 g (0.10 mol) of phenylphosphonic acid and 8.20 g (0.10 mol) of phosphorous acid were dissolved in 350 g of water, and adjusted to pH = 8.5 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 24.07 g (0.20 mol) of magnesium sulfate was dissolved in 240 g of water to obtain a magnesium sulfate solution.

在70℃下将硫酸镁溶液滴加到混合酸溶液中。滴加结束之后升温至回流，搅拌2小时，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120℃下真空烘干，得到的分产品Mg(O ₃PH) _0.35(O ₃PPh) _0.65。 The magnesium sulfate solution was added dropwise to the mixed acid solution at 70 ° C. After completion of the dropwise addition, the temperature was raised to reflux and stirred for 2 hours to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and vacuum-dried at 120 ° C. The obtained fraction Mg (O ₃ PH) _0.35 (O ₃ PPh) _0.65 .

对样品进行 ³¹P NMR测试：将固体样品溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR表明亚磷酸和苯膦酸的比例为0.35:0.65。 The sample was subjected to ³¹ P NMR test: the solid sample was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR, the ratio of phosphorous acid and phenylphosphonic acid was 0.35: 0.65.

对样品进行XRD测试，所得XRD测定的层间距为

实施例8 Zn(O ₃POH) _0.36(O ₃PPh) _0.64的制备 Example 8 Preparation of Zn (O ₃ POH) _0.36 (O ₃ PPh) _0.64

取15.81克(0.10摩尔)苯膦酸和9.80克(0.10摩尔)磷酸溶解于280克水中，用5％的氢氧化钠水溶液调至pH＝8.3，得到混合酸溶液。另取27.26克(0.20摩尔)氯化锌溶于190克水中，得到氯化锌溶液。15.81 g (0.10 mol) of phenylphosphonic acid and 9.80 g (0.10 mol) of phosphoric acid were dissolved in 280 g of water, and adjusted to pH = 8.3 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 27.26 g (0.20 mole) of zinc chloride was dissolved in 190 g of water to obtain a zinc chloride solution.

在室温下将氯化锌溶液滴加到混合酸溶液中。滴加结束之后保持搅拌2小时，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120℃下真空烘干，得到产品Zn(O ₃POH) _0.36(O ₃PPh) _0.64。 The zinc chloride solution was added dropwise to the mixed acid solution at room temperature. After completion of the dropwise addition, stirring was continued for 2 hours to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and vacuum-dried at 120 ° C to obtain the product Zn (O ₃ POH) _0.36 (O ₃ PPh) _0.64 .

对样品进行 ³¹P NMR测试：将固体样品溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR表明磷酸和苯膦酸的比例为0.36:0.64。 The sample was subjected to ³¹ P NMR test: the solid sample was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR, the ratio of phosphoric acid and phenylphosphonic acid was 0.36: 0.64.

对样品进行XRD测试，所得XRD测定的层间距为

实施例9 Mg(O ₃POH) _0.49(O ₃PPh) _0.51的制备 Example 9 Preparation of Mg (O ₃ POH) _0.49 (O ₃ PPh) _0.51

取15.81克(0.10摩尔)苯膦酸和9.80克(0.10摩尔)磷酸溶解于280克水中，用5％的氢氧化钠水溶液调至pH＝8.3，得到混合酸溶液。另取19.04克(0.20摩尔)氯化镁溶于190克水中，得到氯化镁溶液。15.81 g (0.10 mol) of phenylphosphonic acid and 9.80 g (0.10 mol) of phosphoric acid were dissolved in 280 g of water, and adjusted to pH = 8.3 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 19.04 g (0.20 mol) of magnesium chloride was dissolved in 190 g of water to obtain a magnesium chloride solution.

在室温下将氯化镁水溶液滴加到混合酸溶液中。滴加结束之后保持搅拌2小时，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120℃下真空烘干，得到产品Mg(O ₃POH) _0.49(O ₃PPh) _0.51。 An aqueous magnesium chloride solution was added dropwise to the mixed acid solution at room temperature. After completion of the dropwise addition, stirring was continued for 2 hours to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and vacuum-dried at 120 ° C to obtain the product Mg (O ₃ POH) _0.49 (O ₃ PPh) _0.51 .

对样品进行 ³¹P NMR测试：将固体样品溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR表明磷酸和苯膦酸的比例为0.49:0.51。 The ³¹ P NMR test was performed on the sample: the solid sample was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR, the ratio of phosphoric acid and phenylphosphonic acid was 0.49: 0.51.

对样品进行XRD测试，所得XRD测定的层间距为

实施例10 Ca(O ₃POH) _0.50(O ₃PPh) _0.50的制备 Example 10 Preparation of Ca (O ₃ POH) _0.50 (O ₃ PPh) _0.50

取15.81克(0.10摩尔)苯膦酸和9.80克(0.10摩尔)磷酸溶解于280克水中，用5％的氢氧化钠水溶液调至pH＝8.3，得到混合酸溶液。另取22.20克(0.20摩尔)氯化钙溶于190克水中，得到氯化钙溶液。15.81 g (0.10 mol) of phenylphosphonic acid and 9.80 g (0.10 mol) of phosphoric acid were dissolved in 280 g of water, and adjusted to pH = 8.3 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 22.20 g (0.20 mol) of calcium chloride was dissolved in 190 g of water to obtain a calcium chloride solution.

在室温下将氯化钙水溶液滴加到混合酸溶液中。滴加结束之后保持搅拌2小时，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120℃下真空烘干，得到产品Ca(O ₃POH) _0.50(O ₃PPh) _0.50。 An aqueous calcium chloride solution was added dropwise to the mixed acid solution at room temperature. After completion of the dropwise addition, stirring was continued for 2 hours to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and dried under vacuum at 120 ° C to obtain the product Ca (O ₃ POH) _0.50 (O ₃ PPh) _0.50 .

