CN105367825B - 膨胀阻燃剂用层状磷酸铝阻燃协效剂、制备方法及组合物 - Google Patents
膨胀阻燃剂用层状磷酸铝阻燃协效剂、制备方法及组合物 Download PDFInfo
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- CN105367825B CN105367825B CN201510885170.7A CN201510885170A CN105367825B CN 105367825 B CN105367825 B CN 105367825B CN 201510885170 A CN201510885170 A CN 201510885170A CN 105367825 B CN105367825 B CN 105367825B
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
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- C08K3/02—Elements
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
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- 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
- C08K7/00—Use of ingredients characterised by shape
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- 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
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- 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
- C08K9/10—Encapsulated ingredients
-
- 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
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
- C08K3/02—Elements
- C08K2003/026—Phosphorus
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Abstract
本发明涉及一种膨胀阻燃剂用的层状磷酸铝阻燃协效剂及组合物，该协效剂采用磷酸、铝源、杂原子源以及脂肪胺反应形成有机‑无机层状磷酸铝，无机骨架是由Al(Me)—O—P—O化学键交替连接而成的无机板层结构，无机板层之间是脂肪胺；无机骨架中，Me为掺杂原子，Me占Me、Al和P总元素摩尔含量的5～20.0％。本协效剂可与磷源、氮源及碳源形成阻燃剂组合物，实验和应用证明利用该组合物作为阻燃剂，在聚丙烯、聚乙烯和聚酰胺中有很好的阻燃效果，与市场上同类产品相比添加较少的量，就能达到相同的阻燃效果。
Description
技术领域
本发明涉及一种膨胀阻燃剂用的层状磷酸铝阻燃协效剂、制备方法及其组合物。
背景技术
