CN112399981B - 含磷低聚物和聚合物 - Google Patents
含磷低聚物和聚合物 Download PDFInfo
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- CN112399981B CN112399981B CN201980046939.2A CN201980046939A CN112399981B CN 112399981 B CN112399981 B CN 112399981B CN 201980046939 A CN201980046939 A CN 201980046939A CN 112399981 B CN112399981 B CN 112399981B
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- KKKKCPPTESQGQH-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-yl)-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=NCCO1 KKKKCPPTESQGQH-UHFFFAOYSA-N 0.000 description 1
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明开发出了含不饱和乙烯基基团的反应性有机磷化合物,其可以灵活且高度受控的方式用于经由自由基反应或经由与合适的亲核体的迈克尔加成来制备各种大分子衍生物。基于一方面的仲胺基团和另一方面的乙烯基基团可充当相互连接位点的事实,可构建新颖且有用的加成产物库。通过选择参与反应的各方的仲胺位点和乙烯基位点的数量,可形成非常不同的加成产物。特别地,可形成直链型大分子(即线型低聚物或聚合物)或高度交联的网络聚合物。
Description
技术领域
本发明涉及新型含磷低聚物和聚合物,涉及方法或其制备并且涉及含磷水凝胶或有机凝胶。
背景技术
聚酰胺(尤其是聚酰胺6或"PA6")和聚酯(PET)常用于制造纺织纤维。对于防火应用而言,这样的聚合物需要是阻燃的。这样的聚合物的阻燃性可通过在聚合物的主链中引入阻燃部分(共聚)来实现,或通过在其热加工期间引入非反应性添加剂来实现。在聚合物加工期间在聚合物中引入添加剂提供了灵活性和简单性的优点。然而,这样的非反应性添加剂会在其随后的湿法加工期间浸出,特别是在温度高于100℃的纺织纤维染色期间。避免这样的问题的两种可能方式是,在热加工期间将反应性添加剂接枝至聚合物链的主链,或在聚合物的热加工期间产生不浸出的(non-leaching)大分子(macromolecular)添加剂。将添加剂化学接枝至聚合物主链会防止其在随后的湿法处理期间的浸出,而大分子形式的添加剂会与聚合物链缠结,且从而会防止在随后的处理后期间从聚合物中迁移出。这两种使聚合物具有阻燃性的方式是相当新颖的,且在文献中知之甚少。关于用以提高PA6的阻燃性和热稳定性的PA6的反应性挤出仅存在有限的知识。
反应性受阻酚是有效的热稳定剂,其可捕集RO和ROO自由基通过贡献氢原子和形成稳定的自由基来抑制老化过程。这样的酚可在反应性挤出过程中以高接枝效率接枝至PA6的主链上从而改进热氧化稳定性[1]。在挤出过程中由三聚氰胺和氰尿酸的反应原位制备三聚氰胺氰尿酸酯-PA6纳米复合物[2]是有效的且创新性的改进聚合物的阻燃性的方法;然而,这样的聚合物配制物无法纺成纺织纤维。由此原位形成的三聚氰胺氰尿酸酯会附聚形成大颗粒,所述大颗粒可在正常纺丝过程中成为阻塞。