对样品进行 ³¹P NMR测试：将固体样品溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR表明磷酸和苯膦酸的比例为0.50:0.50。 The ³¹ P NMR test was performed on the sample: the solid sample was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR, the ratio of phosphoric acid and phenylphosphonic acid was 0.50: 0.50.

对样品进行XRD测试，所得XRD测定的层间距为

实施例11 Zn _0.58Ca _0.42(O ₃PH) _0.45(O ₃PPh) _0.55的制备 Example 11 Preparation of Zn _0.58 Ca _0.42 (O ₃ PH) _0.45 (O ₃ PPh) _0.55

取23.71克(0.15摩尔)苯膦酸和12.30克(0.15摩尔)亚磷酸溶解于250克水中，用5％的氢氧化钠水溶液调至pH＝11，得到混合酸溶液。另取16.65克(0.15摩尔)氯化钙和20.44克(0.15摩尔)氯化锌溶于360克水中，得到氯化锌、氯化钙混合溶液。将氯化锌、氯化钙混合溶液慢慢滴加到混合酸溶液中，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体分。随后置于真空烘箱中在120℃下真空烘干，得到的分产品Zn _0.58Ca _0.42(O ₃PH) _0.45(O ₃PPh) _0.55。 Take 23.71 g (0.15 mol) of phenylphosphonic acid and 12.30 g (0.15 mol) of phosphorous acid and dissolve them in 250 g of water, and adjust the pH to 11 with a 5% sodium hydroxide aqueous solution to obtain a mixed acid solution. Another 16.65 g (0.15 mole) of calcium chloride and 20.44 g (0.15 mole) of zinc chloride were dissolved in 360 g of water to obtain a mixed solution of zinc chloride and calcium chloride. A mixed solution of zinc chloride and calcium chloride was slowly added dropwise to the mixed acid solution to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to obtain a white solid. It was then placed in a vacuum oven and vacuum-dried at 120 ° C. The obtained Zn _0.58 Ca _0.42 (O ₃ PH) _0.45 (O ₃ PPh) _{0.55 was obtained} .

对样品进行 ³¹P NMR测试：将固体样品溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR表明亚磷酸和苯膦酸的比例为0.45:0.55。 The sample was subjected to ³¹ P NMR test: the solid sample was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR, the ratio of phosphorous acid and phenylphosphonic acid was 0.45: 0.55.

对样品进行XRD测试，所得XRF测定Zn/Ca摩尔比例为0.58/0.42。XRD测定的层间距为11.071A。An XRD test was performed on the sample, and the obtained XRF determined that the Zn / Ca molar ratio was 0.58 / 0.42. The interlayer distance measured by XRD was 11.071A.

对比例1 Zn(O ₃PPh)的制备 Comparative Example 1 Preparation of Zn (O ₃ PPh)

取39.52克(0.25摩尔)苯膦酸溶解于356克水中，用10％的氢氧化钠水溶液调至pH＝11。另取34.08克(0.25摩尔)氯化锌溶于307克水中。39.52 g (0.25 mol) of phenylphosphonic acid was dissolved in 356 g of water, and the pH was adjusted to 11 with a 10% aqueous sodium hydroxide solution. Another 34.08 g (0.25 mole) of zinc chloride was dissolved in 307 g of water.

将氯化锌水溶液慢慢滴加到由苯膦酸配制的溶液中，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120度下真空烘干，得到产品Zn(O ₃PPh)。 A zinc chloride aqueous solution was slowly added dropwise to a solution prepared with phenylphosphonic acid to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and dried under vacuum at 120 degrees to obtain the product Zn (O ₃ PPh).

对样品进行XRD测试，所得XRD测定的层间距为

对比例2 Zn(O ₃PH)的制备 Comparative Example 2 Preparation of Zn (O ₃ PH)

取16.40克(0.20摩尔)亚磷酸溶解于148克水中，用10％的氢氧化钠水溶液调至pH＝11。另取27.26克(0.20摩尔)氯化锌溶于245克水中。16.40 g (0.20 mol) of phosphorous acid was dissolved in 148 g of water, and the pH was adjusted to 11 with a 10% sodium hydroxide aqueous solution. Another 27.26 grams (0.20 mole) of zinc chloride was dissolved in 245 grams of water.

将氯化锌水溶液慢慢滴加到由亚磷酸配制的溶液中，得到白色沉淀物。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120℃下真空烘干得到产品Zn(O ₃PH)。 A zinc chloride aqueous solution was slowly added dropwise to a solution prepared with phosphorous acid to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and vacuum-dried at 120 ° C to obtain the product Zn (O ₃ PH).

对样品进行XRD测试，所得XRD测定的层间距为

对比例3 Zn(O ₃PH) _0.73(O ₃PPh) _0.27的制备 Comparative Example 3 Preparation of Zn (O ₃ PH) _0.73 (O ₃ PPh) _0.27

取11.07克(0.070摩尔)苯膦酸和17.22克(0.21摩尔)亚磷酸溶解于443克水中，用5％的氢氧化钠水溶液调至pH＝11。另取38.16克(0.28摩尔)氯化锌溶于380克水中。Take 11.07 grams (0.070 moles) of phenylphosphonic acid and 17.22 grams (0.21 moles) of phosphorous acid and dissolve them in 443 grams of water, and adjust the pH to 11 with a 5% sodium hydroxide aqueous solution. Another 38.16 g (0.28 mol) of zinc chloride was dissolved in 380 g of water.

将氯化锌水溶液慢慢滴加到由混合酸配制的溶液中，得到白色沉淀。经抽滤去除溶剂，得到滤饼用乙醇洗涤得到白色固体。随后置于真空烘箱中在120度下真空烘干，得到体产品Zn(O ₃PH) _0.73(O ₃PPh) _0.27。 A zinc chloride aqueous solution was slowly added dropwise to a solution prepared from a mixed acid to obtain a white precipitate. The solvent was removed by suction filtration, and the filter cake was washed with ethanol to give a white solid. It was then placed in a vacuum oven and dried under vacuum at 120 degrees to obtain the bulk product Zn (O ₃ PH) _0.73 (O ₃ PPh) _0.27 .

