CN111138816A - Use of fluorine-containing sulfonate as flame retardant in polylactic acid PLLA and flame retardant composition comprising the same - Google Patents

Abstract

Translated fromChinese

本发明提供了一种含氟磺酸盐在聚乳酸PLLA中作为阻燃剂的用途及包含其的阻燃组合物，通过将含氟磺酸盐与DOPO类阻燃剂协同作用阻燃PLLA，所述阻燃组合物包括含氟磺酸盐、DOPO类阻燃剂，所述阻燃组合物能够用作PLLA阻燃剂，并使得阻燃PLLA在保持良好的纺丝能力的情况下，同时具有优异的抗熔滴性能以及阻燃性能。The invention provides the use of a fluorine-containing sulfonate as a flame retardant in polylactic acid PLLA and a flame retardant composition containing the same. The flame retardant composition includes fluorine-containing sulfonate and DOPO type flame retardant, and the flame retardant composition can be used as a PLLA flame retardant, and enables the flame retardant PLLA to maintain good spinning ability while maintaining good spinning ability. Has excellent anti-droplet properties and flame retardant properties.

Description

Translated fromChinese

一种含氟磺酸盐在聚乳酸PLLA中作为阻燃剂的用途以及包含其的阻燃组合物Use of a fluorine-containing sulfonate in polylactic acid PLLA as a flame retardant and containingits flame retardant composition

技术领域technical field

本发明涉及高分子材料领域，特别涉及一种用于阻燃PLLA的含氟磺酸盐的阻燃剂以及含有该含氟磺酸盐的阻燃组合物。The invention relates to the field of polymer materials, in particular to a fluorosulfonate-containing flame retardant used for flame retarding PLLA and a flame retardant composition containing the fluorosulfonate.

背景技术Background technique

聚乳酸PLLA，又名聚丙交酯，属于聚酯家族，聚乳酸是以乳酸为主要原料聚合得到的聚合物，原料来源充分而且可以再生；但其耐热性差，而且聚乳酸PLLA易于燃烧，需要通过改性的方法赋予聚乳酸PLLA阻燃性能。Polylactic acid PLLA, also known as polylactide, belongs to the polyester family. Polylactic acid is a polymer obtained by polymerizing lactic acid as the main raw material. The source of raw materials is sufficient and can be regenerated; but its heat resistance is poor, and polylactic acid PLLA is easy to burn. The flame retardant properties of polylactic acid PLLA are imparted by the method of modification.

CN201410444423.2公开了一种具有阻燃功能的聚乳酸复合材料的制备，将聚乳酸、核/壳-聚甲基硅氧烷/聚甲基丙烯酸甲酯粒子以及多聚芳基磷酸酯混合，在168～180℃温度下，用转矩流变仪熔融共混，得到具有阻燃功能的聚乳酸复合材料，其中，核/壳-聚甲基硅氧烷/聚甲基丙烯酸甲酯粒子的质量分数为0～25％；多聚芳基磷酸酯的质量分数为0～25％，且核/壳-聚甲基硅氧烷/聚甲基丙烯酸甲酯粒子以及多聚芳基磷酸酯不能同时为0，该方法存在阻燃剂添加量高，所选材料有一定毒害，不符合绿色环保的主题，且其极限氧指数LOI仍较低。CN201410444423.2 discloses the preparation of a polylactic acid composite material with flame retardant function, which comprises mixing polylactic acid, core/shell-polymethylsiloxane/polymethyl methacrylate particles and polyaryl phosphate, At a temperature of 168-180 °C, melt blending with a torque rheometer to obtain a polylactic acid composite material with flame retardant function, wherein the core/shell-polymethylsiloxane/polymethylmethacrylate particles are The mass fraction is 0 to 25%; the mass fraction of polyaryl phosphate is 0 to 25%, and the core/shell-polymethylsiloxane/polymethyl methacrylate particles and polyarylphosphate cannot At the same time, it is 0. This method has a high amount of flame retardants, and the selected materials are toxic to a certain extent, which is not in line with the theme of green environmental protection, and its limiting oxygen index LOI is still low.

在专利文献CN1823127、CN101260227、CN101440156中分别报道了一系列常规无卤阻燃剂和常规膨胀型阻燃剂阻燃聚乳酸的应用。然而膨胀型阻燃剂及无机阻燃剂应用时主要限制问题在于其添加量较大，会影响聚乳酸物理机械性能，因此其阻燃效率仍有待提高。In the patent documents CN1823127, CN101260227 and CN101440156, the application of a series of conventional halogen-free flame retardants and conventional intumescent flame retardants to flame retardant polylactic acid is reported respectively. However, the main limitation in the application of intumescent flame retardants and inorganic flame retardants is that they are added in large amounts, which will affect the physical and mechanical properties of polylactic acid, so their flame retardant efficiency still needs to be improved.

在日本专利JP5378904 B9中，提出了除聚乳酸之外还含有热塑性树脂、磷系或氮系或金属氧化物系阻燃剂和阻燃助剂的聚乳酸树脂组合物，但阻燃性仅评价了UL94，不能准确地得知阻燃效果，而且未提供纺丝性能数据。In Japanese Patent JP5378904 B9, a polylactic acid resin composition containing thermoplastic resin, phosphorus-based or nitrogen-based or metal oxide-based flame retardant and flame retardant auxiliary in addition to polylactic acid is proposed, but the flame retardancy is only evaluated. According to UL94, the flame retardant effect cannot be accurately known, and no spinning performance data is provided.

因此，亟需提供一种具有阻燃性能的化合物和含有其的阻燃组合物用于阻燃PLLA，并提供一种阻燃PLLA的制备方法，以使得阻燃PLLA在保持良好的纺丝能力的情况下，同时具有优异的阻燃性能以及抗熔滴性能。Therefore, there is an urgent need to provide a compound with flame retardant properties and a flame retardant composition containing the same for flame retardant PLLA, and to provide a preparation method of the flame retardant PLLA, so that the flame retardant PLLA can maintain a good spinning ability. It has excellent flame retardant properties and anti-droplet properties at the same time.

发明内容SUMMARY OF THE INVENTION

为了解决上述问题，本发明人进行了锐意研究，结果发现：一种含氟磺酸盐在聚乳酸PLLA(聚左旋乳酸)中作为阻燃剂的用途以及包含其的阻燃组合物，所述含氟磺酸盐与DOPO类阻燃剂协同作用阻燃PLLA；所述阻燃组合物包括含氟磺酸盐、DOPO类阻燃剂，所述阻燃组合物能够用作PLLA阻燃剂，并使得阻燃PLLA在保持良好的纺丝能力的情况下，同时具有优异的抗熔滴性能以及阻燃性能，从而完成了本发明。In order to solve the above-mentioned problems, the present inventors have carried out intensive research, and found that: the use of a fluorine-containing sulfonate as a flame retardant in polylactic acid PLLA (poly-L-lactic acid) and a flame retardant composition comprising the same, the Fluorine-containing sulfonate and DOPO flame retardant act synergistically to flame retardant PLLA; the flame retardant composition includes fluorine sulfonate and DOPO flame retardant, and the flame retardant composition can be used as a PLLA flame retardant, And the flame-retardant PLLA has excellent anti-droplet performance and flame-retardant performance while maintaining good spinning ability, thereby completing the present invention.

本发明的目的在于提供以下方面：The object of the present invention is to provide the following aspects:

第一方面，本发明提供一种包含含氟磺酸盐并用作PLLA阻燃剂的阻燃组合物，所述阻燃组合物包括含氟磺酸盐和DOPO类阻燃剂。In a first aspect, the present invention provides a flame retardant composition comprising a fluorosulfonate and used as a PLLA flame retardant, the flame retardant composition comprising a fluorosulfonate and a DOPO-based flame retardant.