众所周知，高分子材料凭借优良的性能，目前已被广泛用于交通、建筑、运输、通信等领域。但高分子材料大多易燃，随着高分子材料应用范围的不断扩大，近年来对高分子材料的阻燃要求越来越高。含氯阻燃剂的阻燃效率高，并且性价比高，长期以来一直作为主要的有机阻燃剂用于高分子材料的阻燃，但燃烧时，卤素阻燃剂分解产生烟、腐蚀性、有毒气体对环境和人们的生命安全造成了严重的影响。因此，卤素阻燃剂必将被其他阻燃剂所取代，开发新型无卤环保阻燃剂成为未来发展的趋势。膨胀阻燃剂(IFR)作为一种新型环境友好型阻燃剂，在世界阻燃领域获得广泛的关注，但这种阻燃剂有很多自身的局限性，如阻燃效率低，与含卤阻燃剂相比所需求的添加量大，导致聚合物力学性能大大降低。因此，常规的膨胀阻燃剂并不能完全满足阻燃聚合物材料的性能需求，近年来，对膨胀阻燃协效剂的研究，已成为研究的热点。
有机-无机层状磷酸铝是一种有独特结构的磷酸盐，采用长链脂肪胺为模板剂，可以得到较大的层间距，并且这种材料的亲有机性，使得磷酸铝在高分子聚合物中有很好的分散性，得到插层或剥离的聚合物纳米复合材料。层状磷酸铝作为一种固体酸催化剂，具有催化成炭作用，增加成炭量，提高碳层品质，从提高高分子聚合物的阻燃性。江赛华等发现有机-无机层状磷酸铝能很好的分散到聚氨酯中，形成剥离的聚氨酯纳米复合材料。添加5％的有机-无机层状磷酸铝可以使聚氨酯的极限氧指数提高5％，峰值热释放速率降低了84.6W/g，储能模量提高了30％。但关于有机-无机层状磷酸铝作为阻燃协效剂用于热塑性塑料从未被报道。虽然层状磷酸铝与粘土结构相似，但没有处理的粘土与聚合物的兼容性较差，因此使用前需要对粘土做有机改性，增大层间距和提高它在高分子聚合物中的兼容性，以便层状粘土在聚合物中达到纳米级分散，制备工艺相对复杂。
发明内容
鉴于现有技术存在的上述问题，本发明提供一种膨胀阻燃剂用的层状磷酸铝阻燃协效剂、制备方法及其组合物。该协效剂采用一步法合成工艺简单，有较高的性价比，与有机高分子材料有很好的兼容性，能够在高分子基体中达到纳米级分散，与膨胀阻燃剂有较好的协效作用，添加少量的该协效剂能明显提高高分子聚合物膨胀阻燃体系阻燃性能和力学性能。
本发明膨胀阻燃剂用的层状磷酸铝阻燃协效剂，是采用磷酸、铝源、杂原子源以及脂肪胺合成的有机-无机层状磷酸铝，无机骨架是由Al(Me)—O—P—O化学键交替连接而成的无机板层结构，层间距d为2.7～4.5nm，无机板层之间是脂肪胺；无机骨架中，Me为掺杂原子，Me占Me、Al和P总元素摩尔含量的5～20.0％。
其中，所述的杂原子Me是B、Mg、Ca、Ti、Mn、Fe、Zn、Ni的一种或者多种。
所述的脂肪胺是含碳为8～18的直链脂肪族伯胺，即，n-CmH2m+1NH2(m＝8～18)。
所述的铝源是氧化铝、醋酸铝、拟薄水铝石、硝酸铝或硫酸铝。
上述层状磷酸铝阻燃协效剂可以与磷源(主成分)、氮源及碳源形成阻燃剂组合物，用于塑料(如聚丙烯、聚乙烯、聚酰胺)的无卤阻燃改性。该阻燃剂组合物中各组分的重量百分含量是：层装磷酸铝协效阻燃剂0.5～10wt％，磷源50～80wt％，氮源0～30wt％，碳源0～30wt％。
该阻燃剂组合物制备工艺为：将层状磷酸铝协效阻燃剂与磷源、碳源、氮源按比例配比后，放进高速混合机中混合均匀，所得即为阻燃剂组合物。
该阻燃剂组合物中，所述的磷源选自二乙基次磷酸铝，聚磷酸铵，硅烷包覆聚磷酸铵，三聚氰胺聚磷酸，红磷，三聚氰胺包覆红磷，甘油磷酸铁(Fe2(C3H5(OH)2PO4)3)，二水磷酸铁(FePO4·2H2O)，甘油磷酸锰(Mn(C3H5(OH)2PO4))，三水磷酸锰(Mn3(PO4)2·3H2O),酸式磷酸锰(Mn(H2PO4)2·2H2O)，甘油磷酸钙(Ca(C3H5(OH)2PO4))中的一种或者多种。
所述的氮源为三聚氰胺、苯代三聚氰胺、胍、氰尿酸三聚氰胺的一种或者多种。
所述的碳源为季戊四醇、壳聚糖、酚醛树脂、环己六醇、丁四醇中的一种或多种。
上述层状磷酸铝协效阻燃剂的制备方法，包括如下步骤：