对样品进行 ³¹P NMR测试：将固体样品溶解于浓盐酸中，按前述核磁共振测试方法进行NMR测试，由所得 ³¹P NMR表明亚磷酸和苯膦酸的比例为0.73:0.27。 The sample was subjected to ³¹ P NMR test: the solid sample was dissolved in concentrated hydrochloric acid, and the NMR test was performed according to the aforementioned nuclear magnetic resonance test method. From the obtained ³¹ P NMR, the ratio of phosphorous acid and phenylphosphonic acid was 0.73: 0.27.

对样品进行XRD测试，所得XRD测定的层间距为

由 ³¹P NMR结果可知，所得产物中苯基膦酸含量太低。同时结合XRD结果可知，产物中亚磷酸金属盐、芳基膦酸金属盐仅为物理混合物，而不具有单一相层状结构。 From the ³¹ P NMR results, it was found that the phenylphosphonic acid content in the obtained product was too low. At the same time combined with XRD results, it can be known that the metal phosphite and arylphosphonic acid metal salts in the product are only physical mixtures, and do not have a single-phase layered structure.

实施例12 高分子材料阻燃性能测试实验和析出Example 12 Testing Experiment and Precipitation of Flame Retardant Performance of Polymer Materials

1)、按照GB/T 2408-2008标准中的方法对样品的阻燃性能(燃烧测试标准)进行测定。1) The flame retardant performance (flame test standard) of the sample was measured according to the method in GB / T 2408-2008 standard.

按UL94(Underwriter实验室)评定高分子材料的消防等级。According to UL94 (Underwriter Laboratory), the fire rating of polymer materials is evaluated.

根据UL 94得出如下消防等级：According to UL 94, the following fire rating is obtained:

V-0级为不超过10秒的续燃，10次点火的续燃时间总和不大于50秒，没有燃烧滴落，试样没有完全燃尽，点火结束之后大于30秒无试样残炽；The V-0 level is the afterburning not exceeding 10 seconds, the sum of the afterburning time of 10 ignitions is not more than 50 seconds, there is no burning dripping, the sample is not completely burned out, and there is no sample remaining after 30 seconds of ignition;

V-1级为点火结束后续燃时间不超过30秒，10次点火的总续燃时间不超过250秒，点火结束后大于60秒无试样残炽，其余标准同V-0的情况；The V-1 level means that the ignition time after ignition is no more than 30 seconds, the total afterburning time of 10 ignitions is not more than 250 seconds, and there is no sample remaining after more than 60 seconds after ignition, the rest of the standards are the same as V-0;

V-2级为通过燃烧滴落引燃棉花，其余标准同V-1的情况；V-2 is for igniting cotton by burning drips, the rest of the standards are the same as V-1;

不可分级的(nkl)：不满足消防等级V-2。Non-gradable (nkl): Does not meet fire rating V-2.

2)、析出性能测试：将试样放置于温度为85℃湿度为85％的恒温烘箱里7天，然后取出晾干表面。如有白霜，即为阻燃体系析出。析出性用“+”的多少表示，“+”越多，析出越多。2) Precipitation performance test: Place the sample in a constant temperature oven with a temperature of 85 ° C and a humidity of 85% for 7 days, and then remove the surface to dry. If there is white frost, it is the precipitation of flame retardant system. The precipitation is expressed by the number of "+", the more "+", the more precipitation.

一个+号代表基本没有析出；2个+号表示有明显析出；3个+号表示析出严重。A + sign indicates that there is almost no precipitation; 2 + signs indicate that there is significant precipitation; 3 + signs indicate that the precipitation is severe.

实施例13Example 13

将聚酰胺PA66、DePAl、实施例1的产品(Zn(O ₃PH) _0.44(O ₃PPh) _0.56)和复配抗氧剂按照81.6：14：4：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。 Polyamide PA66, DePAl, the product of Example 1 (Zn (O ₃ PH) _0.44 (O ₃ PPh) _0.56 ), and a compounded antioxidant were weighted at a ratio of 81.6: 14: 4: 0.4 at a speed of 50 revolutions. Mix in an internal mixer / minute, set the temperature to 280 ° C, and take it out for cooling and drying after 5 minutes.

然后将其填充于模具中，在280℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试。It was then filled in a mold, preheated for 10 minutes at a plate vulcanizer at 280 ° C, and held at 10 MPa for 5 minutes, followed by cold pressing. Cut samples and test after cooling.

按实施例12中的方法，测试阻燃高分子材料的阻燃性能和抗析出性能：试样厚度1.6mm，阻燃级别为V-0；析出性为+。According to the method in Example 12, the flame retardancy and precipitation resistance of the flame-retardant polymer material were tested: the thickness of the sample was 1.6 mm, and the flame retardancy was V-0; the precipitation was +.

实施例14Example 14

将聚酰胺PA66、DePAl、实施例3的产品(Zn(O ₃PH) _0.37(O ₃PPh) _0.63)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为 280℃，5分钟后取出冷却、干燥。 Polyamide PA66, DePAl, the product of Example 3 (Zn (O ₃ PH) _0.37 (O ₃ PPh) _0.63 ), and a compounded antioxidant were used at a weight ratio of 82.6: 14: 3: 0.4 at a speed of 50 revolutions. Mix in an internal mixer / minute, set the temperature to 280 ° C, and take it out for cooling and drying after 5 minutes.

实施例15Example 15

将聚酰胺PA66、DePAl、实施例5的产品(Zn(O ₃PH) _0.68(O ₃PPh) _0.32)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。 Polyamide PA66, DePAl, the product of Example 5 (Zn (O ₃ PH) _0.68 (O ₃ PPh) _0.32 ), and a compounded antioxidant were weighted at 82.6: 14: 3: 0.4 at a rotation speed of 50 revolutions. Mix in an internal mixer / minute, set the temperature to 280 ° C, and take it out for cooling and drying after 5 minutes.

