CN111138816A

CN111138816A - Application of fluorine-containing sulfonate as flame retardant in polylactic acid PLLA and flame-retardant composition containing fluorine-containing sulfonate

Info

Publication number: CN111138816A
Application number: CN201811300602.3A
Authority: CN
Inventors: 王锐; 张安莹; 李海阔; 王照颖; 董振峰; 张秀芹
Original assignee: Beijing Institute of Clothing Technology
Current assignee: Beijing Institute of Clothing Technology; Beijing Institute Fashion Technology
Priority date: 2018-11-02
Filing date: 2018-11-02
Publication date: 2020-05-12

Abstract

The invention provides an application of fluorosulfonate as a flame retardant in polylactic acid PLLA and a flame retardant composition containing the same.

Description

Application of fluorine-containing sulfonate as flame retardant in polylactic acid PLLA and flame-retardant composition containing fluorine-containing sulfonate

Technical Field

The invention relates to the field of high polymer materials, in particular to a flame retardant containing fluorosulfonate for flame retarding PLLA and a flame retardant composition containing the fluorosulfonate.

Background

Polylactic acid PLLA, also known as polylactide, belongs to a family of polyesters, and is a polymer obtained by polymerizing lactic acid serving as a main raw material, wherein the raw material source is sufficient and can be regenerated; however, the polylactic acid PLLA is poor in heat resistance and is easily combustible, and it is necessary to impart flame retardancy to the polylactic acid PLLA by a modification method.

CN201410444423.2 discloses a preparation method of a polylactic acid composite material with a flame retardant function, which comprises the steps of mixing polylactic acid, core/shell-polymethyl siloxane/polymethyl methacrylate particles and polyaryl phosphate, and carrying out melt blending by using a torque rheometer at 168-180 ℃ to obtain the polylactic acid composite material with the flame retardant function, wherein the mass fraction of the core/shell-polymethyl siloxane/polymethyl methacrylate particles is 0-25%; the mass fraction of the polyaryl phosphate is 0-25%, and the core/shell-polymethylsiloxane/polymethyl methacrylate particles and the polyaryl phosphate cannot be 0 at the same time.

The patent documents CN1823127, CN101260227 and CN101440156 respectively report the application of a series of conventional halogen-free flame retardants and conventional intumescent flame retardants to retard flame of polylactic acid. However, the application of intumescent flame retardants and inorganic flame retardants is mainly limited in that the addition amount is large, which affects the physical and mechanical properties of polylactic acid, and thus the flame retardant efficiency is still to be improved.

In JP 5378904B 9, a polylactic acid resin composition containing a thermoplastic resin, a phosphorus-based or nitrogen-based or metal oxide-based flame retardant and a flame retardant aid in addition to polylactic acid is proposed, but the flame retardancy is evaluated only in UL94, the flame retardant effect cannot be accurately known, and no spinning performance data is provided.

Therefore, it is highly desirable to provide a compound with flame retardant property and a flame retardant composition containing the same for flame retardant PLLA, and to provide a preparation method of flame retardant PLLA, so that the flame retardant PLLA has excellent flame retardant property and anti-dripping property while maintaining good spinning ability.

Disclosure of Invention

In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: the use of fluorosulfonate as a flame retardant in polylactic acid (PLLA) and flame retardant compositions comprising the same, said fluorosulfonate and DOPO-based flame retardants synergistically act to retard flame of PLLA; the flame-retardant composition comprises fluorosulfonate and DOPO flame retardants, can be used as a PLLA flame retardant, and enables flame-retardant PLLA to have excellent anti-dripping performance and flame-retardant performance under the condition of keeping good spinning capacity, thereby completing the invention.

The object of the present invention is to provide the following:

in a first aspect, the present invention provides a flame retardant composition comprising a fluorosulfonate salt and used as a PLLA flame retardant, the flame retardant composition comprising a fluorosulfonate salt and a DOPO-based flame retardant.

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

Wherein the DOPO-based flame retardant is selected from DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP, and OD-PN.