其中，所述含氟磺酸盐与DOPO类阻燃剂的质量比为(0.1～30):100。Wherein, the mass ratio of the fluorine-containing sulfonate to the DOPO flame retardant is (0.1-30):100.

其中，所述DOPO类阻燃剂选自DOPO-TRIOL，DOPO-NQ，DOPO-HPM，DOPO-HAM，DOPO-BQ，DDP，和OD-PN。Wherein, the DOPO-based flame retardant is selected from DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP, and OD-PN.

其中，所述含氟磺酸盐为全氟磺酸盐，如全氟烷基磺酸盐、全氟芳基磺酸盐。Wherein, the fluorine-containing sulfonate is perfluorosulfonate, such as perfluoroalkylsulfonate and perfluoroarylsulfonate.

第二方面，本发明还提供一种含氟磺酸盐用作PLLA阻燃剂的用途，所述含氟磺酸盐为全氟磺酸盐，优选为全氟烷基磺酸盐、全氟芳基磺酸盐；In the second aspect, the present invention also provides the use of a fluorine-containing sulfonate as a PLLA flame retardant, wherein the fluorine-containing sulfonate is perfluorosulfonate, preferably perfluoroalkanesulfonate, perfluoroalkanesulfonate Aryl sulfonate;

更优选地，所述含氟磺酸盐选自全氟辛基磺酸盐、全氟庚基磺酸盐、全氟己基磺酸盐、全氟戊基磺酸盐、全氟丁基磺酸盐、全氟丙基磺酸盐、全氟乙基磺酸盐、全氟甲基磺酸盐、全氟壬基苯磺酸盐、全氟壬氧基苯磺酸盐、全氟乙基苯磺酸盐和全氟甲基苯磺酸盐。More preferably, the fluorine-containing sulfonate is selected from perfluorooctylsulfonate, perfluoroheptylsulfonate, perfluorohexylsulfonate, perfluoropentylsulfonate, perfluorobutylsulfonate salt, perfluoropropyl sulfonate, perfluoroethyl sulfonate, perfluoromethanesulfonate, perfluorononylbenzenesulfonate, perfluorononyloxybenzenesulfonate, perfluoroethylbenzene Sulfonates and perfluoromethylbenzene sulfonates.

其中，所述含氟磺酸盐与DOPO类阻燃剂组合用作PLLA阻燃剂。Wherein, the fluorine-containing sulfonate is used as a PLLA flame retardant in combination with a DOPO flame retardant.

其中，所述DOPO类阻燃剂选自DOPO-TRIOL，DOPO-NQ，DOPO-HPM，DOPO-HAM，DOPO-BQ，DDP，和OD-PN；优选地，所述DOPO类阻燃剂选自DOPO-NQ或DDP。Wherein, the DOPO flame retardant is selected from DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP, and OD-PN; preferably, the DOPO flame retardant is selected from DOPO-NQ or DDP.

附图说明Description of drawings

图1(a)示出对比例1～对比例6产品的DSC升温曲线图；Fig. 1 (a) shows the DSC heating curve of the products of Comparative Example 1 to Comparative Example 6;

图1(b)示出对比例1～对比例6产品的DSC降温曲线图；Fig. 1(b) shows the DSC cooling curves of the products of Comparative Examples 1 to 6;

图2(a)示出对比例1，对比例5以及实施例1～实施例5产品的DSC升温曲线图；Figure 2 (a) shows the DSC heating curve diagrams of Comparative Example 1, Comparative Example 5 and the products of Examples 1 to 5;

图2(b)示出对比例1，对比例5以及实施例1～实施例5产品的DSC降温曲线图；Figure 2 (b) shows the DSC cooling curves of Comparative Example 1, Comparative Example 5 and the products of Examples 1 to 5;

图3(a)示出对比例1～对比例6产品的TG曲线图；Figure 3 (a) shows the TG curves of the products of Comparative Example 1 to Comparative Example 6;

图3(b)示出对比例1～对比例6产品的DTG曲线图；Figure 3(b) shows the DTG curves of the products of Comparative Example 1 to Comparative Example 6;

图4(a)示出对比例1，对比例5以及实施例1～实施例5产品的TG曲线图；Figure 4(a) shows the TG curves of Comparative Example 1, Comparative Example 5 and the products of Examples 1 to 5;

图4(b)示出对比例1，对比例5以及实施例1～实施例5产品的DTG曲线图；Figure 4(b) shows the DTG curves of Comparative Example 1, Comparative Example 5 and the products of Examples 1 to 5;

图5(a)示出对比例1～对比例6产品的锥形量热HRR曲线图；Figure 5(a) shows the cone calorimetry HRR curves of the products of Comparative Examples 1 to 6;

图5(b)示出对比例1～对比例6产品的锥形量热THR曲线图；Figure 5(b) shows the cone calorimetry THR curves of the products of Comparative Examples 1 to 6;

图6(a)示出对比例5以及实施例1～实施例5产品的锥形量热HRR曲线图；Figure 6(a) shows the cone calorimetry HRR curves of Comparative Example 5 and the products of Examples 1 to 5;

图6(b)示出对比例5以及实施例1～实施例5产品的锥形量热THR曲线图；Figure 6(b) shows the cone calorimetry THR curves of Comparative Example 5 and the products of Examples 1 to 5;

图7示出对比例1～对比例6产品的SEM图；Figure 7 shows the SEM images of the products of Comparative Example 1 to Comparative Example 6;

图8示出对比例5以及实施例1～实施例5产品的SEM图。FIG. 8 shows the SEM images of Comparative Example 5 and the products of Examples 1 to 5.

具体实施方式Detailed ways

下面通过对本发明进行详细说明，本发明的特点和优点将随着这些说明而变得更为清楚、明确。The features and advantages of the present invention will become clearer and clearer through the detailed description of the present invention below.

以下详述本发明。The present invention is described in detail below.

本发明人经过大量研究和实验发现，一种含氟磺酸盐以及包含其的阻燃组合物可用于提高PLLA的阻燃性以及抗熔滴性，并同时保持其较好的纺丝性能。The inventors have found through extensive research and experiments that a fluorosulfonate and a flame retardant composition containing the same can be used to improve the flame retardancy and anti-droplet properties of PLLA, while maintaining its good spinning performance.

根据本发明的第一方面，提供包含含氟磺酸盐并用作PLLA阻燃剂的阻燃组合物，所述阻燃组合物包括含氟磺酸盐和DOPO类阻燃剂。According to a first aspect of the present invention, there is provided a flame retardant composition comprising a fluorosulfonate and used as a PLLA flame retardant, the flame retardant composition comprising a fluorosulfonate and a DOPO-based flame retardant.

其中，所述含氟磺酸盐与DOPO类阻燃剂的质量比为(0.1～30):100；Wherein, the mass ratio of the fluorine-containing sulfonate to the DOPO flame retardant is (0.1-30):100;

进一步优选地，所述含氟磺酸盐与DOPO类阻燃剂的质量比为(0.5～28):100。Further preferably, the mass ratio of the fluorine-containing sulfonate to the DOPO flame retardant is (0.5-28):100.

在一种实施方式中，所述DOPO类阻燃剂选自DOPO-TRIOL，DOPO-NQ，DOPO-HPM，DOPO-HAM，DOPO-BQ，DDP，和OD-PN。In one embodiment, the DOPO-based flame retardant is selected from DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP, and OD-PN.