实施例16Example 16

将聚酰胺PA66、DePAl、实施例7的产品(Mg(O ₃PH) _0.35(O ₃PPh) _0.65)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。 Polyamide PA66, DePAl, the product of Example 7 (Mg (O ₃ PH) _0.35 (O ₃ PPh) _0.65 ), and a compounded antioxidant were used at a weight ratio of 82.6: 14: 3: 0.4 at a speed of 50 revolutions. Mix in an internal mixer / minute, set the temperature to 280 ° C, and take it out for cooling and drying after 5 minutes.

实施例17Example 17

将聚酰胺PA66、DePAl、实施例8的产品(Zn(O ₃POH) _0.36(O ₃PPh) _0.64)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。 Polyamide PA66, DePAl, the product of Example 8 (Zn (O ₃ POH) _0.36 (O ₃ PPh) _0.64 ), and a compounded antioxidant were weighted at 82.6: 14: 3: 0.4 at a rotation speed of 50 revolutions. Mix in an internal mixer / minute, set the temperature to 280 ° C, and take it out for cooling and drying after 5 minutes.

实施例18Example 18

将聚酰胺PA66、DePAl、实施例9的产品(Mg(O ₃POH) _0.49(O ₃PPh) _0.51)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。 Polyamide PA66, DePAl, the product of Example 9 (Mg (O ₃ POH) _0.49 (O ₃ PPh) _0.51 ), and a compounded antioxidant were used at a weight ratio of 82.6: 14: 3: 0.4 at a speed of 50 revolutions. Mix in an internal mixer / minute, set the temperature to 280 ° C, and take it out for cooling and drying after 5 minutes.

按实施例12中的方法，测试阻燃高分子材料的阻燃性能抗析出性能：试样厚度1.6mm，阻燃级别为V-0；析出性为+。The method of Example 12 was used to test the flame retardancy and precipitation resistance of the flame-retardant polymer material: the thickness of the sample was 1.6 mm, the flame retardancy was V-0, and the precipitation was +.

实施例19Example 19

将聚酰胺PA66、DePAl、实施例11的产品(Zn _0.58Ca _0.42(O ₃PH) _0.45(O ₃PPh) _0.55)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。 The polyamide PA66, DePAl, the product of Example 11 (Zn _0.58 Ca _0.42 (O ₃ PH) _0.45 (O ₃ PPh) _0.55 ) and the compounded antioxidant were mixed at a weight ratio of 82.6: 14: 3: 0.4 at a speed of Mix in an internal mixer at a speed of 50 rpm, set the temperature to 280 ° C, and take it out for cooling and drying after 5 minutes.

实施例20Example 20

将聚酰胺PA6、DePAl、实施例2的产品(Zn(O ₃PH) _0.57(O ₃PPh) _0.43)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为250℃，5分钟后取出冷却、干燥。 Polyamide PA6, DePAl, the product of Example 2 (Zn (O ₃ PH) _0.57 (O ₃ PPh) _0.43 ), and a compounded antioxidant were weighted at a ratio of 82.6: 14: 3: 0.4 at a speed of 50 revolutions. Mix in a mixer / min, set the temperature to 250 ° C, and take it out for cooling and drying after 5 minutes.

然后将其填充于模具中，在250℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试料。Then, it was filled in a mold, preheated for 10 minutes at a plate vulcanizing machine at 250 ° C., and held at 10 MPa for 5 minutes, followed by cold pressing. Cut samples and test materials after cooling.

实施例21Example 21

将聚酯PBT、DePAl、实施例4的产品(Zn(O ₃PH) _0.19(O ₃PPh) _0.81)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为250℃，5分钟后取出冷却、干燥。 Polyester PBT, DePAl, the product of Example 4 (Zn (O ₃ PH) _0.19 (O ₃ PPh) _0.81 ), and a compounded antioxidant were used at a weight ratio of 82.6: 14: 3: 0.4 at a speed of 50 revolutions. Mix in a mixer / min, set the temperature to 250 ° C, and take it out for cooling and drying after 5 minutes.

然后将其填充于模具中，在250℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试。Then, it was filled in a mold, preheated for 10 minutes at a plate vulcanizing machine at 250 ° C., and held at 10 MPa for 5 minutes, followed by cold pressing. Cut samples and test after cooling.

按实施例12中的方法，测试阻燃高分子材料的阻燃性能和抗析出性能：试样厚度1.6mm，的阻燃级别为V-0；析出性为+。According to the method in Example 12, the flame retardancy and precipitation resistance of the flame-retardant polymer material were tested: the thickness of the sample was 1.6 mm, and the flame retardancy was V-0; the precipitation was +.

实施例22Example 22

将聚酯PBT、DePAl、实施例6的产品(Ca(O ₃PH) _0.51(O ₃PPh) _0.49)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为250℃，5分钟后取出冷却、干燥。 Polyester PBT, DePAl, the product of Example 6 (Ca (O ₃ PH) _0.51 (O ₃ PPh) _0.49 ), and a compounded antioxidant were weighted at 82.6: 14: 3: 0.4 at a speed of 50 revolutions. Mix in a mixer / min, set the temperature to 250 ° C, and take it out for cooling and drying after 5 minutes.

然后将其填充于模具中，在250℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试。按实施例12中的方法，测试阻燃高分子材料的阻燃性能和抗析出性能：试样厚度1.6mm，阻燃级别为V-0；析出性为+。Then, it was filled in a mold, preheated for 10 minutes at a plate vulcanizing machine at 250 ° C., and held at 10 MPa for 5 minutes, followed by cold pressing. Cut samples and test after cooling. According to the method in Example 12, the flame retardancy and precipitation resistance of the flame-retardant polymer material were tested: the thickness of the sample was 1.6 mm, and the flame retardancy was V-0; the precipitation was +.