扩链形式的反应性挤出已被广泛用于聚合物例如PA-6和PET的改性,并且通过将扩链剂添加至挤出过程的反应性挤出,可以提高这些聚合物的分子量。最常用的扩链剂是用于PA-6的1,1'间苯二甲酰基双己内酰胺和2,2'-双(2-噁唑啉)[3,4],和用于PET的均苯四甲酸二酐和三缩水甘油基异氰脲酸酯[5]。然而,在这些情形中,没有实现阻燃性。
近年来,水不溶性和水溶胀性凝胶在广范围的生物医学应用中引起了越来越多的兴趣,例如在医药领域中,作为递送各种药物、肽和蛋白质的载体。它们的可逆溶胀能力使它们能够根据外部刺激(例如pH、温度、离子强度、电场或特定分析物浓度梯度)调节释放行为[6-10]。已开发了多种制备交联聚合物凝胶的方法,比如经由热能产生的自由基引发[11]或引发剂分子的光裂解[12]、和“点击”化学[13],但是由于所用催化剂或引发剂的毒性,上述方法的应用受到限制,并且复杂的化学合成使其仍然是一个巨大的挑战。
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发明内容
本发明人已发现含不饱和乙烯基基团的反应性有机磷化合物可以灵活且高度受控的方式用于经由自由基反应或经由与合适的亲核体的迈克尔加成来制备各种大分子衍生物。基于一方面的仲胺基团和另一方面的乙烯基基团可充当相互连接位点的事实,可构建新颖且有用的加成产物库。从下面概述的各个方面将理解,选择参与反应的各方的仲胺位点和乙烯基位点的数量允许产生非常不同的加成产物。特别地,可形成直链型大分子(即线型低聚物或聚合物)或高度交联的网络聚合物。
因此,根据本发明的一个方面,提供具有通式(A)的含磷的线型低聚物或聚合物
其中
n为至少2;
R1选自苯基、取代的苯基、苄基、取代的苄基、具有最高达5个碳原子的线型或支化的烷基基团、和具有最高达5个碳原子的线型或支化的烷氧基基团;
-X-R'-X-选自
其中R"为在邻位、间位或对位的具有最高达5个碳原子的线型或支化的烷基基团,
或者-X-R'-X-为-NR2-R"'-NR2-其中
R2为甲基或烷基基团并且
R"'选自:
具有最高达5个碳原子的线型或支化的烷基基团、
根据本发明的另一个方面,制备以上定义的含磷的低聚物或聚合物(A)的方法包括二乙烯基氧化膦(B)和根据如下(C)的含两个仲胺基团的胺化合物(C)的加成反应:
H-X-R'-X-H (C)
其中-X-R'-X-如上文刚定义的。
根据本发明的另外的方面,提供通式(D)的含磷交联网络聚合物
其中R选自
根据本发明的还另外的方面,制备如上文定义的交联网络聚合物(D)的方法包括三乙烯基氧化膦(E)和根据如下(F)的含两个仲胺基团的胺化合物(F)的加成反应:
H-N-R-N-H(F)
其中-N-R-N-选自
根据本发明的还另外的方面,提供通式(G)的含磷交联网络聚合物
其中R选自
根据本发明的还另一个方面,制备如上文定义的交联网络聚合物(G)的方法包括三乙烯基氧化膦(E)和根据如下(H)的含三个仲胺基团的胺化合物(H)的加成反应:
-HN-R(NH-)-NH- (H)
其中-N-R(N-)-N-选自
根据本发明的还另外的方面,提供通式(J)的含磷交联网络聚合物
其中R选自
并且其中R1选自
具有最高达5个碳原子的线型或支化的烷基基团、和
具有最高达5个碳原子的线型或支化的烷氧基基团。
根据本发明的另一个方面,制备如上文定义的交联网络聚合物(J)的方法包括二乙烯基氧化膦(K)和根据如下(H)的含三个仲胺基团的胺化合物(H)的加成反应:
其中R1是如上文针对(J)所定义的,
-HN-R(NH-)-NH-(H)
其中-N-R(N-)-N-选自
根据本发明的另外的方面,提供含磷水凝胶或有机凝胶,其包含在水中的或在有机溶剂中的如上文定义的交联网络聚合物。