Wherein the fluorine-containing sulfonate is perfluorosulfonate, such as perfluoroalkyl sulfonate and perfluoroaryl sulfonate.

In a second aspect, the invention also provides a use of a fluorosulfonate as a PLLA flame retardant, the fluorosulfonate being a perfluorosulfonate, preferably a perfluoroalkylsulfonate, a perfluoroarylsulfonate;

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 and perfluoromethyl benzene sulfonate.

Wherein the fluorosulfonate salt is used in combination with a DOPO-based flame retardant as a PLLA flame retardant.

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.

Drawings

FIG. 1(a) shows DSC temperature rise profiles of comparative examples 1 to 6;

FIG. 1(b) shows DSC temperature drop profiles for comparative examples 1-6;

FIG. 2(a) shows DSC temperature rise profiles for the products of comparative example 1, comparative example 5 and examples 1-5;

FIG. 2(b) shows DSC decreasing temperature profiles of the products of comparative example 1, comparative example 5 and examples 1 to 5;

FIG. 3(a) shows TG curves of comparative examples 1 to 6;

FIG. 3(b) shows DTG profiles of comparative examples 1 to 6;

FIG. 4(a) shows TG curves of the products of comparative example 1, comparative example 5 and examples 1 to 5;

FIG. 4(b) shows DTG profiles of the products of comparative example 1, comparative example 5 and examples 1 to 5;

FIG. 5(a) shows the cone calorimetry HRR plots for the products of comparative examples 1 to 6;

FIG. 5(b) shows the cone calorimetry THR curves for the products of comparative examples 1 to 6;

FIG. 6(a) shows the cone calorimetry HRR plots for the products of comparative example 5 and examples 1-5;

FIG. 6(b) shows the cone calorimetry THR plot for the products of comparative example 5 and examples 1-5;

FIG. 7 shows SEM images of comparative examples 1 to 6;

fig. 8 shows SEM images of the products of comparative example 5 and examples 1 to 5.

Detailed Description

The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.

The present invention is described in detail below.

Through a great deal of research and experiments, the inventor finds that the fluorine-containing sulfonate and the flame-retardant composition containing the same can be used for improving the flame retardance and the melt-drip resistance of PLLA, and simultaneously keeps better spinning performance.

According to a first aspect of the present invention there is provided a flame retardant composition comprising a fluorosulfonate salt and used as a PLLA flame retardant, said flame retardant composition comprising a fluorosulfonate salt and a DOPO-based flame retardant.

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

further preferably, the mass ratio of the fluorine-containing sulfonate to the DOPO flame retardant is (0.5-28): 100.

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.

In a further preferred embodiment, the DOPO-based flame retardant is selected from DOPO-NQ or DDP;

in a still further preferred embodiment, the DOPO-based flame retardant is DDP.

In a preferred embodiment, the fluorosulfonate salt is a perfluorosulfonate salt, such as a perfluoroalkylsulfonate salt, a perfluoroarylsulfonate salt; more preferably a potassium or sodium sulfonate salt.

In a further preferred embodiment, 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, and perfluoromethyl benzene sulfonate.

In a still further preferred embodiment, the fluorosulfonate salt is perfluoromethylbenzenesulfonate or perfluorobutylsulfonate;

in a still further preferred embodiment, the fluorosulfonate salt is a perfluorobutylsulfonate salt, such as potassium perfluorobutylsulfonate or sodium perfluorobutylsulfonate; more preferably potassium perfluorobutylsulfonate.

The inventor finds that the fluorine-containing sulfonate is matched with the DOPO flame retardant for use, so that the combustion time of a PLLA system is shortened to a certain extent, UL-94 can smoothly reach the V-0 level, the flame retardance is improved, and the anti-dripping performance is greatly enhanced.

In the invention, DOPO is a short name of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the structure of the DOPO contains a P-H bond, so that the DOPO has high activity on olefin, epoxy compounds and carbonyl compounds. The DOPO flame retardant refers to DOPO and derivatives thereof, and the molecular structure of the DOPO flame retardant contains a biphenyl ring, a phenanthrene ring and an O ═ P-O bond, so that the DOPO flame retardant has stronger flame retardant performance than common organic phosphate.