在进一步优选的实施方式中，所述DOPO类阻燃剂选自DOPO-NQ或DDP；In a further preferred embodiment, the DOPO flame retardant is selected from DOPO-NQ or DDP;

在更进一步优选的实施方式中，所述DOPO类阻燃剂为DDP。In a further preferred embodiment, the DOPO-based flame retardant is DDP.

在一种优选的实施方式中，所述含氟磺酸盐为全氟磺酸盐，如全氟烷基磺酸盐、全氟芳基磺酸盐；更优选为磺酸钾或磺酸钠盐。In a preferred embodiment, the fluorine-containing sulfonate is perfluorosulfonate, such as perfluoroalkylsulfonate, perfluoroarylsulfonate; more preferably potassium sulfonate or sodium sulfonate Salt.

在进一步优选的实施方式中，所述含氟磺酸盐选自全氟辛基磺酸盐、全氟庚基磺酸盐、全氟己基磺酸盐、全氟戊基磺酸盐、全氟丁基磺酸盐、全氟丙基磺酸盐、全氟乙基磺酸盐、全氟甲基磺酸盐、全氟壬基苯磺酸盐、全氟壬氧基苯磺酸盐、全氟乙基苯磺酸盐和全氟甲基苯磺酸盐。In a further preferred embodiment, the fluorine-containing sulfonate is selected from the group consisting of perfluorooctylsulfonate, perfluoroheptylsulfonate, perfluorohexylsulfonate, perfluoropentylsulfonate, perfluoro Butanesulfonate, perfluoropropylsulfonate, perfluoroethylsulfonate, perfluoromethanesulfonate, perfluorononylbenzenesulfonate, perfluorononyloxybenzenesulfonate, perfluorononylbenzenesulfonate Fluoroethylbenzenesulfonate and perfluoromethylbenzenesulfonate.

在更进一步优选的实施方式中，所述含氟磺酸盐为全氟甲基苯磺酸盐或全氟丁基磺酸盐；In a further preferred embodiment, the fluorine-containing sulfonate is perfluoromethylbenzenesulfonate or perfluorobutanesulfonate;

在更进一步优选的实施方式中，所述含氟磺酸盐为全氟丁基磺酸盐，如全氟丁基磺酸钾或全氟丁基磺酸钠；更优选为全氟丁基磺酸钾。In a further preferred embodiment, the fluorine-containing sulfonate is perfluorobutanesulfonate, such as potassium perfluorobutanesulfonate or sodium perfluorobutanesulfonate; more preferably, perfluorobutanesulfonate Potassium acid.

本发明人发现，含氟磺酸盐与DOPO类阻燃剂配合使用，在一定程度上缩短了PLLA体系的燃烧时间，UL-94可顺利达到V-0级别，阻燃性得到提高，抗熔滴性能也大大加强。The inventors found that the use of fluorine-containing sulfonate in combination with DOPO flame retardants shortens the burning time of the PLLA system to a certain extent, UL-94 can smoothly reach the V-0 level, the flame retardancy is improved, and the melting resistance is improved. Drip performance is also greatly enhanced.

本发明中，DOPO是9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物的简称，其结构中含有P-H键，对烯烃、环氧化合物和羰基化合物极具活性。DOPO类阻燃剂指的是DOPO及其衍生物，它们由于分子结构中含有联苯环、菲环、O＝P-O键，所以比普通的有机磷酸酯具有更强的阻燃性能。In the present invention, DOPO is the abbreviation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which contains P-H bonds in its structure and is very active to olefins, epoxy compounds and carbonyl compounds . DOPO flame retardants refer to DOPO and its derivatives, which have stronger flame retardant properties than ordinary organic phosphates because they contain biphenyl rings, phenanthrene rings, and O=P-O bonds in their molecular structures.

本发明中，所述DOPO类阻燃剂中DOPO-TRIOL，DOPO-NQ，DOPO-HPM，DOPO-HAM，DOPO-BQ，DDP，和OD-PN的分子式结构如下所示：In the present invention, the molecular structures of DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP, and OD-PN in the DOPO flame retardant are as follows:

所述的阻燃组合物的制备方法包括将所述含氟磺酸盐、DOPO类阻燃剂混合的步骤。The preparation method of the flame retardant composition includes the step of mixing the fluorine-containing sulfonate and the DOPO type flame retardant.

本发明中，阻燃组合物的制备方法没有特别限制，优选地，所述制备方法包括将所述含氟磺酸盐、DOPO类阻燃剂按一定质量比混合后使用。In the present invention, the preparation method of the flame retardant composition is not particularly limited. Preferably, the preparation method includes mixing the fluorine-containing sulfonate and the DOPO type flame retardant in a certain mass ratio before use.

根据本发明的第二方面，提供一种含氟磺酸盐用作PLLA阻燃剂的用途，所述含氟磺酸盐为全氟磺酸盐，优选为全氟烷基磺酸盐、全氟芳基磺酸盐；更优选为磺酸钾或磺酸钠盐；According to the second aspect of the present invention, there is provided a use of a fluorosulfonate as a PLLA flame retardant, wherein the fluorosulfonate is a perfluorosulfonate, preferably a perfluoroalkanesulfonate, perfluoroalkanesulfonate, perfluoroalkanesulfonate Fluoroarylsulfonate; more preferably potassium or sodium sulfonate;

更优选地，所述含氟磺酸盐选自全氟辛基磺酸盐、全氟庚基磺酸盐、全氟己基磺酸盐、全氟戊基磺酸盐、全氟丁基磺酸盐、全氟丙基磺酸盐、全氟乙基磺酸盐、全氟甲基磺酸盐、全氟壬基苯磺酸盐、全氟壬氧基苯磺酸盐、全氟乙基苯磺酸盐和全氟甲基苯磺酸盐。More preferably, the fluorine-containing sulfonate is selected from perfluorooctylsulfonate, perfluoroheptylsulfonate, perfluorohexylsulfonate, perfluoropentylsulfonate, perfluorobutylsulfonate salt, perfluoropropyl sulfonate, perfluoroethyl sulfonate, perfluoromethanesulfonate, perfluorononylbenzenesulfonate, perfluorononyloxybenzenesulfonate, perfluoroethylbenzene Sulfonates and perfluoromethylbenzene sulfonates.

在进一步优选的实施方式中，所述含氟磺酸盐为全氟甲基苯磺酸盐或全氟丁基磺酸盐。In a further preferred embodiment, the fluorine-containing sulfonate is perfluoromethylbenzenesulfonate or perfluorobutanesulfonate.

在更进一步优选的实施方式中，所述含氟磺酸盐为全氟丁基磺酸盐，如全氟丁基磺酸钾或全氟丁基磺酸钠；In a further preferred embodiment, the fluorine-containing sulfonate is perfluorobutanesulfonate, such as potassium perfluorobutanesulfonate or sodium perfluorobutanesulfonate;

在更进一步优选的实施方式中，所述含氟磺酸盐为全氟丁基磺酸钾。In a further preferred embodiment, the fluorine-containing sulfonate is potassium perfluorobutanesulfonate.

在一种优选的实施方式中，所述含氟磺酸盐与DOPO类阻燃剂组合用作PLLA阻燃剂。In a preferred embodiment, the fluorine-containing sulfonate is used as a PLLA flame retardant in combination with a DOPO-based flame retardant.