在有利的实施方式中,上文定义的方法在共混物的热加工期间进行,所述共混物包含热塑性基础聚合物和以下的掺合物:
-如上文定义的含至少两个乙烯基基团的氧化膦(B)、(E)或(K;和
-如上文定义的含至少两个仲胺基团的胺化合物(C)、(F)或(H)。
有利地,所述热塑性基础聚合物为聚酰胺、聚烯烃、聚酯或聚碳酸酯。
根据本发明的另一个方面,提供形成含磷聚合物的方法,所述方法包括以下步骤:
a)提供基础聚合物和含至少一个乙烯基基团的氧化膦(L)的混合物
其中,
R1选自具有最高达5个碳原子的线型或支化的烷基基团,苯基基团和乙烯基基团,并且
R2独立地选自具有最高达5个碳原子的线型或支化的烷基基团,苯基基团,乙烯基基团,具有最高达5个碳原子的线型或支化的烷氧基基团,和苯氧基基团;
所述混合物任选地含自由基引发剂;
以及
b)使所述混合物经历自由基引发,由此引起其中氧化膦接枝至基础聚合物的加成反应。
根据一种有利的实施方式,基础聚合物为聚酰胺或聚酯。
正如在原理上已知的,存在不同的实现自由基引发的方式。根据一个实施方式,自由基形成是通过热活化即加热引起的。所述过程可以是自催化的或其可通过加入自由基引发剂而促进。根据另一个实施方式,自由基形成是通过紫外线辐照或电子束辐照引起的,其通常需要提供薄层或纤维形式的混合物。
根据另外的方面,如上文定义的含磷低聚物或聚合物被用作阻燃组分(组合物,composition)。
根据还另一方面,提供具有改进的阻燃性的聚合物材料,其包含掺合在可熔融加工的聚合物中的如上文定义的含磷低聚物或聚合物。
附图说明
通过结合附图参考以下对本发明的各种实施方式的描述,本发明的上述和其他特征和目的以及实现它们的方式将变得更加明晰,并且将更好地理解本发明本身,在所述附图中显示的为:
图1用于制备阻燃聚合物的途径的概述;
图2凝胶A在不同pH值下24小时后对酸性蓝(Acid Blue)80的释放行为;和
图3凝胶A在不同pH值下24小时后对亚甲基蓝的释放行为。
具体实施方式
在以下表1中给出在本研究中起到重要作用的官能性添加剂的概述:
表1:本研究中使用的官能性磷化合物和哌嗪衍生物的化学结构。
生产阻燃聚合物体系
如图1中示意性地显示的,无浸出的阻燃聚合物体系可通过经由三种不同途径永久性地固定具有阻燃部分的磷添加剂而获得:
1)第一种途径在于通过在挤出机或捏合机中的自由基反应将含乙烯基的磷添加剂(DPVPO、DVPPO和TVPO)接枝至基础聚合物的主链(反应性挤出)。所述自由基反应可以是自催化的或可通过添加自由基引发剂而得到促进:
途径1
在此方式中,标记为"P"的阻燃含磷部分直接附接至基础聚合物的主链。
2)第二种途径在于在基础聚合物的热加工期间DVPPO或TVPO与亲核体(迈克尔加成)的原位聚合(反应性挤出)。
途径2
迈克尔加成反应
这导致在形成基础聚合物的聚合物链网络内缠结的长链含磷大分子的形成。虽然具有阻燃效果的物种没有附接至基础聚合物的主链,但由于缠结将防止其浸出。
3)第三种途径在于在挤出机或捏合机中物理混合含乙烯基的磷添加剂(DPVPO、DVPPO和TVPO)和合适的基础聚合物。然后,将挤出的聚合物转化为薄壁材料如纤维和膜,并且随后使其经受UV或电子束辐照,导致自由基形成并且由此将添加剂交联至基础聚合物的主链。
途径3
第三种途径潜在地导致类似于第一种途径的结构,但经由不同的路线。
制备凝胶
所述凝胶可通过使二乙烯基或三乙烯基磷化合物与合适的亲核体(参见概图1)在水适合的有机溶剂中经由迈克尔加成反应进行反应而制备。
概图1:用于合成凝胶的含胺亲核体的一般结构
由三乙烯基磷衍生物(TVPO)制备的凝胶的一般结构示于概图2中:
概图2:凝胶(TVPPO衍生物)的一般化学结构
