CN115637032B - Heat-resistant and flame-retardant polylactic acid material and preparation method thereof - Google Patents
Heat-resistant and flame-retardant polylactic acid material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a heat-resistant flame-retardant polylactic acid material and a preparation method thereof, wherein the heat-resistant flame-retardant polylactic acid material is prepared by blending polylactic acid and an organic hypophosphite flame retardant, the polylactic acid is one or more selected from L-polylactic acid and D-polylactic acid, the heat-resistant flame-retardant polylactic acid material has good flame retardant property, and the carbon forming effect, the heat resistance and the anti-dripping performance of the polylactic acid material are further improved by adding the organic hypophosphite flame retardant, and the preparation method of the polylactic acid material is simple and low in cost, is suitable for large-scale industrial production, and further expands the application of the polylactic acid material.
Description
Technical Field
The invention belongs to the technical field of polylactic acid materials, and particularly relates to a heat-resistant flame-retardant polylactic acid material and a preparation method thereof.
Background
Polylactic acid (PLA), also known as polylactide, is a polyester polymerized from lactic acid as a raw material. Polylactic acid is a nontoxic and non-irritating synthetic polymer material, and the raw material lactic acid is mainly from fermentation of starch and the like, can also be obtained by taking cellulose, kitchen waste or fish waste as raw materials, has wide sources of PLA raw materials, can be directly subjected to composting or incineration treatment after being used, and can be finally completely degraded into carbon dioxide and water, thereby meeting the requirement of sustainable development. PLA has good transparency, certain toughness, biocompatibility, heat resistance and other properties, and simultaneously has excellent biodegradability, compatibility and absorbability. In addition, PLA has thermoplasticity, can be applied to various fields, and products prepared by the PLA, such as packaging materials, fibers and the like, are mainly used in the fields of disposable articles, such as disposable tableware and packaging materials, automobile doors, foot pads, vehicle seats, clothes, electric appliances, medical sanitation (orthopedic internal fixing materials, disassembly-free operation suture lines and the like), and the like.
However, polylactic acid is a flammable material, and has a limiting oxygen index of about 20%, and has poor heat resistance and a low use temperature. Along with the increasingly wide application of polylactic acid in industries such as electronics and automobiles, the requirements of people on the safety and the use temperature of the polylactic acid are higher and higher, so that how to improve the heat resistance and the flame retardant property of the polylactic acid becomes a problem to be solved urgently at present.
Disclosure of Invention
Based on the technical background, the inventor makes a keen approach, and found that: the mixture of the L-polylactic acid and the D-polylactic acid is adopted, and the organic hypophosphite flame retardant is adopted for blending, so that the polylactic acid material with good flame retardant property can be prepared, particularly, the addition of the flame retardant has good carbon promoting effect, the heat deformation temperature and the Vicat softening temperature of the polylactic acid material can be greatly improved, the excellent heat resistance is provided, and the anti-dripping performance is improved, so that the invention is completed.
The first aspect of the invention provides a heat-resistant flame-retardant polylactic acid material, which is prepared by blending polylactic acid and an organic hypophosphite flame retardant;
the polylactic acid is selected from one or two of L-polylactic acid and D-polylactic acid.
The second aspect of the invention provides a method for preparing the heat-resistant flame-retardant polylactic acid according to the first aspect of the invention, which comprises the following steps:
step 1, drying polylactic acid and an organic hypophosphite flame retardant;
and 2, placing the dried material in the step 1 into an internal mixer for blending.
The heat-resistant flame-retardant polylactic acid material and the preparation method thereof provided by the invention have the following advantages:
(1) The heat-resistant flame-retardant polylactic acid material has good flame retardant property, heat resistance and anti-dripping property;
(2) The preparation method of the heat-resistant flame-retardant polylactic acid material is simple and is suitable for industrial mass production.