In the DOPO flame retardant, the molecular formula structures of DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP and OD-PN are as follows:

the preparation method of the flame-retardant composition comprises the step of mixing the fluorine-containing sulfonate and the DOPO flame retardant.

In the present invention, the preparation method of the flame retardant composition is not particularly limited, and preferably, the preparation method comprises mixing the fluorosulfonate and the DOPO flame retardant in a certain mass ratio for use.

According to a second aspect of the present invention there is provided the use of a fluorosulfonate salt as a flame retardant for PLLA, said fluorosulfonate salt being a perfluorosulfonate salt, preferably a perfluoroalkylsulfonate salt, a perfluoroarylsulfonate salt; more preferably a potassium or sodium sulfonate salt;

In a further preferred embodiment, the fluorosulfonate salt is perfluoromethylbenzenesulfonate or perfluorobutylsulfonate.

In a still further preferred embodiment, the fluorosulfonate salt is a perfluorobutylsulfonate salt, such as potassium perfluorobutylsulfonate or sodium perfluorobutylsulfonate;

in a still further preferred embodiment, the fluorosulfonate salt is potassium perfluorobutylsulfonate.

In a preferred embodiment, the fluorosulfonate salt is used as a PLLA flame retardant in combination with a DOPO-based flame retardant.

In the present invention, 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;

in a preferred embodiment, the DOPO-based flame retardant is DDP.

The inventor of the invention discovers through a great deal of research that the fluorine-containing sulfonate can achieve the synergistic flame retardant effect only by adding a small amount.

In one embodiment, the mass ratio of the fluorine-containing sulfonate to the DOPO flame retardant is (0.1-30): 100;

in a preferred embodiment, the mass ratio of the fluorine-containing sulfonate to the DOPO-based flame retardant is (0.5-28): 100.

The inventor finds that after the fluorine-containing sulfonate is added, the combustion time is obviously shortened, and UL-94 can smoothly reach the V-0 level. Flame retardant PLLA/DOPO based flame retardants/fluorosulfonate blends with increased fluorosulfonate content₁、t₂The DOPO flame retardant and the fluorine-containing sulfonate have certain synergistic flame retardant effect. However, the amount of the added fluorosulfonate is not too large, so that the synergistic flame retardant effect is not enhanced, and the mechanical properties of the flame retardant PLLA are reduced.

In the present invention, flame retardant PLLA can be prepared by using the flame retardant composition comprising fluorosulfonate of the present invention as a flame retardant or flame retardant PLLA can be prepared by using the fluorosulfonate of the present invention in cooperation with a DOPO-based flame retardant, preferably, the method for preparing flame retardant PLLA comprises the steps of:

step 1, drying each raw material;

step 2, melting and mixing the dried raw materials according to a set proportion;

step 3, extruding by using an extruder to obtain flame-retardant PLLA;

more preferably still, the first and second liquid crystal compositions are,

in the step 1, the raw materials comprise fluorine-containing sulfonate, DOPO flame retardant and matrix polylactic acid PLLA;

in one embodiment, the fluorosulfonate salt is a perfluorosulfonate salt, such as a perfluoroalkylsulfonate salt, a perfluoroarylsulfonate salt;

the DOPO 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.

Wherein, the limit oxygen index LOI of the flame-retardant PLLA prepared by the flame-retardant composition containing the fluorosulfonate can reach 28 percent, and the fire-retardant rating UL-94 reaches V-0 level. In addition, the flame-retardant PLLA provided by the invention has good spinnability.