由二乙烯基磷衍生物制备的凝胶的一般结构示于概图3中:
概图3:凝胶(二乙烯基磷衍生物)的一般化学结构
实施例
1.阻燃聚合物
加工(途径1)
此研究中使用的所有基于磷的添加剂均含有一个或多个可通过自由基反应与PA6和PET的亚甲基基团(-CH2-)反应的乙烯基基团。表2汇总了对反应性磷添加剂进行的加工试验的列表。为了促进自由基反应,在一些实验中添加了自由基引发剂。
使用布拉本德(Brabender)混合器在30rpm对PA-6在240℃和对PET在260℃进行捏合试验。首先进料聚合物并且在两分钟后进料添加剂,总混合时间为10分钟。
%wt=重量百分数
表2:捏合试验的配制物的细节(途径1)
加工(途径2)
此研究中使用的磷添加剂的乙烯基基团可通过迈克尔加成反应与PA-6和/或哌嗪的氨基基团(-NH-)反应。表3说明了对反应性磷添加剂进行的试验。试验使用布拉本德混合器在240℃和30rpm下进行。
%wt=重量百分数
PIP=哌嗪
表3:挤出试验的配制物的细节(途径2)
加工(途径3)
第三种途径在于阻燃添加剂和聚合物通过捏合而物理混合以及随后进行电子束处理以将添加剂交联至聚合物主链。此物理混合不认为是反应性挤出;然而,我们不能避免磷添加剂的一些乙烯基基团与聚合物的反应,甚至在不存在任何自由基引发剂时也是如此。经由途径1和2获得的材料中的一些用于后期交联实验;列表示于表4中。
通过压缩模塑(对于PA6为260℃并且对于PET为290℃)制备以上材料的板(150*50*0.5mm)。随后使板暴露于电子辐照。通过电子束供应的能量允许添加剂中存在的乙烯基基团和聚合物链之间的反应。
将所述板以6m/min的速度在200kV下在N2氛围中在两面上进行处理(电子束的穿透为200-250μm)。为了评估反应的添加剂的量随供应的能量的变化,使用了50、100和200kGy的剂量。
表4:捏合试验的配制物的细节(途径3)
热数据
表5汇总了通过途径1和途径2获得的所有聚合物配制物的热数据。由进行的热重分析(TGA)清楚的是:添加剂降低了PA在空气和氮气中的分解温度并且此效果在用DCP加工的材料中更明显。由差示扫描量热法分析(DSC)未检测到熔化温度的显著不同和结晶温度的显著不同。
*经由途径2获得的材料
表5:所有配制物的热数据
评估各种聚合物配制物(途径1和2)的磷含量和保留
然后对挤出的聚合物进行研磨并且用氯仿进行提取。对各样品在提取之前和之后进行使用ICP设备的磷分析以计算保留的阻燃物。使用ICP-OES方法对各种配制物评估%磷含量。为了评价%磷保留,将聚合物配制物用氯仿在100℃提取1小时并且然后评价%磷保留。表6呈现了磷含量及其在溶剂提取后的保留。
*经由途径2获得的材料
**在氯仿中(1ml溶剂/100mg材料)在100℃、30巴下进行提取1小时。对溶液进行搅拌。
%wt=重量百分数
表6:所有配制物的磷含量和保留
试验的PA6/DV/PIP已显示出有前途的可加工性特性以及较高的磷保留,这导致生产出以千克量计的配混物(PA6/DV/PIP-Comp)和后续的纤维(PA6/DV/PIP-FB),其具有相同浓度的添加剂。将原始的PA-6先在真空烘箱中在100℃干燥12小时,并然后与添加剂物理预混合30分钟。使用同向旋转双螺杆(16mm)配混机获得该配混物;加工温度和模头温度分别为在110rpm下265℃和251℃。配混机的输出速率为500g/hr。使用相同的配混物生产纤维;加工温度和纺丝组件温度分别为275℃和245℃,并且输出速率为360cm3/hr。将所得的丝拉伸直至拉伸比为4,导致最终纤维直径为70μm。
%wt=重量百分数
Virg=原始的,Comp=配混物,FB=纤维