将铝源与含有杂原子Me的氧化物、氢氧化物、醋酸盐或者硝酸盐分散到水中，搅拌30min，加入浓磷酸，再搅拌1h后倒入脂肪胺，继续搅拌2h得浆料；其中，以下式给出浆料中各物质量的比例：Al:Me:P2O5:脂肪胺:H2O＝1.0:2(1.0-x):1.0:1.0:60.0，x＝1.0～0.8；所述脂肪胺是含碳为8～18的直链脂肪族伯胺；然后，将所得的浆料转移到有聚四氟乙烯内衬的反应釜中，放入100℃的烘箱中反应24h，取出、冷去至室温，抽滤、洗涤、干燥。
所述的杂原子Me是B、Mg、Ca、Ti、Mn、Fe、Zn、Ni的一种或者多种。所述浓磷酸的浓度为85wt％；干燥温度为80℃。
所述铝源是醋酸铝、拟薄水铝石、硝酸铝、或硫酸铝或氧化铝。
本发明阻燃协效剂采用超分子自组装技术，以脂肪胺为模板剂，一步法合成有机-无机层状磷酸铝。这类层状磷酸铝的共同特点为由一系列片层结构按一定的方式堆积起来，层内存在强的共价键，但层与层之间的作用力为较弱的氢键或离子键，并且有机模板剂的存在，使层状磷酸铝具有较大的层间距和亲有机性，这易于磷酸铝在高分子基体中分散和高分子链进入层间，得到插层甚至剥离的纳米聚合物复合材料。
层状磷酸铝分子筛开放骨架机构由Al中心多面体和P中心多面体组成，Al和P原子可以被杂原子取代，得到杂原子取代的磷酸铝分子筛。可以掺入磷酸铝的杂原子种类很多，包括Li、Be、B、Mg、Si、Ga、Ti、Mn、Fe、Zn、Ni、Cu等。磷酸铝材料中杂原子的加入可以为分子筛带来布朗酸性位点和催化活性中心，这有利于聚合物催化脱氢、交联成炭，促进炭层提早出现和提高炭层的致密性和稳定性，这有利于阻燃性能的提高。
本发明有机-无机层状磷酸铝制备方法中采用水作为溶剂，成本较低；作为地壳中含量最多的金属元素，磷酸铝的性价比要比其它膨胀阻燃协效剂要高，如氧化镧、氧化铁、含镍催化剂等。
本方法制备的有机-无机层状磷酸铝没有硬颗粒存在，使用前无需研磨、粉碎等处理，制备工艺交简单。
本发明层状磷酸铝阻燃协效剂可以与磷源、氮源及碳源形成阻燃剂组合物。大量的实验和应用证明：利用该组合物作为阻燃剂，在聚丙烯、聚乙烯和聚酰胺中有很好的阻燃效果，与市场上同类产品相比添加较少的量，就能达到相同的阻燃效果(如添加20％，聚合物塑料的UL-94就能达到V-00)。并且有机-无机层状磷酸铝的存在明显提高了材料的机械性能和加工性能。
附图说明
图1为本发明有机-无机层状磷酸铝结构示意图；
图2为LABP-C12与LAP-C12的热重结果；
图3为LAP-Cn X射线衍射测试结果；
图4表示LAP-Cn(n＝8，12，18)在PP中的状态；
图5表示0-2.0wt.％LABP-C12在PA66中的分散状态(PA66/LABP-C12-2.0wt.％)。
具体实施方式
以下结合实施例对本发明详细说明。
参照结构示意图1，本发明阻燃协效剂是采用磷酸、铝源、掺杂原子源以及脂肪胺合成的有机-无机层装磷酸铝，其中，无机骨架是由Al(Me)—O—P—O化学键交替连接而成的无机板层结构，层间距d为2.7-4.5nm，无机板层之间是脂肪胺；无机骨架中Me为杂原子，Me占Me、Al和P总元素摩尔含量的5～20.0％。所述杂原子Me为B、Mg、Ca、Ti、Mn、Fe、Zn、Ni的一种或者多种。所述脂肪胺是含碳为8～18的直链脂肪族伯胺，
以下所列的数据都是质量百分含量；有机-无机层状磷酸铝用LAP-Cm(m＝8-18)表示，其中Cm指n-CmH2m+1NH2(m＝8-18)；其它元素掺杂的层状磷酸铝用LAMeP-Cn表示，其中，Me为掺杂原子符号。浆料中物质量的比例以下式表示：Al:Me:P2O5:伯胺:H2O＝1.0:2(1.0-x):1.0:1.0:60.0，x＝1.0～0.8。下列实施例给出参数x的取值和掺杂元素的种类的原料。
实施例一