本发明中，所述DOPO类阻燃剂选自DOPO-TRIOL，DOPO-NQ，DOPO-HPM，DOPO-HAM，DOPO-BQ，DDP，和OD-PN；优选地，所述DOPO类阻燃剂选自DOPO-NQ或DDP；In the present invention, the DOPO flame retardant is selected from DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP, and OD-PN; preferably, the DOPO flame retardant Selected from DOPO-NQ or DDP;

在一种优选的实施方式中，所述DOPO类阻燃剂为DDP。In a preferred embodiment, the DOPO-based flame retardant is DDP.

而本发明人经过大量研究发现，含氟磺酸盐只需要添加很少的量就可以起到协同阻燃的效果。However, the inventors have found through extensive research that the fluorosulfonate only needs to be added in a small amount to achieve a synergistic flame retardant effect.

在一种实施方式中，所述含氟磺酸盐与DOPO类阻燃剂的质量比为(0.1～30):100；In one embodiment, the mass ratio of the fluorine-containing sulfonate to the DOPO flame retardant is (0.1-30):100;

在一种优选的实施方式中，所述含氟磺酸盐与DOPO类阻燃剂的质量比为(0.5～28):100。In a preferred embodiment, the mass ratio of the fluorine-containing sulfonate to the DOPO flame retardant is (0.5-28):100.

本发明人发现，加入含氟磺酸盐后，燃烧时间均有显著缩短，UL-94可顺利达到V-0级别。随着含氟磺酸盐含量的增加，阻燃PLLA/DOPO类阻燃剂/含氟磺酸盐共混物的t₁、t₂呈明显降低的趋势，DOPO类阻燃剂与含氟磺酸盐有一定的协效阻燃作用。但，加入的含氟磺酸盐的量也不能太多，一则协效阻燃效果并不会跟着增强，二则会降低阻燃PLLA的力学性能。The inventors found that after adding the fluorosulfonate, the burning time was significantly shortened, and the UL-94 could reach the V-0 level smoothly. With the increase of fluorosulfonate content, the t₁ and t₂ of the flame retardant PLLA/DOPO flame retardant/fluorosulfonate blend tended to decrease significantly. Acid has a certain synergistic flame retardant effect. However, the amount of fluorosulfonic acid salt added should not be too much. First, the synergistic flame retardant effect will not be enhanced, and second, the mechanical properties of the flame retardant PLLA will be reduced.

本发明中，用本发明的包含含氟磺酸盐的阻燃组合物作为阻燃剂可制备得到阻燃PLLA或者用本发明的含氟磺酸盐与DOPO类阻燃剂协同使用可制备得到阻燃PLLA，优选地，制备阻燃PLLA的方法包括以下步骤：In the present invention, the flame retardant PLLA can be prepared by using the flame retardant composition comprising a fluorosulfonate of the present invention as a flame retardant, or can be prepared by using the fluorosulfonate of the present invention in conjunction with a DOPO flame retardant. Flame retardant PLLA, preferably, the method for preparing flame retardant PLLA comprises the following steps:

步骤1，将各原料进行干燥；Step 1, drying each raw material;

步骤2，将干燥后的原料按照设定配比进行熔融混合；Step 2, the dried raw materials are melt-mixed according to the set ratio;

步骤3，使用挤出机挤出，得到阻燃PLLA；Step 3, use an extruder to extrude to obtain flame retardant PLLA;

更优选地，More preferably,

步骤1中，所述各原料包括含氟磺酸盐、DOPO类阻燃剂以及基体聚乳酸PLLA；Instep 1, the raw materials include fluorine-containing sulfonate, DOPO flame retardant and matrix polylactic acid PLLA;

在一种实施方式中，所述含氟磺酸盐为全氟磺酸盐，如全氟烷基磺酸盐、全氟芳基磺酸盐；In one embodiment, the fluorine-containing sulfonate is perfluorosulfonate, such as perfluoroalkanesulfonate, perfluoroarylsulfonate;

所述DOPO类阻燃剂选自DOPO-TRIOL，DOPO-NQ，DOPO-HPM，DOPO-HAM，DOPO-BQ，DDP，和OD-PN；优选地，所述DOPO类阻燃剂选自DOPO-NQ或DDP；进一步优选地，所述DOPO类阻燃剂为DDP。The DOPO-based flame retardant is selected from DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP, and OD-PN; preferably, the DOPO-based flame retardant is selected from DOPO- NQ or DDP; further preferably, the DOPO-based flame retardant is DDP.

其中，用以上方面所述的含氟磺酸盐的阻燃组合物制备的阻燃PLLA，其极限氧指数LOI可达28％，且防火等级UL-94达到V-0级。并且，本发明提供的阻燃PLLA的可纺性良好。Wherein, the flame retardant PLLA prepared with the above-mentioned fluorosulfonate-containing flame retardant composition has a limiting oxygen index LOI of up to 28%, and a fire rating of UL-94 up to V-0. In addition, the flame-retardant PLLA provided by the present invention has good spinnability.

根据本发明提供的一种含氟磺酸盐在聚乳酸PLLA中作为阻燃剂的用途以及包含其的阻燃组合物，具有以下有益效果：According to the use of a fluorine-containing sulfonate in polylactic acid PLLA as a flame retardant and a flame retardant composition comprising the same, the present invention has the following beneficial effects:

(1)本发明提供的含氟磺酸盐能够用于阻燃PLLA的用途，起到协同阻燃的效果；(1) The fluorine-containing sulfonate provided by the present invention can be used for the purpose of flame retardant PLLA, and has the effect of synergistic flame retardant;

(2)本发明提供的阻燃组合物能够用作PLLA阻燃剂，使得PLLA在保持纺丝能力的情况下，同时具有优异的抗熔滴性能以及阻燃性能；(2) The flame retardant composition provided by the present invention can be used as a PLLA flame retardant, so that PLLA has excellent anti-droplet performance and flame retardant performance while maintaining the spinning ability;

(3)本发明中添加少量含氟磺酸盐和DOPO类阻燃剂后，阻燃PLLA的热稳定性测试中800℃时的残炭量和最大热失重速率均有所降低；阻燃PLLA的锥形量热测试中，点燃时间明显延长；(3) After adding a small amount of fluorine-containing sulfonate and DOPO flame retardant in the present invention, the residual carbon amount and the maximum thermal weight loss rate at 800°C in the thermal stability test of the flame retardant PLLA are reduced; the flame retardant PLLA In the cone calorimetry test of , the ignition time was significantly prolonged;

(4)本发明提供的阻燃PLLA的LOI可达到28％，UL-94达到V-0级；且加入含氟磺酸盐和DOPO类阻燃剂后，阻燃PLLA的燃烧时间均有显著缩短，UL-94可顺利达到V-0级别。(4) The LOI of the flame-retardant PLLA provided by the present invention can reach 28%, and the UL-94 can reach the V-0 level; and after adding the fluorosulfonate and DOPO type flame retardants, the burning time of the flame-retardant PLLA is remarkable. Shortened, UL-94 can reach V-0 level smoothly.

实施例Example

实施例1Example 1

将一定量的PLLA，全氟丁基磺酸钾，DDP置于真空干燥箱中80℃下真空干燥12h；Put a certain amount of PLLA, potassium perfluorobutanesulfonate and DDP in a vacuum drying oven at 80°C for vacuum drying for 12h;

取干燥后的PLLA90.8g，全氟丁基磺酸钾0.2g，DDP9.0g加入到双螺杆挤出机(PolyOS，HAAKE，德国)中熔融混合；Take 90.8g of dried PLLA, 0.2g of potassium perfluorobutanesulfonate, and 9.0g of DDP into a twin-screw extruder (PolyOS, HAAKE, Germany) to melt and mix;

用双螺杆挤出机，螺杆转速为50rpm，螺杆各区温度依次为205℃，210℃，210℃，210℃，210℃，205℃，挤压成型，得到阻燃PLLA。Using a twin-screw extruder, the screw speed is 50 rpm, and the temperature of each zone of the screw is 205°C, 210°C, 210°C, 210°C, 210°C, 205°C, and extruded to obtain flame retardant PLLA.