表7:配混物和纤维的磷含量和保留
如表7中所示,配混和捏合(PA6/DV/PIP-Comp和PA6/DV/PIP)在磷保留方面得到了相似的结果。相反,对于纤维的%磷保留显著提高,这可能是因为所述材料的较长加工所致,这导致较高的反应产率(迈克尔加成)。
纤维的机械性质
研究了纤维的机械性质;将其汇总于表8中并且所呈现的数据是对20次测量的平均值。
表8:获得的纤维的机械性质
各种聚合物配制物(途径3)的磷含量和保留的评估
然后对经电子束处理的板进行研磨并且用氯仿进行提取。对各样品在提取之前和之后进行使用ICP设备的磷分析以计算保留的阻燃物。使用ICP-OES方法对各种配制物进行%磷含量评估。为了评价%磷保留,将聚合物配制物用氯仿在100℃提取1小时,和然后对%磷保留进行评价。表9汇总了各种聚合物配制物,电子束处理强度及其%磷含量和保留。
#"戈瑞"(Gy)被定义为每千克物质吸收一焦耳的辐射能量。
表9:经电子束处理的材料的磷含量和保留(途径3)
如表9中所示,即便用低电子束辐照,所有基于PA-6的材料也均实现了高于90%的磷保留。因此,此程序提供了将FR添加剂永久性地固定在聚合物中的新型方式。对于基于PET的材料,在电子束辐照之后,磷保留显著提高但数值仍是低的。
经由途径2获得的材料的着火测试(fire test)
对各种配制物进行小规模着火测试以评估其着火行为。对PA6-MB和PA6/DV/PIP-Comp的板进行极限氧指数(LOI)测试和垂直燃烧测试(BKZ-Swiss标准)。对两种测试,已通过在260℃的压缩模塑制备以上材料的板(150*50*0.5mm)。
LOI为将支持聚合物燃烧的最低氧浓度(表示为百分数);其通过使氧气和氮气的混合物在燃烧着的样品上流动而测量,降低氧浓度重复进行测试直到火焰不蔓延。
所述测试包括将样品的下边缘与丙烷气体火焰(长度为40±2mm)接触15s。使燃烧器相对于竖直线倾斜45°。测量损毁长度(damaged length)和阴燃时间(afterglow time)。
□所述数值是3次测试的平均。
表10:着火测试结果
因此,明显的是这样的阻燃改性显著地改进了聚酰胺6的着火保护。
2.凝胶
凝胶A的合成
将TVPO(64.02mg,0.50mmol)和哌嗪(64.60mg,0.75mmol)添加到水(2.5ml)。将所得混合物在90℃搅拌0.5h并且获得了无色透明的凝胶。通过冷冻干燥蒸发溶剂。
概图4.凝胶A的合成
凝胶A1的合成
将TVPO(64.02mg,0.50mmol)、哌嗪(64.60mg,0.75mmol)、聚乙二醇(20K)(12.80mg,10%)添加到水(2.5ml)。将所得混合物在90℃搅拌0.5h。
通过冷冻干燥蒸发溶剂。
概图5.凝胶A1的合成
凝胶A2的合成
将TVPO(64.02mg,0.50mmol)、哌嗪(64.60mg,0.75mmol)、聚乙二醇(200K)(6.40mg,5%)添加到水(2.5ml)。将所得混合物在90℃搅拌0.5h。通过冷冻干燥蒸发溶剂。
概图6.凝胶A2的合成
凝胶A3的合成
将TVPO(64.02mg,0.50mmol)、哌嗪(64.60mg,0.75mmol)、聚乙二醇(300K)(6.90mg,5%)添加到水(2.5ml)。将所得混合物在90℃搅拌0.5h。通过冷冻干燥蒸发溶剂。
概图7.凝胶A3的合成
凝胶B的合成
将TVPO(128mg,1mmol)和DPP(157.7mg,0.75mmol)添加到乙醇(2.5ml)。将所得混合物在80℃搅拌1.5h。通过冷冻干燥蒸发溶剂。
概图8.凝胶B的合成
凝胶C的合成