实施例23Example 23

将聚酯PBT、DePAl、实施例10的产品(Ca(O ₃POH) _0.50(O ₃PPh) _0.50)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为250℃，5分钟后取出冷却、干燥。 Polyester PBT, DePAl, the product of Example 10 (Ca (O ₃ POH) _0.50 (O ₃ PPh) _0.50 ), and a compounded antioxidant were used at a weight ratio of 82.6: 14: 3: 0.4 at a speed of 50 revolutions. Mix in a mixer / min, set the temperature to 250 ° C, and take it out for cooling and drying after 5 minutes.

实施例24Example 24

将聚酰胺PA66、DePAl、实施例7(Mg(O ₃PH) _0.35(O ₃PPh) _0.65)的产品和复配抗氧剂按照78.6：20：1：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为 280℃，5分钟后取出冷却、干燥。 The polyamide PA66, DePAl, the product of Example 7 (Mg (O ₃ PH) _0.35 (O ₃ PPh) _0.65 ), and the compounded antioxidant were weighted at a speed ratio of 78.6: 20: 1: 0.4 at a speed of 50 revolutions. Mix in an internal mixer / minute, set the temperature to 280 ° C, and take it out for cooling and drying after 5 minutes.

对比例4Comparative Example 4

将聚酰胺PA66、DePAl、对比例1的产品(ZnO ₃PPh)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。 The polyamide PA66, DePAl, the product of Comparative Example 1 (ZnO ₃ PPh) and the compounded antioxidant were mixed in an internal mixer at a speed of 50 rpm in a weight ratio of 82.6: 14: 3: 0.4 and set. The temperature was 280 ° C. After 5 minutes, it was taken out to cool and dry.

按实施例12中的方法，测试阻燃高分子材料的阻燃性能和抗析出性能：试样厚度1.6mm，阻燃级别为无级别；析出性为+。According to the method in Example 12, the flame retardancy and precipitation resistance of the flame-retardant polymer material were tested: the thickness of the sample was 1.6 mm, the flame retardancy level was no level, and the precipitation was +.

对比例5Comparative Example 5

将聚酰胺PA66、DePAl、对比例2的产品(ZnO ₃PH)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。 The polyamide PA66, DePAl, the product of Comparative Example 2 (ZnO ₃ PH), and the compounded antioxidant were mixed in an internal mixer with a rotation speed of 50 rpm in a weight ratio of 82.6: 14: 3: 0.4 and set. The temperature was 280 ° C. After 5 minutes, it was taken out to cool and dry.

按实施例12中的方法，测试阻燃高分子材料的阻燃性能和抗析出性能：试样厚度1.6mm，阻燃级别为V-0；析出性为+++。According to the method in Example 12, the flame retardancy and precipitation resistance of the flame-retardant polymer material were tested: the thickness of the sample was 1.6 mm, and the flame retardancy was V-0; the precipitation was +++.

对比例6Comparative Example 6

将聚酯PBT-2、DePAl、Mg ₃(PO ₄) ₂和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为250℃，5分钟后取出冷却、干燥。 The polyester PBT-2, DePAl, Mg ₃ (PO ₄ ) ₂ and the compounded antioxidant were mixed in an internal mixer with a rotation speed of 50 rpm at a weight ratio of 82.6: 14: 3: 0.4, and the temperature was set. The temperature was 250 ° C. After 5 minutes, it was taken out and cooled and dried.

按实施例12中的方法，测试阻燃高分子材料的阻燃性能和抗析出性能：试样厚度1.6mm，阻燃级别为无级别；析出性为+++。According to the method in Example 12, the flame retardancy and precipitation resistance of the flame-retardant polymer material were tested: the thickness of the sample was 1.6 mm, the flame retardancy level was no level, and the precipitation was +++.

对比例7Comparative Example 7

将聚酰胺PA66、DePAl、对比例3的产品(Zn(O ₃PH) _0.73(O ₃PPh) _0.27)和复配抗氧剂按照82.6：14：3：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。 The polyamide PA66, DePAl, the product of Comparative Example 3 (Zn (O ₃ PH) _0.73 (O ₃ PPh) _0.27 ) and the compounded antioxidant were weighted at 82.6: 14: 3: 0.4 at a speed of 50 revolutions. Mix in an internal mixer / minute, set the temperature to 280 ° C, and take it out for cooling and drying after 5 minutes.

按实施例12中的方法，测试阻燃高分子材料4的阻燃性能和抗析出性能：试样厚度1.6mm，阻燃级别为V-0；析出性为++。According to the method in Example 12, the flame retardancy and precipitation resistance of the flame-retardant polymer material 4 were tested: the thickness of the sample was 1.6 mm, and the flame retardancy was V-0; the precipitation was ++.

对比例8Comparative Example 8

将聚酰胺PA66、DePAl和复配抗氧剂按照69.6：30：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为280℃，5分钟后取出冷却、干燥。The polyamide PA66, DePAl and the compounded antioxidant were mixed in an internal mixer with a rotation speed of 50 rpm at a weight ratio of 69.6: 30: 0.4, and the set temperature was 280 ° C. After 5 minutes, the mixture was taken out for cooling and drying.

然后将其填充于模具中，在280℃的平板硫化机预热10分钟，10MPa保压5分钟后，冷压。待其冷却后切样、测试。It was then filled in a mold, preheated for 10 minutes at a plate vulcanizer at 280 ° C, and held at 10 MPa for 5 minutes, and then cold-pressed. Cut samples and test after cooling.

按实施例12中的方法，测试阻燃高分子材料5的阻燃性能和抗析出性能：试样厚度1.6mm，阻燃级别为无级别；析出性为+。According to the method in Example 12, the flame retardancy and precipitation resistance of the flame retardant polymer material 5 were tested: the thickness of the sample was 1.6 mm, the flame retardancy level was no level, and the precipitation was +.