表1-协效剂LAP-C12对传统膨胀阻燃剂阻燃性能的影响，以聚丙烯(PP)为例。其中LAP-C12磷酸铝制备，脂肪胺模板剂为十二烷基伯胺，铝源为醋酸铝，x＝1.0。
传统膨胀阻燃剂(IFR)配方：聚磷酸胺(APP)70.0wt.％，季戊四醇30.0wt.％；马来酸酐接枝的聚丙烯(PP-g-MAH)为兼容剂。其样品配方如表1：
表1
实施例二
表2-有机-无机层状磷酸铝层间距的大小对其分散状态、协效阻燃性、力学性能的影响。其中有机-无机层状磷酸铝的制备中铝源为拟薄水铝石，模板剂为n-CmH2m+1NH2(m＝8，12，18)，x＝1.0，不同层间距的层状磷酸铝用LAP-Cm(m＝8，12，18)表示。阻燃剂组合物(IFR-1-LAP-Cm)为：聚磷酸铵60.0wt.％，甘油磷酸锰10.0wt.％，LAP-Cm为10.0wt.％，壳聚糖5.0wt.％、酚醛树脂15.0wt.％。IFR-1与IFR-1-LAP-Cm区别为不加LAP-Cm。样品配方如表2：
表2
实施例三
表3-有机-无机杂原子掺杂的层状磷酸铝对协效阻燃剂协效阻燃性能的影响。其中杂原子掺杂的层状磷酸铝的制备中脂肪胺模板剂为十二烷基伯胺，铝源为硝酸铝，x＝0.9，Me为Ni、Co、Cu、Mn、Mg和Zn，Me:Al＝1:9，杂原子掺杂的层状磷酸铝用LMeAP-C12表示。阻燃剂组合物IFR-2-LAMeP-C12为：LAMeP-C1210.0wt.％，聚磷酸密胺50.0wt.％，胍9.0wt.％，环己六醇30.0wt.％，红磷1.0wt.％。IFR-2与IFR-2-LAMP-C12的区别为不加LAMP-C12。样品配方如表3下：
表3
实施例四
表4-LABP-C12对PA66/IFR体系中的阻燃性能的影响。其中B掺杂的层状磷酸铝(LABP-C12)的制备中B:Al＝2:8，脂肪胺模板剂为十二胺，铝源为硫酸铝。阻燃组合物(IFR-3-LABP-C12)为：LABP-C125.0wt.％，三聚氰胺聚磷酸：80.0wt.％，二水磷酸铁5.0wt.％，氰尿酸三聚氰胺10.0wt.％。IFR-3与IFR--3LABP-C12区别为不加LABP-C12。样品配方如表4：
表4
实施例五
表5-IFR-4-LAP-C12对LDPE阻燃性能的影响。LAP-C12的制备条件如实施例一。其中IFR-4-LAP-C12配方为：LAP-C12：2.0wt.％，三水磷酸锰5.0wt.％，三聚氰胺包覆红磷2.0wt.％，聚磷酸65.0wt.％，季戊四醇26.0wt.％。IFR-4与IFR-4-LAP-C12区别为不加LAP-C12。样品配方如表5：
表5
实施例六
表6-LAP-C12的协效阻燃性能与有机改性的蒙脱土(OMT)比较。LAP-C12的制备方法与实施例一相同，膨胀阻燃剂的配方为：聚磷酸铵70.0wt.％，季戊四醇30.0wt.％。有机改性的蒙脱土来源于盛德化工有限公司。具体配方如表6：
表6
实施例七
阻燃剂组合物与市场上磷氮系阻燃剂性能对比。阻燃剂组合物(IFR-5-LANiP-C12)配方如下：LANiP-C12含量10.0wt.％，三聚氰胺包覆红磷含量1.0wt.％，甘油磷酸锰2.0wt.％，二水磷酸铁2.0wt.％，硅烷包覆聚磷酸铵60.0wt.％，硅烷包覆季戊四醇25.0wt.％。样品配方：聚丙烯75.0wt.％，马来酸酐接枝的聚丙烯5.0wt.％，阻燃剂20.0wt.％。市场上磷氮阻燃剂来源为：万盛、麦太FR-486，琪原NP-35A，赛达1001S。
实验结果与讨论
表7-ICP和CHN分析结果；
表7
LABP-C12与LAP-C12的热重结果见图2；LAP-Cn X射线衍射测试结果见图3。
图4表示LAP-Cn(n＝8，12，18)在PP中的状态，其中A：PP/LAP-C8-2.5wt.％，B：PP/LAP-C8-2.5wt.％，C：PP/LAP-C8-2.5wt.％。