将TVPO(64.02mg,0.50mmol)和1,10-二(哌嗪-1-基)癸烷(232.89mg,0.75mmol)添加到乙醇(5ml)。将所得混合物在85℃搅拌8h并且获得了无色透明的凝胶。通过冷冻干燥蒸发溶剂。
概图9.凝胶C的合成
凝胶D的合成
将TVPO(64.02mg,0.50mmol)和2,4,6-三(哌嗪-1-基)-1,3,5-三嗪(166.72mg,0.50mmol)添加到乙醇(5ml)。将所得混合物在85℃搅拌1h并且获得了无色透明的凝胶。通过冷冻干燥蒸发溶剂。
概图10.凝胶D的合成
凝胶E的合成
将DVPO(133.54mg,0.75mmol)和2,4,6-三(哌嗪-1-基)-1,3,5-三嗪(166.72mg,0.50mmol)添加到乙醇(5ml)。将所得混合物在85℃搅拌8h并且获得了无色透明的凝胶。通过冷冻干燥蒸发溶剂。
概图11.凝胶E的合成
凝胶的性质
1.溶胀行为
交联的凝胶的溶胀比通过将凝胶浸泡在特定的溶剂中直至达到平衡溶胀而测量。然后,将经溶胀的凝胶通过刮勺小心地取出到黄油纸(butter paper)上,用湿纸巾(在相应的溶剂中)迅速吸干并且称重。按照下式确定经溶胀的凝胶的溶剂吸收比(溶胀比,SR):
其中,Ws和Wd分别表示经溶胀的和干燥的交联的凝胶的重量。
已在具有不同极性的溶剂中研究了所合成的凝胶的溶胀行为,并且结果汇总在表11中。
表11.凝胶在不同溶剂中的溶胀比
2.水凝胶的pH响应
在室温下在pH 2至7.4的范围内进行水凝胶的pH响应性质。通过0.1N NaOH或0.1NHCl溶液调节含水介质的pH。将经测量的量的凝胶在特定的pH下进行浸泡直至达到平衡溶胀,然后取出,用湿纸巾迅速吸干并且称重。
如先前提及的那样计算溶胀比。
表12.pH对凝胶A的溶胀比的影响
3.凝胶的药物释放性质
凝胶的释放行为描述了被捕集在凝胶基体中的某些物质的释放。这可受到不同因素(例如pH、温度、离子强度、电场或特定分析物浓度梯度)的影响。取决于所述因素,凝胶适合用于不同的应用领域。健康的人类皮肤由于乳酸和皮脂的分泌而是弱酸性的并且pH为约5。在某些伤病中,pH变化为中性或碱性10(血液pH=~7.4)。这样的刺激可用于触发活性成分的释放。一旦皮肤已经恢复,pH降低并且所述释放被抑制或完全停止。可将对pH敏感的凝胶施用至伤口。
为了研究药物释放行为,选择亚甲基蓝和酸性蓝80作为模型分子。首先将所述模型分子溶解在室温下的水中(1mg/1ml),然后将凝胶浸泡在其中。在4h后,从溶液中取出凝胶并且用水反复清洗直到获得无色的水。作为对凝胶A(其作为实例)的定性评价,目视评价酸性蓝80的释放。附图(图2)清楚地表明酸性蓝80优先在高于7的pH释放。
类似地,还记录了含亚甲基蓝(模型碱性药物)的凝胶A的释放行为的定性评价。附图(图3)清楚地表明亚甲基蓝优先在较低的pH具有较高的释放。
Claims (8)
2.根据权利要求1所述的含磷的线型聚合物,其包括线型低聚物。
3.根据权利要求1或2所述的含磷的线型聚合物,其中R2为甲基基团。
5.根据权利要求4所述的方法,其在共混物的热加工期间进行,所述共混物包含热塑性基础聚合物并且包含以下的掺合物:
- 如权利要求4中定义的含至少两个乙烯基基团的氧化膦(B);和
- 如权利要求4中定义的含至少两个仲胺基团的胺化合物(C)。
6.根据权利要求5所述的方法,其中所述热塑性基础聚合物为聚酰胺、聚烯烃、聚酯或聚碳酸酯。
7.根据权利要求1-3任一项所述的含磷的线型聚合物作为阻燃组分的用途。
8.具有改进的阻燃性的聚合物材料,其包含掺合在可熔融加工的聚合物中的根据权利要求1-3任一项所述的含磷的线型聚合物。
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