实施例2Example 2

与实施例1的方法相同，其区别在于，步骤2中，取干燥后的PLLA 90.5g，全氟丁基磺酸钾0.5g，DDP 9.0g；得到阻燃PLLA。The method is the same as that in Example 1, except that instep 2, 90.5 g of dried PLLA, 0.5 g of potassium perfluorobutanesulfonate, and 9.0 g of DDP are taken to obtain flame-retardant PLLA.

实施例3Example 3

与实施例1的方法相同，其区别在于，步骤2中，取干燥后的PLLA 90.0g，全氟丁基磺酸钾1.0g，DDP 9.0g；得到阻燃PLLA。The method is the same as that in Example 1, except that instep 2, 90.0 g of dried PLLA, 1.0 g of potassium perfluorobutanesulfonate, and 9.0 g of DDP are taken to obtain flame-retardant PLLA.

实施例4Example 4

与实施例1的方法相同，其区别在于，步骤2中，取干燥后的PLLA 89.5g，全氟丁基磺酸钾1.5g，DDP 9.0g；得到阻燃PLLA。The method is the same as that in Example 1, except that instep 2, 89.5 g of dried PLLA, 1.5 g of potassium perfluorobutanesulfonate, and 9.0 g of DDP are taken to obtain flame-retardant PLLA.

实施例5Example 5

与实施例1的方法相同，其区别在于，步骤2中，取干燥后的PLLA 89.0g，全氟丁基磺酸钾2.0g，DDP 9.0g；得到阻燃PLLA。The method is the same as that in Example 1, except that instep 2, 89.0 g of dried PLLA, 2.0 g of potassium perfluorobutanesulfonate, and 9.0 g of DDP are taken to obtain flame-retardant PLLA.

对比例Comparative ratio

对比例1Comparative Example 1

与实施例1的方法相同，其区别在于，步骤2中，仅取干燥后的PLLA 100.0g；最后挤压成型，得到PLLA。The method is the same as that of Example 1, except that instep 2, only 100.0 g of dried PLLA is taken; finally, PLLA is obtained by extrusion molding.

对比例2Comparative Example 2

与实施例1的方法相同，其区别在于，步骤2中，仅取干燥后的PLLA 97.0g，DDP3.0g；最后挤压成型，得到阻燃PLLA。The method is the same as that of Example 1, the difference is that, instep 2, only 97.0 g of dried PLLA and 3.0 g of DDP are taken; finally, the flame retardant PLLA is obtained by extrusion molding.

对比例3Comparative Example 3

与对比例2的方法相同，其区别在于，步骤2中，仅取干燥后的PLLA 95.0g，DDP5.0g；最后挤压成型，得到阻燃PLLA。The method is the same as that of Comparative Example 2, the difference is that, instep 2, only 95.0 g of dried PLLA and 5.0 g of DDP are taken; finally, the flame retardant PLLA is obtained by extrusion molding.

对比例4Comparative Example 4

与对比例2的方法相同，其区别在于，步骤2中，仅取干燥后的PLLA 93.0g，DDP7.0g；最后挤压成型，得到阻燃PLLA。The method is the same as that of Comparative Example 2, except that, instep 2, only 93.0 g of dried PLLA and 7.0 g of DDP are taken; finally, the flame retardant PLLA is obtained by extrusion molding.

对比例5Comparative Example 5

与对比例2的方法相同，其区别在于，步骤2中，仅取干燥后的PLLA 91.0g，DDP9.0g；最后挤压成型，得到阻燃PLLA。The method is the same as that of Comparative Example 2, the difference is that, instep 2, only 91.0 g of dried PLLA and 9.0 g of DDP are taken; finally, the flame retardant PLLA is obtained by extrusion molding.

对比例6Comparative Example 6

与对比例2的方法相同，其区别在于，步骤2中，仅取干燥后的PLLA 89.0g，DDP11.0g；最后挤压成型，得到阻燃PLLA。The method is the same as that of Comparative Example 2, the difference is that, instep 2, only 89.0 g of dried PLLA and 11.0 g of DDP are taken; finally, the flame retardant PLLA is obtained by extrusion molding.

对比例7Comparative Example 7

将干燥后的基体PLLA372g与阻燃剂聚四氟乙烯28g熔融共混，得到阻燃PLLA。The dried base PLLA 372g and the flame retardant polytetrafluoroethylene 28g were melt-blended to obtain flame retardant PLLA.

实验例Experimental example

实验例1样品的热稳定性DSC分析DSC Analysis of Thermal Stability of Samples in Experimental Example 1

将对比例1～对比例6以及实施例1～5进行DSC升温和降温分析，相关数据如表1和表2所示，以及DSC曲线图如图1(a)，图1(b)，和图2(a)，图2(b)所示。Comparative Examples 1 to 6 and Examples 1 to 5 were subjected to DSC heating and cooling analysis, the relevant data are shown in Table 1 and Table 2, and the DSC curves are shown in Figure 1(a), Figure 1(b), and Figure 2(a), Figure 2(b).

表1为对比例1～6的DSC升温和降温的数据表；Table 1 is a data table of the DSC heating and cooling of Comparative Examples 1 to 6;

表2为对比例1，对比例5，以及实施例1～实施例5的DSC升温和降温的数据表；Table 2 is the data table of the DSC heating and cooling of Comparative Example 1, Comparative Example 5, and Examples 1 to 5;

图1(a)为对比例1～对比例6的DSC升温曲线；Figure 1(a) is the DSC heating curve of Comparative Examples 1 to 6;

图1(b)为对比例1～对比例6的DSC降温曲线；Figure 1(b) shows the DSC cooling curves of Comparative Examples 1 to 6;

图2(a)为对比例1，对比例5，以及实施例1～实施例5的DSC升温曲线；Figure 2(a) is the DSC heating curve of Comparative Example 1, Comparative Example 5, and Examples 1 to 5;

图2(b)为对比例1，对比例5，以及实施例1～实施例5的DSC降温曲线；Figure 2(b) is the DSC cooling curve of Comparative Example 1, Comparative Example 5, and Examples 1 to 5;

表1对比例1～对比例6产品的DSC测试结果Table 1 DSC test results of products from Comparative Example 1 to Comparative Example 6

样品编号Sample serial numberT_cc(℃)T_cc(℃)T_m(℃)T_m(℃)T_mc(℃)T_mc(℃)T₀(℃)T₀(℃)T_m-T₀(℃)T_m-T₀(℃)对比例1Comparative Example 19898174174999991918383对比例2Comparative Example 29696173173979787878686对比例3Comparative Example 39898172172939390908282对比例4Comparative Example 49797172172929289898383对比例5Comparative Example 59797172172919189898383对比例6Comparative Example 69898170170919189898181

表2对比例1，对比例5以及实施例1～实施例5产品的DSC测试结果Table 2 Comparative Example 1, Comparative Example 5 and the DSC test results of the products of Examples 1 to 5

样品编号Sample serial numberT_cc(℃)T_cc(℃)T_m(℃)T_m(℃)T_mc(℃)T_mc(℃)对比例1Comparative Example 198981741749999对比例5Comparative Example 595951711719090实施例1Example 194941711718989实施例2Example 293931721728686实施例3Example 394941701708787实施例4Example 493931721728888实施例5Example 592921721729090

从表1以及图1(a)和图1(b)中可以看出，随着DOPO类阻燃剂含量的增加，PLLA/DOPO类阻燃剂共混物的熔点逐渐降低。加入DOPO类阻燃剂时与纯PLLA的T_CC(冷结晶温度)相比总体上有降低的趋势，说明DOPO类阻燃剂具有一定的增塑作用，结晶可在低温下完成。It can be seen from Table 1 and Figures 1(a) and 1(b) that with the increase of DOPO-based flame retardant content, the melting point of the PLLA/DOPO-based flame retardant blend gradually decreases. Compared with pure PLLA, the_TCC (cold crystallization temperature) of DOPO-based flame retardants tended to decrease as a whole, indicating that DOPO-based flame retardants have a certain plasticizing effect, and crystallization can be completed at low temperatures.