对比例9Comparative Example 9

将聚酰胺PA6、DePAl和复配抗氧剂按照79.6：20：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为250℃，5分钟后取出冷却、干燥。The polyamide PA6, DePAl, and the compounded antioxidant were mixed in an internal mixer with a rotation speed of 50 rpm at a weight ratio of 79.6: 20: 0.4, and the temperature was set at 250 ° C. After 5 minutes, the mixture was taken out for cooling and drying.

对比例10Comparative Example 10

将聚酯PBT、DePAl和复配抗氧剂按照83.6：16：0.4的重量比例，在转速为50转/分钟的密炼机中混合，设置温度为250℃，5分钟后取出冷却、干燥。The polyester PBT, DePAl, and the compounded antioxidant were mixed in an internal mixer with a rotation speed of 50 rpm at a weight ratio of 83.6: 16: 0.4, and the temperature was set at 250 ° C. After 5 minutes, the mixture was taken out for cooling and drying.

实施例1～11所得阻燃剂的组分A和对比例1～3中所得产物，所用原料和所得结果列于表2中。The components A of the flame retardants obtained in Examples 1 to 11 and the products obtained in Comparative Examples 1 to 3. The raw materials used and the results obtained are shown in Table 2.

表2Table 2

由表2可见，本发明提供的方法能制备得到具有层状单一相的阻燃剂的组分A，尤其是当化学式I的产物中苯膦酸的比例大于0.3后，所得产物中能具有单一的层相结构。由对比例3可知当苯膦酸的比例小于0.3时，所得产物不具有单一的层相结构。It can be seen from Table 2 that the method provided by the present invention can prepare component A having a layered single phase flame retardant, especially when the proportion of phenylphosphonic acid in the product of Chemical Formula I is greater than 0.3, the resulting product can have a single Layer structure. From Comparative Example 3, it can be known that when the ratio of phenylphosphonic acid is less than 0.3, the obtained product does not have a single layer structure.

实施例13～24以及对比例4～10中制备阻燃高分子材料，所用原料和所得结果列于表3中。The flame-retardant polymer materials were prepared in Examples 13 to 24 and Comparative Examples 4 to 10. The raw materials used and the results obtained are shown in Table 3.

表3table 3

a：未使用阻燃剂的组分A，该质量比为高分子材料、阻燃剂和复配抗氧剂的质量比。a: Component A without a flame retardant, the mass ratio is the mass ratio of the polymer material, the flame retardant and the compounded antioxidant.

b：表3中+号的个数代表高分子材料表面阻燃剂析出程度：一个+号代表基本没有析出；2个+号表示有明显析出；3个+号表示析出严重。b: The number of + signs in Table 3 represents the degree of precipitation of flame retardants on the surface of polymer materials: a + sign means that there is almost no precipitation; 2 + signs indicate obvious precipitation; 3 + signs indicate serious precipitation.

由表3可见，采用本发明提供的组分A能较好的缓解阻燃剂在高分子材料中析出的问题，且所得材料的阻燃性能较好，均可达V-0级。比较实施例和对比例可以得出本发明的阻燃剂在合适的范围内给高分子材料提供了杰出的阻燃性能以及良好的抗析出性能。It can be seen from Table 3 that the use of component A provided by the present invention can better alleviate the problem of the precipitation of flame retardants in polymer materials, and the flame retardancy of the obtained materials is good, which can reach V-0 level. Comparing the examples and the comparative examples, it can be concluded that the flame retardant of the present invention provides the polymer material with excellent flame retardancy and good resistance to precipitation within a suitable range.

作为对比例，对比例4中采用对比例1中不含亚磷酸的产物作为组分A，与二乙基次膦酸铝共同使用时，高分子材料无法发挥阻燃效果。As a comparative example, in Comparative Example 4, the product containing no phosphorous acid in Comparative Example 1 was used as component A. When used together with aluminum diethylphosphinate, the polymer material could not exert the flame retardant effect.

对比例5中采用对比例2中不含苯膦酸的产物作为组分A，与二乙基次膦酸铝共同使用时，虽然能发挥阻燃效果，但阻燃剂析出严重。In Comparative Example 5, the product containing no phenylphosphonic acid in Comparative Example 2 was used as component A. When it was used together with aluminum diethylphosphinate, although the flame retardant effect could be exerted, the precipitation of the flame retardant was serious.

而采用对比例3中所得没有单一层状相结构的产物作为用于阻燃剂的组分A，该组分A中各物质仅为物理混合状态，与二乙基次膦酸铝共同使用时，所得高分子材料4虽然具有阻燃性，但阻燃剂在高分子材料表面析出明显，影响使用感受。Whereas, the product obtained in Comparative Example 3 without a single layered phase structure was used as the component A for the flame retardant, and each substance in the component A was only in a physically mixed state, and when used together with aluminum diethylphosphinate Although the obtained polymer material 4 has flame retardancy, the flame retardant precipitates significantly on the surface of the polymer material and affects the use experience.

而对比例8-10中，未使用组分A，仅使用二乙基次膦酸铝，其中所用无卤阻燃剂在高分子材料中的阻燃效果较差。In Comparative Examples 8-10, component A was not used, and only diethylphosphinate was used. The halogen-free flame retardant used in the polymer material had a poor flame retardancy effect.

比较上述实施例和对比例可以看出，本发明提供的阻燃剂在合适的范围内给高分子材料提供了杰出的阻燃性能以及良好的抗析出性能，与之相比，单纯物理混合阻燃剂(对比例7)，以及单一阻燃剂(对比例5和对比例6)与二乙基次膦酸铝同时使用时，阻燃性能和抗析出性能不能同时兼得。Comparing the above examples and comparative examples, it can be seen that the flame retardant provided by the present invention provides the polymer material with excellent flame retardancy and good anti-precipitation performance within a suitable range. When the flammable agent (Comparative Example 7) and the single flame retardant (Comparative Example 5 and Comparative Example 6) are used together with aluminum diethylphosphinate, the flame retardancy and precipitation resistance cannot be obtained at the same time.