According to the application of the fluorine-containing sulfonate as the flame retardant in the polylactic acid PLLA and the flame retardant composition containing the same, the invention has the following beneficial effects:

(1) the fluorine-containing sulfonate provided by the invention can be used for flame retarding PLLA, and has a synergistic flame retarding effect;

(2) the flame-retardant composition provided by the invention can be used as a PLLA flame retardant, so that the PLLA has excellent anti-dripping performance and flame-retardant performance under the condition of keeping the spinning capacity;

(3) after a small amount of fluorine-containing sulfonate and DOPO flame retardant are added, the carbon residue amount and the maximum thermal weight loss rate at 800 ℃ in the thermal stability test of the flame-retardant PLLA are reduced; in a cone calorimetry test of the flame-retardant PLLA, the ignition time is obviously prolonged;

(4) the LOI of the flame-retardant PLLA provided by the invention can reach 28%, and UL-94 reaches V-0 level; after the fluorine-containing sulfonate and the DOPO flame retardant are added, the combustion time of the flame-retardant PLLA is obviously shortened, and UL-94 can smoothly reach the V-0 level.

Examples

Example 1

Putting a certain amount of PLLA, potassium perfluorobutane sulfonate and DDP into a vacuum drying oven, and vacuum-drying for 12 hours at the temperature of 80 ℃;

adding dried PLLA90.8g, potassium perfluorobutylsulfonate 0.2g and DDP9.0g into a twin-screw extruder (PolyOS, HAAKE, Germany) for melt mixing;

and (3) extruding and forming by using a double-screw extruder at the screw rotating speed of 50rpm and the temperatures of all zones of the screw of 205 ℃, 210 ℃, 210 ℃, 210 ℃ and 205 ℃ in sequence to obtain the flame-retardant PLLA.

Example 2

The same procedure as in example 1, except that in step 2, 90.5g of dried PLLA, 0.5g of potassium perfluorobutylsulfonate and 9.0g of DDP were taken; obtaining the flame-retardant PLLA.

Example 3

The same procedure as in example 1, except that in step 2, 90.0g of dried PLLA, 1.0g of potassium perfluorobutylsulfonate and 9.0g of DDP were taken; obtaining the flame-retardant PLLA.

Example 4

The same procedure as in example 1, except that in step 2, 89.5g of dried PLLA, 1.5g of potassium perfluorobutylsulfonate and 9.0g of DDP were taken; obtaining the flame-retardant PLLA.

Example 5

The same procedure as in example 1, except that in step 2, 89.0g of dried PLLA, 2.0g of potassium perfluorobutylsulfonate and 9.0g of DDP were taken; obtaining the flame-retardant PLLA.

Comparative example

Comparative example 1

The same procedure as in example 1, except that, in step 2, 100.0g of dried PLLA alone was taken; and finally, performing extrusion forming to obtain PLLA.

Comparative example 2

The same procedure as in example 1 was followed, except that, in step 2, only 97.0g of dried PLLA and 3.0g of dried DDP3; and finally, performing extrusion forming to obtain the flame-retardant PLLA.

Comparative example 3

The same procedure as in comparative example 2, except that, in step 2, only 95.0g of dried PLLA and 5.0g of DDP5; and finally, performing extrusion forming to obtain the flame-retardant PLLA.

Comparative example 4

The same procedure as in comparative example 2, except that, in step 2, only 93.0g of dried PLLA and 7.0g of DDP7; and finally, performing extrusion forming to obtain the flame-retardant PLLA.

Comparative example 5

The same procedure as in comparative example 2 except that, in step 2, 91.0g of dried PLLA and 9.0g of DDP9; and finally, performing extrusion forming to obtain the flame-retardant PLLA.

Comparative example 6

The same procedure as in comparative example 2, except that, in step 2, only 89.0g of dried PLLA and 11.0g of DDP11; and finally, performing extrusion forming to obtain the flame-retardant PLLA.

Comparative example 7

And (3) melting and blending the dried matrix PLLA372g with 28g of flame retardant polytetrafluoroethylene to obtain the flame retardant PLLA.

Examples of the experiments

DSC analysis of thermal stability of sample of Experimental example 1

DSC temperature rise and fall analysis was performed on comparative examples 1 to 6 and examples 1 to 5, and the relevant data are shown in tables 1 and 2, and DSC graphs are shown in FIG. 1(a), FIG. 1(b), FIG. 2(a), and FIG. 2 (b).