从表2以及图2(a)和图2(b)中可以看出，与纯PLLA相比，实施例1～实施例5产品的冷结晶在较低温度下发生，说明分子链运动能力有所增加。还可以看出，加入含氟磺酸盐后熔融结晶峰消失，这可能是由于含氟磺酸盐对PLLA的晶体生长起到了抑制的作用，阻碍了PLLA的结晶。As can be seen from Table 2 and Figures 2(a) and 2(b), compared with pure PLLA, the cold crystallization of the products of Examples 1 to 5 occurred at a lower temperature, indicating that the molecular chain movement ability has increased. It can also be seen that the melting crystallization peak disappears after the addition of fluorosulfonate, which may be because the fluorosulfonate inhibits the crystal growth of PLLA and hinders the crystallization of PLLA.

实验例2样品的热稳定性分析Thermal stability analysis of samples in experimental example 2

将对比例1～对比例6以及实施例1～5进行热稳定性分析，相关数据如表3和表4所示，以及热稳定性曲线图如图3(a)，图3(b)，和图4(a)，图4(b)所示。The thermal stability analysis of Comparative Examples 1 to 6 and Examples 1 to 5 was carried out. The relevant data are shown in Table 3 and Table 4, and the thermal stability curves are shown in Figure 3(a) and Figure 3(b), and Figure 4(a), Figure 4(b).

表3示出对比例1～对比例6的热失重结果表；Table 3 shows the thermal weight loss result table of Comparative Examples 1 to 6;

表4示出对比例1，对比例5和实施例1～实施例5的热失重结果表；Table 4 shows the thermal weight loss result table of Comparative Example 1, Comparative Example 5 and Examples 1 to 5;

图3(a)和图3(b)示出对比例1～对比例6的TG和DTG分析曲线图；Figure 3(a) and Figure 3(b) show the TG and DTG analysis curves of Comparative Examples 1 to 6;

图4(a)，图4(b)示出对比例1，对比例5和实施例1～实施例5的TG和DTG分析曲线图。FIG. 4( a ) and FIG. 4( b ) show the TG and DTG analysis graphs of Comparative Example 1, Comparative Example 5 and Examples 1 to 5.

表3对比例1～对比例6的产品的热失重结果表Table 3 Thermal weight loss results of the products of Comparative Examples 1 to 6

注：T_5wt％热失重5wt％对应温度，T_max：最大热失重速率对应温度Note: T_5wt% thermal weight loss corresponds to temperature of 5wt%,_Tmax : maximum thermal weight loss rate corresponds to temperature

表4对比例1，对比例5和实施例1～实施例5的热失重结果表Table 4 Comparative Example 1, Comparative Example 5 and the results of thermal weight loss of Examples 1 to 5

注：T_5wt％热失重5wt％对应温度，T_max：最大热失重速率对应温度Note: T_5wt% thermal weight loss corresponds to temperature of 5wt%,_Tmax : maximum thermal weight loss rate corresponds to temperature

从表3和图3(a)，图3(b)可以看出，随着DOPO类阻燃剂含量的增加，PLLA/DOPO类阻燃剂共混物的熔点逐渐降低。加入DOPO类阻燃剂时与纯PLLA的T_CC(冷结晶温度)相比总体上有降低的趋势，说明DOPO类阻燃剂具有一定的增塑作用，结晶可在低温下完成。T_mc(熔融结晶温度)总体呈现降低的趋势，且随着DOPO类阻燃剂含量的不断增多，其熔融结晶峰减弱甚至消失，可能是由于DOPO类阻燃剂的加入，使其与PLLA分子间相互作用，导致共混物成核和晶粒增长更为困难，降低了PLLA的结晶性能。(T_m-T₀)表示过冷度，过冷度越大，则切片可纺性越好。加入DOPO类阻燃剂后，过冷度并没有多大的变化，而添加9％DOPO类阻燃剂(对比例5)时的过冷度与纯PLLA相同，因此也可以表明DOPO类阻燃剂的加入一定程度上没有降低材料的可纺性。It can be seen from Table 3 and Figures 3(a) and 3(b) that with the increase of DOPO-based flame retardant content, the melting point of the PLLA/DOPO-based flame retardant blend gradually decreases. Compared with pure PLLA, the_TCC (cold crystallization temperature) of DOPO-based flame retardants tended to decrease as a whole, indicating that DOPO-based flame retardants have a certain plasticizing effect, and crystallization can be completed at low temperatures. T_mc (melt crystallization temperature) generally showed a decreasing trend, and with the continuous increase of DOPO flame retardant content, its melting crystallization peak weakened or even disappeared, which may be due to the addition of DOPO flame retardant, which made it and PLLA molecules The interaction between the two makes the nucleation and grain growth of the blends more difficult and reduces the crystalline properties of PLLA. (T_m -T₀ ) represents the degree of subcooling, and the greater the degree of subcooling, the better the spinnability of the slices. After adding DOPO flame retardant, the degree of supercooling did not change much, while the supercooling degree when adding 9% DOPO flame retardant (Comparative Example 5) was the same as that of pure PLLA, so it can also indicate that DOPO flame retardant The addition of the material did not reduce the spinnability of the material to a certain extent.

从表4，图4(a)，图4(b)中可以看出，随着阻燃剂含氟磺酸盐含量的增加，实施例1～实施例5中共混物达到最大热分解速率时所对应的温度基本维持在363℃左右，最大热失重速率从33.8％/min增加到34.5％/min，共混物残炭量由9.1％增加到11.8％。但与只添加9％DOPO类阻燃剂(对比例5)相比，添加少量含氟磺酸盐后，800℃时的残炭量和最大热失重速率均有所降低。与纯PLLA相比，加入DOPO类阻燃剂、含氟磺酸盐的阻燃组合物的复合阻燃剂后残炭量的增加并不明显，起始分解和最大热分解速率时的温度略有下降，说明DOPO类阻燃剂、含氟磺酸盐的阻燃组合物的复合阻燃剂对PLLA热稳定性有一定影响。It can be seen from Table 4, Figure 4(a) and Figure 4(b) that with the increase of the content of fluorosulfonate in the flame retardant, when the blends of Examples 1 to 5 reach the maximum thermal decomposition rate The corresponding temperature was maintained at about 363℃, the maximum thermal weight loss rate increased from 33.8%/min to 34.5%/min, and the carbon residue in the blend increased from 9.1% to 11.8%. However, compared with only adding 9% DOPO flame retardant (Comparative Example 5), after adding a small amount of fluorosulfonate, the amount of carbon residue and the maximum thermal weight loss rate at 800°C are both reduced. Compared with pure PLLA, the increase of carbon residue after adding DOPO flame retardant and composite flame retardant of fluorosulfonate-containing flame retardant composition is not obvious, and the temperature at initial decomposition and maximum thermal decomposition rate is slightly lower. There is a decrease, indicating that the DOPO type flame retardant and the composite flame retardant of the fluorosulfonate-containing flame retardant composition have a certain influence on the thermal stability of PLLA.