以上所述，仅是本发明的几个实施例，并非对本发明做任何形式的限制，虽然本发明以较佳实施例揭示如上，然而并非用以限制本发明，任何熟悉本专业的技术人员，在不脱离本发明技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。The above are just a few examples of the present invention, and are not intended to limit the present invention in any form. Although the present invention is disclosed in the preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art, Without departing from the scope of the technical solution of the present invention, making some changes or modifications using the technical content disclosed above is equivalent to equivalent implementation cases, and all fall within the scope of the technical solution.

Claims

一种阻燃剂，其特征在于，所述阻燃剂是磷酸-芳基膦酸金属盐和/或亚磷酸-芳基膦酸金属盐；A flame retardant, characterized in that the flame retardant is a phosphoric acid-arylphosphonic acid metal salt and / or a phosphorous acid-arylphosphonic acid metal salt;

所述磷酸-芳基膦酸金属盐和所述亚磷酸-芳基膦酸金属盐均为层状单一相。Both the phosphoric acid-arylphosphonic acid metal salt and the phosphorous acid-arylphosphonic acid metal salt are layered single phases.
根据权利要求1所述的阻燃剂，其特征在于，所述亚磷酸-芳基膦酸金属盐选自具有式I所示化学式的化合物中的至少一种：The flame retardant according to claim 1, wherein the phosphorous acid-arylphosphonic acid metal salt is selected from at least one compound having a chemical formula represented by Formula I:

J(O ₃PH) _x1(O ₃PR ¹) _y1·z ₁H ₂O 式I J (O ₃ PH) _x1 (O ₃ PR ¹ ) _y1z ₁ H ₂ O Formula I

其中，J为至少一种二价金属阳离子，R ¹为芳香基，x ₁+y ₁＝1，0.15<x ₁<0.70，0.30<y ₁<0.85，0≤z ₁<1.2。 Wherein, J is at least one divalent metal cation, R ¹ is an aromatic group, x ₁ + y ₁ = _1, 0.15 <x ₁ <0.70, 0.30 <y ₁ <0.85, and ₀ ≦ z ₁ <1.2.
根据权利要求2所述的阻燃剂，其特征在于，所述式I中0.32≤y ₁≤0.83；0≤z ₁≤1.1；所述J为碱土金属离子或锌离子。 The flame retardant according to claim 2, wherein in formula I, 0.32 ≦ y ₁ ≦ 0.83; 0 ≦ z ₁ ≦ 1.1; and J is an alkaline earth metal ion or zinc ion.
根据权利要求2所述的阻燃剂，其特征在于，所述式I中0.40≤y ₁≤0.81；z ₁为0；所述J为Ca ²⁺、Mg ²⁺、Zn ²⁺中的至少一种；所述R ¹为苯基。 The flame retardant according to claim 2, wherein in formula I, 0.40 ≦ y ₁ ≦ 0.81; z ₁ is 0; and J is at least one of Ca ²⁺ , Mg ²⁺ , and Zn ²⁺ One; the R ¹ is phenyl.
根据权利要求1所述的阻燃剂，其特征在于，所述磷酸-芳基膦酸金属盐选自具有式II所示化学式的化合物中的至少一种：The flame retardant according to claim 1, wherein the phosphoric acid-arylphosphonic acid metal salt is selected from at least one compound having a chemical formula represented by Formula II:

Q(O ₃POH) _x2(O ₃PR ²) _y2·z ₂H ₂O 式II Q (O ₃ POH) _x2 (O ₃ PR ² ) _y2 · z ₂ H ₂ O Formula II

其中，Q为至少一种二价金属阳离子，R ²为芳香基，x ₂+y ₂＝1，0.15<x ₂<0.70，0.30<y ₂<0.85，0≤z ₂<1.2。 Wherein, Q is at least one divalent metal cation, R ² is an aromatic group, x ₂ + y ₂ = 1, 0.15 <x ₂ <0.70, 0.30 <y ₂ <0.85, and ₀ ≦ z ₂ <1.2.
根据权利要求5所述的阻燃剂，其特征在于，所述式II中0.32≤y ₂≤0.83；0≤z ₂≤1.1；所述Q为碱土金属离子或锌离子。 The flame retardant according to claim 5, wherein, in Formula II, 0.32≤y ₂ ≤0.83; 0≤z ₂ ≤1.1; and Q is an alkaline earth metal ion or zinc ion.
根据权利要求5所述的阻燃剂，其特征在于，所述化学式II中0.40≤y ₂≤0.81；z ₂为0；所述Q为Ca ²⁺，Mg ²⁺，Zn ²⁺中的至少一种；所述R ²为苯基。 The flame retardant according to claim 5, wherein in the chemical formula II, 0.40 ≦ y ₂ ≦ 0.81; z ₂ is 0; and Q is at least one of Ca ²⁺ , Mg ²⁺ , and Zn ²⁺ One; the R ² is phenyl.
一种复合阻燃剂，其特征在于，所述复合阻燃剂包括组分A和组分B；A composite flame retardant, characterized in that the composite flame retardant includes component A and component B;

其中，所述组分A选自权利要求1～7中任一项所述的阻燃剂；Wherein, the component A is selected from the flame retardant according to any one of claims 1 to 7;

所述组分B选自二烷基次膦酸盐中的至少一种。The component B is selected from at least one of dialkylphosphinates.
根据权利要求8所述的复合阻燃剂，其特征在于，所述二烷基次膦酸盐选自具有式III所示化学式的化合物或式IV所示化学式的化合物中的至少一种：The composite flame retardant according to claim 8, wherein the dialkylphosphinate is selected from at least one of a compound having a chemical formula represented by Formula III or a compound having a chemical formula represented by Formula IV:

其中，R ₅和R ₆分别独立地选自C ₁～C ₈的烷基； Wherein R ₅ and R ₆ are each independently selected from C ₁ to C ₈ alkyl groups;