Table 1 is a data table of DSC temperature rise and drop of comparative examples 1 to 6;

table 2 is a table of DSC temperature rise and fall data for comparative example 1, comparative example 5, and examples 1-5;

FIG. 1(a) is a DSC temperature rise curve of comparative example 1 to comparative example 6;

FIG. 1(b) is a DSC cooling curve of comparative example 1 to comparative example 6;

FIG. 2(a) is a DSC temperature rise curve of comparative example 1, comparative example 5, and examples 1 to 5;

FIG. 2(b) is a DSC cooling curve of comparative example 1, comparative example 5, and examples 1 to 5;

TABLE 1 DSC test results of comparative examples 1 to 6

Sample numbering	T_cc(℃)	T_m(℃)	T_mc(℃)	T₀(℃)	T_m-T₀(℃)
						Comparative example 1	98	174	99	91	83
Comparative example 2	96	173	97	87	86
						Comparison ofExample 3	98	172	93	90	82
Comparative example 4	97	172	92	89	83
						Comparative example 5	97	172	91	89	83
Comparative example 6	98	170	91	89	81

TABLE 2 DSC test results of the products of comparative example 1, comparative example 5 and examples 1 to 5

Sample numbering	T_cc(℃)	T_m(℃)	T_mc(℃)
				Comparative example 1	98	174	99
Comparative example 5	95	171	90
				Example 1	94	171	89
Example 2	93	172	86
				Example 3	94	170	87
Example 4	93	172	88
				Example 5	92	172	90

As can be seen from Table 1 and FIGS. 1(a) and 1(b), the melting point of the PLLA/DOPO based flame retardant blends gradually decreased with increasing levels of DOPO based flame retardant. T of pure PLLA when DOPO flame retardant is added_CCThe (cold crystallization temperature) ratio generally tends to decrease, which indicates that the DOPO flame retardant has a certain plasticizing effect and the crystallization can be completed at a low temperature.

As can be seen from Table 2 and FIGS. 2(a) and 2(b), cold crystallization of the products of examples 1 to 5 occurred at a lower temperature than that of pure PLLA, indicating an increase in the molecular chain mobility. It can also be seen that the melting crystallization peak disappears after the fluorosulfonate salt is added, probably because the fluorosulfonate salt acts to inhibit the crystal growth of PLLA, hindering the crystallization of PLLA.

Experimental example 2 analysis of thermal stability of sample

Comparative examples 1 to 6 and examples 1 to 5 were subjected to thermal stability analysis, and the relevant data are shown in tables 3 and 4, and the thermal stability profiles are shown in fig. 3(a), 3(b), 4(a), and 4 (b).

Table 3 shows the results of the weight loss by heat of comparative examples 1 to 6;

table 4 shows the results of the weight loss on heating of comparative example 1, comparative example 5 and examples 1 to 5;

FIGS. 3(a) and 3(b) show graphs of TG and DTG analyses of comparative examples 1 to 6;

fig. 4(a), fig. 4(b) show TG and DTG analysis graphs of comparative example 1, comparative example 5 and examples 1 to 5.

TABLE 3 table of results of weight loss by heat for the products of comparative examples 1 to 6

Note: t is_5wt％5 wt% of thermal weight loss corresponding to temperature, T_max: maximum rate of thermal weight lossCorresponding temperature

TABLE 4 table of results of weight loss by heat for comparative example 1, comparative example 5 and examples 1 to 5

Note: t is_5wt％5 wt% of thermal weight loss corresponding to temperature, T_max: maximum rate of thermal weight loss versus temperature