实验例3样品的燃烧性能分析The combustion performance analysis of the sample of experimental example 3

将对比例1～对比例6以及实施例1～5进行燃烧性能分析，即锥形量热测试，相关数据如表5和表6所示，以及锥形量热曲线图如图5(a)，图5(b)，和图6(a)，图6(b)所示。其中，The combustion performance analysis of Comparative Examples 1 to 6 and Examples 1 to 5, that is, cone calorimetry test, the relevant data are shown in Table 5 and Table 6, and the cone calorimetry curve is shown in Figure 5(a) , Figure 5(b), and Figure 6(a), Figure 6(b). in,

表5示出对比例1～对比例6的产品的锥形量热测试结果；Table 5 shows the cone calorimetry test results of the products of Comparative Examples 1 to 6;

表6示出对比例1，对比例5和实施例1～实施例5的产品的锥形量热测试结果；Table 6 shows the cone calorimetry test results of Comparative Example 1, Comparative Example 5 and the products of Examples 1 to 5;

图5(a)和图5(b)示出对比例1～对比例6的产品的锥形量热图；Figures 5(a) and 5(b) show the cone calorimetry diagrams of the products of Comparative Examples 1 to 6;

图6(a)和图6(b)示出对比例5和实施例1～实施例5的产品的锥形量热图；Figure 6(a) and Figure 6(b) show the cone calorimetry diagrams of the products of Comparative Example 5 and Examples 1 to 5;

表5对比例1～对比例6的产品的锥形量热测试结果Table 5 Cone calorimetry test results of the products of Comparative Examples 1 to 6

表6对比例1，对比例5和实施例1～实施例5的产品的锥形量热测试结果Table 6 Cone calorimetry test results of the products of Comparative Example 1, Comparative Example 5 and Example 1 to Example 5

从表5，图5(a)和图5(b)中可以看出，与纯的PLLA样品相比，加入阻燃剂DOPO类阻燃剂后点燃时间明显(TTI)延长，随着DOPO类阻燃剂的增加，最高热释放速率(pHRR)呈现明显的增大趋势，总热释放量(THR)有降低的趋势，总体上来说，DOPO类阻燃剂对PLLA的燃烧热分解具有一定的抑制作用。综上所述，DOPO类阻燃剂对PLLA具有一定的阻燃作用。From Table 5, Fig. 5(a) and Fig. 5(b), it can be seen that compared with pure PLLA samples, the ignition time (TTI) was significantly prolonged after adding the flame retardant DOPO type flame retardant, with the increase of DOPO type flame retardant. With the increase of flame retardants, the maximum heat release rate (pHRR) showed an obvious increasing trend, and the total heat release rate (THR) showed a decreasing trend. inhibition. In summary, DOPO flame retardants have a certain flame retardant effect on PLLA.

通过对表6，图6(a)和图6(b)数据进行比较分析发现，与只添加9％DOPO类阻燃剂(对比例5)相比，加入含氟磺酸盐后点燃时间明显延长，当含氟磺酸盐添加量达2％时(实施例5)平均热释放速率(mHRR)和平均质量损失速率(mMLR)明显降低，但总释放热(THR)并没有降低。By comparing and analyzing the data in Table 6, Figure 6(a) and Figure 6(b), it is found that compared with only adding 9% DOPO flame retardant (Comparative Example 5), the ignition time after adding fluorosulfonate is obvious Prolonged, when the amount of fluorosulfonate was added up to 2% (Example 5), the average heat release rate (mHRR) and the average mass loss rate (mMLR) decreased significantly, but the total heat release (THR) did not decrease.

实验例4样品的阻燃性能分析Analysis of flame retardant properties of experimental example 4 samples

将对比例1～对比例6以及实施例1～5进行阻燃性能分析，相关数据如表7和表8所示，包括LOI和UL-94测试结果以及熔滴情况；The flame retardant properties of Comparative Examples 1 to 6 and Examples 1 to 5 were analyzed. The relevant data are shown in Table 7 and Table 8, including the test results of LOI and UL-94 and the situation of molten droplets;

其中，表7示出对比例1～对比例6的产品的阻燃性能分析数据；表8示出对比例1，对比例5和实施例1～5的产品的阻燃性能分析数据。Among them, Table 7 shows the flame retardant performance analysis data of the products of Comparative Examples 1 to 6; Table 8 shows the flame retardant performance analysis data of the products of Comparative Example 1, Comparative Example 5 and Examples 1 to 5.

表7对比例1～对比例6的产品的LOI和UL-94测试结果Table 7 LOI and UL-94 test results of the products of Comparative Examples 1 to 6

表8对比例1，对比例5和实施例1～5的产品的LOI和UL-94测试结果Table 8 Comparative Example 1, Comparative Example 5 and LOI and UL-94 test results of the products of Examples 1 to 5

从表7可以看出，随着DOPO类阻燃剂含量的增加，PLLA的LOI值有明显上升的趋势，但是t₁和t₂都有明显的降低趋势，说明随着DOPO类阻燃剂含量的增加，阻燃性能有所提高。当DOPO类阻燃剂添加量9％及以上时(对比例5～6)，阻燃聚乳酸在空气中燃烧出现了自熄的现象，UL-94顺利达到V-0级别。It can be seen from Table 7 that with the increase of DOPO flame retardant content, the LOI value of PLLA has an obvious upward trend, but both t₁ and t₂ have a significant downward trend, indicating that with the increase of DOPO flame retardant content The increase of the flame retardant performance has improved. When the DOPO flame retardant was added in an amount of 9% or more (Comparative Examples 5 to 6), the flame retardant polylactic acid burned in the air and appeared self-extinguishing, and UL-94 successfully reached the V-0 level.

从表7、表8中可以发现，将实施例1～5与对比例1～4相比较可知，加入少量的阻燃剂含氟磺酸盐使得PLLA的LOI有一定的提高，并且加入阻燃剂含氟磺酸盐后，燃烧时间均有显著缩短，UL-94可顺利达到V-0级别。随着含氟磺酸盐含量的增加，阻燃PLLA/DOPO类阻燃剂/含氟磺酸盐共混物的t₁、t₂呈明显降低的趋势，因此，DOPO类阻燃剂与含氟磺酸盐有一定的协效阻燃作用。It can be found from Table 7 and Table 8 that comparing Examples 1 to 5 with Comparative Examples 1 to 4, it can be seen that the addition of a small amount of flame retardant fluorosulfonate can improve the LOI of PLLA to a certain extent, and the addition of flame retardant After the agent contains fluorosulfonate, the burning time is significantly shortened, and UL-94 can reach the V-0 level smoothly. With the increase of fluorosulfonate content, the t₁ and t₂ of the flame retardant PLLA/DOPO flame retardant/fluorosulfonate blend tend to decrease significantly. Fluorosulfonate has a certain synergistic flame retardant effect.