图5表示0-2.0wt.％LABP-C12在PA66中的分散状态(PA66/LABP-C12-2.0wt.％)。
表8-样品的阻燃性能与力学性能，LOI和UL-94样条的厚度为3.2mm的国标标准样条，拉伸性能、弯曲性能和悬臂梁缺口冲击性能测试标准分别为ISO527、ISO178、ISO179。
表8
1.协效剂LAP-C12-1对传统膨胀阻燃剂(IFR)阻燃性能的影响结果：
根据图3可知，LAP-C12颗粒均匀分散在PP基体中，并且层间距比LAP-C12的层间距大，表明聚丙烯链进入了磷酸铝层间，形成了插层的聚丙烯纳米复合材料。
根据表1的配比和结合表8的测试数据可知，但LAP-C12的添加量为1.0-2.5wt.％时，与样品PP1相比，极限氧指数从27提高到30，UL94等级从V-2提高到V-0，阻燃性能大大提高，表明LAP-C12与IFR有很好的协效阻燃性能。当LAP-C12的添加量为5.0wt.％，阻燃性能又下降。力学性能测试结果表明，当LAP-C12的添加量为2.5wt.％时，总体力学性能最好。PP3与样品PP1相比，冲击强度和断裂伸长率增强，韧性提高，而强度有所降低，并且熔融指数从6.2g/min提高到8.3g/min，加工性能提高。
2.有机-无机层状磷酸铝层间距的大小对其分散状态、协效阻燃性、力学性能的影响结果与讨论：
根据图3的测试结果和公式sinθ＝nλ/(2d)可得，LAP-C8、LAP-C12、LAP-C8的层间距分别为2.71nm、3.28nm和4.37nm。根据图4可知，LAP-Cn(n＝8，12)颗粒均匀分散在PP基体中，由于聚丙烯链进入磷酸铝层间使层间距扩大，从而形成了层状磷酸铝聚合物纳米复合材料。虽然LAP-C18在PP基体中发生了一定程度的剥离，但其颗粒在PP中的分散状态较差，出现了大的团聚颗粒。
根据表2的配方和表8的测试数据可知，但LAP-Cn(n＝8，12)在阻燃剂中的添加量为10.0wt.％时，PP6和PP7的力学性能和阻燃性能都比PP5好，这说明LAP-Cn(n＝8，12)与IFR-1有很好的协效作用。
3.有机-无机杂原子掺杂的层状磷酸铝对协效阻燃剂协效阻燃性能的影响结果与讨论：
由表-7的测试结果可知，杂原子Me掺杂进层状磷酸铝中。根据表3的配方和表8的测试数据可知，PP10-PP16的的阻燃性能与PP9的阻燃性能好，这说明LAP-C12和LAMP-C12的添加提高了PP/IFR-2体系的阻燃性能，使LOI值从27％提高到31％，UL-94级别从V-2提高到V-0。而PP11，PP12和PP14的阻燃性与PP10相比能相对较高，这说明Ni、Co和Mn原子的掺杂提高LAP-C12在PP/IFR-2体系的协效阻燃性能，而PP13、PP15和PP16的阻燃性能与PP10相比相对较低，这说明Cu、Mg和Zn的掺杂降低了LAP-C12在PP/IFR-2体系的阻燃性能。从力学性能测试结果可知，LAMP-C12的添加提高阻燃PP的力学性能。
4.LABP-C12对PA66/IFR体系中的阻燃性能的影响结果与讨论。
由表-7的测试结果可知，B原子掺杂进层状磷酸铝中。根据图2可知，B的掺杂提高了了层状磷酸铝的热稳定性，使其满足PA66的加工需求。根据图5可知，层状磷酸硼铝在PA66基体中完全剥离，形成了剥离的尼龙66纳米复合材料
根据表4的配方和表8的阻燃力学测试结果可知，IFR-LABP-C12在PA66中的阻燃性能比IFR-3好，这说明LABP-C12的掺杂提高了阻燃剂的阻燃效率。从力学结果可知，23.0wt.％的IFR-3的添加，明显降低了PA66的断裂伸长率，其他性能都有所提高，而LABP-C12的添加提高了PA66的断裂伸长率，并且，PA66-2的力学性能比PA66-1的好。