From Table 3 and FIG. 3(a), FIG. 3(b), it can be seen that the melting point of the PLLA/DOPO based flame retardant blends gradually decreased with increasing DOPO based flame retardant content. T of pure PLLA when DOPO flame retardant is added_CCThe (cold crystallization temperature) ratio generally tends to decrease, which indicates that the DOPO flame retardant has a certain plasticizing effect and the crystallization can be completed at a low temperature. T is_mcThe (melting crystallization temperature) generally shows a decreasing trend, and with the increasing content of the DOPO flame retardant, the melting crystallization peak is weakened or even disappears, probably because the DOPO flame retardant is added to interact with PLLA molecules, so that the nucleation and the grain growth of the blend are more difficult, and the crystallization property of the PLLA is reduced. (T)_m-T₀) The supercooling degree is shown, and the higher the supercooling degree is, the better the spinnability of the slice is. After the DOPO flame retardant is added, the supercooling degree is not changed greatly, and the supercooling degree when 9 percent of DOPO flame retardant is added (comparative example 5) is the same as that of pure PLLA, so that the spinnability of the material is not reduced to a certain extent by adding the DOPO flame retardant.

As can be seen from Table 4, FIG. 4(a) and FIG. 4(b), as the content of the fluorosulfonate salt of the flame retardant increases, the temperature at which the blends of examples 1 to 5 reach the maximum thermal decomposition rate is substantially maintained at about 363 ℃, the maximum thermal weight loss rate increases from 33.8%/min to 34.5%/min, and the residual carbon content of the blend increases from 9.1% to 11.8%. However, compared with the case where only 9% DOPO flame retardant (comparative example 5) was added, the amount of carbon residue and the maximum rate of thermal weight loss at 800 ℃ were both reduced by adding a small amount of fluorosulfonate. Compared with pure PLLA, the increase of the residual carbon amount is not obvious after the DOPO flame retardant and the composite flame retardant of the flame retardant composition containing the fluorosulfonate are added, and the temperature at the initial decomposition rate and the maximum thermal decomposition rate is slightly reduced, which shows that the DOPO flame retardant and the composite flame retardant of the flame retardant composition containing the fluorosulfonate have certain influence on the thermal stability of the PLLA.

Experimental example 3 analysis of Combustion Performance of sample

Comparative examples 1 to 6 and examples 1 to 5 were subjected to combustion performance analysis, i.e., cone calorimetry test, and the relevant data are shown in tables 5 and 6, and cone calorimetry graphs are shown in fig. 5(a), 5(b), and 6(a), 6 (b). Wherein,

table 5 shows cone calorimetry test results of the products of comparative examples 1 to 6;

table 6 shows cone calorimetry test results of the products of comparative example 1, comparative example 5, and examples 1 to 5;

FIGS. 5(a) and 5(b) show cone calorimetry plots for the products of comparative examples 1 to 6;

FIGS. 6(a) and 6(b) show cone calorimetry plots for the products of comparative example 5 and examples 1-5;

TABLE 5 Cone calorimeter test results for the products of comparative examples 1 to 6

TABLE 6 Cone calorimeter test results for the products of comparative example 1, comparative example 5 and examples 1-5

As can be seen from table 5, fig. 5(a) and 5(b), compared with the pure PLLA sample, the ignition time (TTI) is significantly prolonged after the flame retardant DOPO-based flame retardant is added, the maximum heat release rate (pHRR) shows a significant increase trend with the increase of the DOPO-based flame retardant, the total heat release amount (THR) has a decrease trend, and the DOPO-based flame retardant has a certain inhibition effect on the combustion thermal decomposition of PLLA as a whole. In conclusion, the DOPO flame retardant has a certain flame retardant effect on PLLA.

By comparing the data of Table 6, FIG. 6(a) and FIG. 6(b), it was found that the ignition time after addition of fluorosulfonate was significantly prolonged, the average heat release rate (mHRR) and the average quantity loss rate (mMLR) were significantly decreased when fluorosulfonate was added in an amount of 2% (example 5), but the Total Heat Release (THR) was not decreased, as compared with the case where 9% of DOPO-based flame retardant was added (comparative example 5).