G ^m+表示价态为m的金属G离子，m为金属G的价态； G ^{m +} represents a metal G ion having a valence state of m, and m is a valence state of a metal G;

A选自C ₁～C ₁₆的亚烃基； A is selected from C ₁ to C ₁₆ alkylene groups;

R ₇和R ₈分别独立地选自C ₁～C ₈的烷基； R ₇ and R ₈ are each independently selected from C ₁ to C ₈ alkyl groups;

L ^p+表示价态为p的金属L离子，p为金属L的价态。 L ^{p +} represents a metal L ion having a valence state of p, and p is a valence state of the metal L.
根据权利要求9所述的复合阻燃剂，其特征在于，所述金属离子G ^m+和所述金属离子L ^p+分别独立地选自二价金属阳离子、三价金属阳离子中的至少一种； The composite flame retardant according to claim 9, wherein the metal ion Gm ⁺ and the metal ion ^{Lp +} are each independently selected from at least one of a divalent metal cation and a trivalent metal cation;

所述A选自C ₁～C ₅的亚烷基、C ₆～C ₁₀的亚芳香基、烷基取代亚芳香基和芳基取代亚烷基。 The A is selected from a C ₁ to C ₅ alkylene group, a C ₆ to C ₁₀ arylene group, an alkyl substituted arylene group, and an aryl substituted alkylene group.
根据权利要求9所述的复合阻燃剂，其特征在于，所述金属离子G ^m+和所述金属离子L ^p+分别独立地选自Mg ²⁺、Ca ²⁺、Ba ²⁺、Fe ²⁺、Fe ³⁺、Al ³⁺、Zn ²⁺中的至少一种。 The composite flame retardant according to claim 9, wherein the metal ion G ^{m +} and the metal ion L ^{p +} are independently selected from Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Fe ²⁺ , At least one of Fe ³⁺ , Al ³⁺ , and Zn ²⁺ .
根据权利要求8所述的复合阻燃剂，其特征在于，所述组分B选自二乙基次膦酸铝、二乙基次膦酸锌中的至少一种。The composite flame retardant according to claim 8, wherein the component B is selected from at least one of aluminum diethylphosphinate and zinc diethylphosphinate.
根据权利要求8所述的复合阻燃剂，其特征在于，所述组分A与所述组分B的质量比为0.5～10:30～1。The composite flame retardant according to claim 8, wherein a mass ratio of the component A to the component B is 0.5 to 10:30 to 1.
一种阻燃高分子材料，其特征在于，包含权利要求8～13中任一项所述的复合阻燃剂和高分子材料。A flame-retardant polymer material, comprising the composite flame retardant according to any one of claims 8 to 13 and a polymer material.
根据权利要求14所述的阻燃高分子材料，其特征在于，所述复合阻燃剂中的组分A在所述阻燃高分子材料中的质量百分含量为0.5-10wt％。The flame-retardant polymer material according to claim 14, wherein the mass percentage content of component A in the composite flame retardant in the flame-retardant polymer material is 0.5-10 wt%.
根据权利要求14所述的阻燃高分子材料，其特征在于，所述复合阻燃剂中的组分A在所述阻燃高分子材料中的质量百分含量为0.75-8wt％。The flame-retardant polymer material according to claim 14, wherein the mass percentage content of component A in the composite flame retardant in the flame-retardant polymer material is 0.75-8 wt%.
根据权利要求14所述的阻燃高分子材料，其特征在于，所述复合阻燃剂中的组分A在所述阻燃高分子材料中的质量百分含量为1-5wt％。The flame-retardant polymer material according to claim 14, wherein a mass percentage content of the component A in the composite flame retardant in the flame-retardant polymer material is 1 to 5 wt%.
根据权利要求14所述的阻燃高分子材料，其特征在于，所述复合阻燃剂中的组分B在所述阻燃高分子材料中的质量百分含量为10～20wt％。The flame-retardant polymer material according to claim 14, wherein a mass percentage content of the component B in the composite flame retardant in the flame-retardant polymer material is 10 to 20% by weight.
根据权利要求14所述的阻燃高分子材料，其特征在于，所述阻燃高分子材料中还包括功能添加剂，所述功能添加剂选自抗氧剂、增强剂、抗滴落剂、稳定剂、颜料、染料、成炭催化剂、分散剂、成核剂或无机填料中的至少一种。The flame-retardant polymer material according to claim 14, wherein the flame-retardant polymer material further comprises a functional additive selected from the group consisting of an antioxidant, a reinforcing agent, an anti-dripping agent, and a stabilizer , A pigment, a dye, a carbon-forming catalyst, a dispersant, a nucleating agent, or an inorganic filler.
根据权利要求19所述的阻燃高分子材料，其特征在于，所述功能添加剂在所述阻燃高分子材料中的质量百分含量为10～40％。The flame-retardant polymer material according to claim 19, wherein the mass percentage content of the functional additive in the flame-retardant polymer material is 10 to 40%.
根据权利要求14所述的阻燃高分子材料，其特征在于，所述高分子材料选自热塑性高分子材料中的至少一种。The flame-retardant polymer material according to claim 14, wherein the polymer material is at least one selected from thermoplastic polymer materials.
根据权利要求14所述的阻燃高分子材料，其特征在于，所述高分子材料为聚酰胺、聚酯中的至少一种。The flame-retardant polymer material according to claim 14, wherein the polymer material is at least one of polyamide and polyester.
根据权利要求14所述的阻燃高分子材料，其特征在于，所述高分子材料选自聚酰胺6、聚酰胺66、聚对苯二甲酸乙二酯、聚对苯二甲酸丙二酯、聚对苯二甲酸丁二酯中的至少一种。The flame-retardant polymer material according to claim 14, wherein the polymer material is selected from the group consisting of polyamide 6, polyamide 66, polyethylene terephthalate, polytrimethylene terephthalate, At least one of polybutylene terephthalate.