5.IFR-4-LAP-C12对LDPE阻燃性能的影响结果和讨论。
根据表5的配方和表8的结果可知，IFR-4-LAP-C12的阻燃效率要比IFR-4高，IFR-4需要添加28.0wt.％才能达到V-0级，而，IFR-4-LAP-C12的添加量为25.0wt.％时，UL-94测试就能达到V-0级。并且LDPE-2和LDPE-3的力学性能比LDPE-1好，这说明LAP-C12添加提高了LDPE-IFR-4体系的阻燃性能。
6.LAP-C12的协效阻燃性能与有机改性的蒙脱土(OMT)比较结果和讨论。
根据表6的配方和表8的测试结果可知，OMT与传统膨胀型阻燃剂的协效性比LAP-12的相比较差。
7.阻燃剂组合物与市场上磷氮系阻燃剂性能对比结果与讨论。
实施例7和表8的结果可知，IFR-5-LANiP-C12与市场上同类的阻燃剂相比，具有较高的竞争性。
上述七个实施例说明了，LAP-Cn和LAMP-C12与不同配比的IFR具有较好的协效作用，并且含有有机-无机层状磷酸铝的阻燃剂组合物具有较高的阻燃性能和力学改性性能。
Claims (9)
1.一种膨胀阻燃剂用的层状磷酸铝阻燃协效剂，其特征在于，该阻燃协效剂是采用磷酸、铝源、掺杂原子源以及脂肪胺合成的有机-无机层状磷酸铝，其中，无机骨架是由Al(Me)—O—P—O化学键交替连接而成的无机板层结构，层间距d为2.7-4.5nm，无机板层之间是脂肪胺；无机骨架中Me为杂原子，Me占Me、Al和P总元素摩尔含量的5～20.0％；其中，所述的杂原子Me是B、Mg、Ca、Ti、Mn、Fe、Zn、Ni的一种或者多种。
2.根据权利要求1所述的阻燃协效剂，其特征在于，所述的脂肪胺是含碳为8～18的直链脂肪族伯胺，即，n-CmH2m+1NH2，m＝8～18。
3.采用权利要求1或2所述层状磷酸铝阻燃协效剂的阻燃剂组合物，用于塑料无卤阻燃改性，其特征在于包括：所述层状磷酸铝阻燃协效剂0.5～10wt％，磷源50～80wt％，氮源0～30wt％，碳源0～30wt％。
4.根据权利要求3所述的阻燃剂组合物，其特征在于，所述的磷源选自二乙基次磷酸铝，聚磷酸铵，硅烷包覆聚磷酸铵，三聚氰胺聚磷酸，红磷，三聚氰胺包覆红磷，甘油磷酸铁，二水磷酸铁，甘油磷酸锰，三水磷酸锰,酸式磷酸锰，甘油磷酸钙中的一种或者多种。
5.根据权利要求3所述的阻燃剂组合物，其特征在于，所述的氮源为三聚氰胺、苯代三聚氰胺、胍、氰尿酸三聚氰胺的一种或者多种。
6.根据权利要求3所述的阻燃剂组合物，其特征在于，所述的碳源为季戊四醇、壳聚糖、酚醛树脂、环己六醇、丁四醇中的一种或多种。
7.一种层状磷酸铝阻燃协效剂制备方法，其特征在于包括如下步骤：
(1)、将铝源与含有杂原子Me的氧化物、氢氧化物、醋酸盐或者硝酸盐分散到水中，搅拌30min，加入浓磷酸，再搅拌1h后倒入脂肪胺，继续搅拌2h得浆料；
其中，以下式给出浆料中各物质量的比例：Al:Me:P2O5:脂肪胺:H2O＝1.0:2(1.0-x):1.0:1.0:60.0，x＝1.0～0.8；所述脂肪胺是含碳为8～18的直链脂肪族伯胺；所述杂原子Me是B、Mg、Ca、Ti、Mn、Fe、Zn、Ni的一种或者多种；
(2)、将步骤(1)所得的浆料转移到有聚四氟乙烯内衬的反应釜中，在100℃温度下反应，取出、冷去至室温，抽滤、洗涤、干燥；所得产物经X射线衍射分析具有层状结构，间距为2.7-4.5nm。
8.根据权利要求7所述的制备方法，其特征在于，所述浓磷酸的浓度为85wt％；干燥温度为80℃。
9.根据权利要求7所述的制备方法，其特征在于，所述的铝源是醋酸铝、氧化铝、拟薄水铝石、硝酸铝或硫酸铝。
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