Experimental example 4 flame retardancy analysis of sample

Performing flame retardant performance analysis on comparative examples 1 to 6 and examples 1 to 5, wherein relevant data are shown in tables 7 and 8, including LOI and UL-94 test results and molten drop conditions;

wherein, table 7 shows the flame retardant property analysis data of the products of comparative examples 1 to 6; table 8 shows the flame retardant property analysis data for the products of comparative example 1, comparative example 5 and examples 1-5.

TABLE 7 LOI and UL-94 test results for the products of comparative examples 1-6

TABLE 8 LOI and UL-94 test results for the products of comparative example 1, comparative example 5 and examples 1-5

As can be seen from Table 7, as the content of DOPO-based flame retardant increased, the LOI value of PLLA tended to increase significantly, but t was₁And t₂All have obvious reduction trend, which shows that the flame retardant property is improved along with the increase of the content of the DOPO flame retardant. When the addition amount of the DOPO flame retardant is 9% or more (comparative examples 5-6), the flame-retardant polylactic acid is burnt in the air to generate a self-extinguishing phenomenon, and UL-94 successfully reaches a V-0 grade.

As can be seen from tables 7 and 8, example 1 was usedAs can be seen from comparison of the comparative examples 1 to 4, the LOI of PLLA is improved to a certain extent by adding a small amount of the flame retardant fluorosulfonate, the combustion time is remarkably shortened after the flame retardant fluorosulfonate is added, and UL-94 can smoothly reach the V-0 level. Flame retardant PLLA/DOPO based flame retardants/fluorosulfonate blends with increased fluorosulfonate content₁、t₂The tendency of obvious reduction is shown, therefore, the DOPO flame retardant and the fluorine-containing sulfonate have certain synergistic flame retardant effect.

Experimental example 5 analysis of spinnability of sample

The spinning performance test was performed on the products of comparative example 7 and examples 2 to 5, and the results are shown in tables 9 and 10. Wherein,

table 9 shows the spinning process parameters of the products of comparative example 7 and examples 2-5;

table 10 shows the results of the fiber mechanical property tests of the products of comparative example 7 and examples 2-5;

TABLE 9 sample spinning Process parameters

TABLE 10 sample fiber mechanical Property test results

As can be seen from tables 9 and 10, compared with the spinning performance data of flame-retardant PLLA (comparative example 7) of other flame retardants, the spinning performance (breaking strength and elongation at break) of the flame-retardant PLLA provided by the invention has obvious advantages, and the flame-retardant PLLA provided by the invention has excellent flame-retardant performance, the combustion time is remarkably shortened, and UL-94 can smoothly reach V-0 level.

SEM analysis of sample of Experimental example 6

SEM analysis of the products of comparative examples 1 to 6 and examples 1 to 5 is shown in FIGS. 7 and 8.

FIG. 7 shows SEM images of comparative examples 1 to 6; in FIG. 7, (a) to (f) show SEM images of the products of comparative examples 1 to 6, respectively;

FIG. 8 shows SEM images of comparative example 5 and the products of examples 1 to 5; in FIG. 8, a to f show SEM images of the products of comparative example 5 and examples 1 to 5, respectively.

As shown in fig. 7, it can be seen that no significant agglomeration of the flame retardant occurred in the studied range; and as the flame retardant is increased, it is clear that the particle distribution is denser. In FIG. 7, e is an SEM image of the blend with 9% DOPO-based flame retardant (comparative example 5), in which there is no significant agglomeration and the distribution is relatively uniform and the particles are relatively densely distributed; in FIG. 7, f is an SEM image of the blend with 11% DOPO based flame retardant (comparative example 6), and it can be seen that the distribution in PLLA is more uniform with increasing DOPO based flame retardant content. This is mainly because the blending temperature is higher than the melting point of the DOPO-based flame retardant, which is in a melt-blended state when blended with PLLA, and thus the mixing is relatively uniform.

As can be seen from FIG. 8, in the range studied, the flame retardant was dispersed uniformly without significant agglomeration when the amount of the fluorosulfonate salt added was small (the amount added in examples 1 to 3), while a small amount of agglomeration was observed when the amount added was slightly large (the amount added in examples 4 to 5).

The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims

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.