实验例5样品的可纺性能分析Analysis of the spinnability of the samples in Experimental Example 5

将对比例7以及实施例2～5的产品进行纺丝性能测试，结果见表9，表10。其中，Spinning performance tests were carried out on the products of Comparative Example 7 and Examples 2 to 5. The results are shown in Table 9 and Table 10. in,

表9示出对比例7以及实施例2～5产品的纺丝工艺参数；Table 9 shows the spinning process parameters of Comparative Example 7 and the products of Examples 2 to 5;

表10示出对比例7，实施例2～5产品的纤维力学性能测试结果表；Table 10 shows Comparative Example 7, the fiber mechanical properties test result table of the products of Examples 2 to 5;

表9样品纺丝工艺参数Table 9 Sample spinning process parameters

表10样品纤维力学性能测试结果Table 10 Test results of mechanical properties of sample fibers

从表9和表10可以看出，与其它阻燃剂的阻燃PLLA(对比例7)的纺丝性能数据对比，本发明提供的阻燃PLLA的纺丝性能(断裂强度和断裂伸长率)具有明显的优势，而且，本发明提供的阻燃PLLA的阻燃性能优异，燃烧时间均有显著缩短，UL-94可顺利达到V-0级别。As can be seen from Table 9 and Table 10, compared with the spinning performance data of the flame retardant PLLA of other flame retardants (Comparative Example 7), the spinning performance (breaking strength and elongation at break) of the flame retardant PLLA provided by the present invention ) has obvious advantages, and the flame retardant PLLA provided by the present invention has excellent flame retardant performance, the burning time is significantly shortened, and the UL-94 can reach the V-0 level smoothly.

实验例6样品的SEM分析SEM analysis of the sample of experimental example 6

将对比例1～对比例6以及实施例1～5的产品进行SEM分析，结果如图7和图8所示。SEM analysis was performed on the products of Comparative Examples 1 to 6 and Examples 1 to 5, and the results are shown in FIG. 7 and FIG. 8 .

图7示出对比例1～对比例6产品的SEM图；图7中(a)～(f)分别相应表示对比例1～对比例6的产品的SEM图；Figure 7 shows the SEM images of the products of Comparative Examples 1 to 6; (a) to (f) in Figure 7 respectively represent the SEM images of the products of Comparative Examples 1 to 6;

图8示出对比例5和实施例1～实施例5产品的SEM图；图8中a～f分别相应表示对比例5和实施例1～实施例5产品的SEM图。FIG. 8 shows the SEM images of the products of Comparative Example 5 and Examples 1 to 5; a to f in FIG. 8 respectively represent the SEM images of the products of Comparative Example 5 and Examples 1 to 5.

如图7所示，可以看出在所研究的范围内没有出现明显的阻燃剂团聚现象；而且随着阻燃剂的增加，可以明显的看出粒子分布比较密集。图7中e为添加9％DOPO类阻燃剂(对比例5)时共混物的SEM图，图中无明显的团聚现象且分布比较均匀，粒子分布比较密集；图7中f为添加11％DOPO类阻燃剂(对比例6)时共混物的SEM图，可以看出随着DOPO类阻燃剂含量的增加，在PLLA中的分布还是较为均匀的。这主要是由于共混的温度高于DOPO类阻燃剂的熔点，其在与PLLA共混时处于熔体共混的状态，因此混合较为均匀。As shown in Figure 7, it can be seen that there is no obvious flame retardant agglomeration phenomenon in the studied range; and with the increase of flame retardant, it can be clearly seen that the particle distribution is relatively dense. In Figure 7, e is the SEM image of the blend when 9% DOPO flame retardant (Comparative Example 5) is added. In the figure, there is no obvious agglomeration phenomenon, the distribution is relatively uniform, and the particle distribution is relatively dense; in Figure 7, f is the addition of 11 The SEM image of the blend at % DOPO type flame retardant (Comparative Example 6), it can be seen that with the increase of DOPO type flame retardant content, the distribution in PLLA is relatively uniform. This is mainly because the blending temperature is higher than the melting point of DOPO-based flame retardants, which are in the state of melt blending when blending with PLLA, so the mixing is relatively uniform.

从图8可以看出，在所研究的范围内，添加含氟磺酸盐的质量较少(实施例1～3中的添加量)时阻燃剂分散较均匀并无明显的团聚现象，而当添加量稍多(实施例4～5中的添加量)时，可观察到少量的阻燃剂团聚现象。It can be seen from Figure 8 that within the studied range, when the mass of fluorosulfonate added is less (the amount added in Examples 1 to 3), the flame retardant is dispersed more uniformly and there is no obvious agglomeration, while When the addition amount is slightly larger (the addition amount in Examples 4 to 5), a small amount of flame retardant agglomeration can be observed.

以上结合具体实施方式和范例性实例对本发明进行了详细说明，不过这些说明并不能理解为对本发明的限制。本领域技术人员理解，在不偏离本发明精神和范围的情况下，可以对本发明技术方案及其实施方式进行多种等价替换、修饰或改进，这些均落入本发明的范围内。本发明的保护范围以所附权利要求为准。The present invention has been described in detail above in conjunction with specific embodiments and exemplary examples, but these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that, without departing from the spirit and scope of the present invention, various equivalent replacements, modifications or improvements can be made to the technical solutions of the present invention and the embodiments thereof, which all fall within the scope of the present invention. The scope of protection of the present invention is determined by the appended claims.

Claims (10)

1. A flame retardant composition comprising fluorosulfonate salt and used as a PLLA flame retardant, characterized in that said flame retardant composition comprises fluorosulfonate salt and DOPO-based flame retardant.

2. Flame retardant composition according to claim 1,

the mass ratio of the fluorine-containing sulfonate to the DOPO flame retardant is (0.1-30): 100.

3. The flame retardant composition of claim 1 or 2, wherein the DOPO based flame retardant is selected from DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP, and OD-PN.

4. Flame retardant composition according to claim 1 or 2, wherein the DOPO based flame retardant is selected from DOPO-NQ or DDP.

5. Flame retardant composition according to one of claims 1 to 4, wherein the fluorosulfonate is a perfluorosulfonate, such as a perfluoroalkylsulfonate, perfluoroarylsulfonate.

6. The flame retardant composition of claim 5 wherein the fluorine-containing sulfonate salt is selected from the group consisting of perfluorooctyl sulfonate, perfluoroheptyl sulfonate, perfluorohexyl sulfonate, perfluoropentyl sulfonate, perfluorobutyl sulfonate, perfluoropropyl sulfonate, perfluoroethyl sulfonate, perfluoromethyl sulfonate, perfluorononyl benzene sulfonate, perfluoroethyl benzene sulfonate, perfluoromethyl benzene sulfonate, and perfluoromethyl benzene sulfonate.

7. The flame retardant composition of claim 6 wherein the fluorosulfonate salt is a perfluoromethylbenzenesulfonate salt or a perfluorobutylsulfonate salt.

8. Use of a fluorosulfonate salt as a flame retardant for PLLA, characterized in that said fluorosulfonate salt is a perfluorosulfonate salt, preferably a perfluoroalkylsulfonate salt, a perfluoroarylsulfonate salt;

more preferably, the fluorine-containing sulfonate is selected from the group consisting of perfluorooctyl sulfonate, perfluoroheptyl sulfonate, perfluorohexyl sulfonate, perfluoropentyl sulfonate, perfluorobutyl sulfonate, perfluoropropyl sulfonate, perfluoroethyl sulfonate, perfluoromethyl sulfonate, perfluorononyl benzene sulfonate, perfluorononyl oxy benzene sulfonate, perfluoroethyl benzene sulfonate, perfluoromethyl benzene sulfonate.

9. Use according to claim 8, characterized in that the fluorosulfonate salt is used as a PLLA flame retardant in combination with a DOPO-based flame retardant.

10. Use according to claim 9, wherein the DOPO based flame retardant is selected from DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP, and OD-PN; preferably, the DOPO-based flame retardant is selected from DOPO-NQ or DDP.

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