Drawings
FIG. 1 shows the temperature-lowering DSC curves of the heat-resistant flame-retardant polylactic acid materials prepared in examples 1 to 4 and comparative examples 1 to 2 of the present invention;
FIG. 2 shows the temperature rise DSC curves of the heat-resistant flame-retardant polylactic acid materials prepared in examples 1 to 4 and comparative examples 1 to 2 of the present invention;
FIG. 3a shows TG curves of heat-resistant flame-retardant polylactic acid materials prepared in examples 1 to 4 and comparative examples 1 to 2 of the present invention;
FIG. 3b is an enlarged view of the black box portion of FIG. 3 a;
FIG. 4a shows DTG curves of heat-resistant flame-retardant polylactic acid materials prepared in examples 1 to 4 and comparative examples 1 to 2 of the present invention;
FIG. 4b is an enlarged view of the black box portion of FIG. 4 a;
FIG. 5 shows photographs of heat-resistant flame-retardant polylactic acid materials prepared in examples 1 to 4 and comparative examples 1 to 2 according to the present invention after vertical burning test;
FIG. 6 shows heat release curves of examples 1 to 4 and comparative examples 1 to 2;
Fig. 7 shows the total heat release curves of examples 1 to 4 and comparative examples 1 to 2;
fig. 8 shows total smoke release amounts of examples 1 to 4 and comparative examples 1 to 2;
FIG. 9 shows carbon residue photographs generated after combustion of examples 1 to 4 and comparative examples 1 to 2;
FIG. 10 shows thermal deformation temperature histograms of samples prepared in example 3, examples 6 to 7, comparative example 1 and comparative example 2;
FIG. 11 shows a Vicat softening temperature histogram of the samples prepared in example 3, examples 6 to 7, comparative example 1 and comparative example 2;
FIG. 12 shows temperature deformation curves of samples prepared in example 3, examples 6 to 7, comparative example 1 and comparative example 2;
FIG. 13 shows the amplified temperature deformation curves of the samples prepared in example 3, examples 6 to 7, comparative example 1 and comparative example 2 at 150 to 220 ℃;
FIG. 14 shows the temperature-decreasing DSC curves of the heat-resistant flame-retardant polylactic acid materials prepared in example 3, examples 5 to 7 and comparative examples 1 to 2 of the present invention;
FIG. 15 shows the temperature rise DSC curves of the heat-resistant flame-retardant polylactic acid materials prepared in example 3, examples 5 to 7 and comparative examples 1 to 2 of the present invention;
FIG. 16 shows LOI curves of the heat-resistant flame-retardant polylactic acid materials prepared in example 3, examples 5 to 7 and comparative examples 1 to 2 of the present invention;
FIG. 17 is a photograph showing the heat-resistant flame-retardant polylactic acid material prepared in example 3, examples 5 to 7 and comparative examples 1 to 2 of the present invention after vertical burning test;
FIG. 18 shows heat release rate curves of inventive example 3, examples 6 to 7 and comparative examples 1 to 2;
FIG. 19 shows the total heat release amount curves of example 3, examples 6 to 7 and comparative examples 1 to 2 of the present invention;
FIG. 20 shows top-down photographs of carbon residue generated after combustion in examples 6 and 7 of the present invention;
FIG. 21 is a side view showing the formation of carbon residue after combustion in examples 6 and 7 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and evident from the following detailed description of the invention.
The first aspect of the invention provides a heat-resistant flame-retardant polylactic acid material, which is prepared by blending polylactic acid and an organic hypophosphite flame retardant.
According to a preferred embodiment of the present invention, the polylactic acid is selected from one or two of L-polylactic acid and D-polylactic acid, preferably a mixture of L-polylactic acid and D-polylactic acid.
According to a further preferred embodiment of the present invention, the mass ratio of the L-polylactic acid to the D-polylactic acid is (0.1 to 5): 1, preferably (0.5 to 2): 1, more preferably 1:1.
The polylactic acid belongs to a non-flame-retardant material, particularly the limiting oxygen index of the L-polylactic acid is extremely low, and experiments show that the limiting oxygen index of the L-polylactic acid can be improved by adding the D-polylactic acid into the L-polylactic acid, and the heat resistance of the polylactic acid material can be greatly improved.
The organic hypophosphite flame retardant is selected from one or more of organic hypophosphite halogen-free flame retardants, preferably one or more of diethyl aluminum hypophosphite, diethyl zinc hypophosphite (ZDP), ammonium polyphosphate (APP), [ (6-oxo-6H-dibenzo- (c, e) (1, 2) -oxaphosphorin-6-one) -methyl ] -succinic acid (DDP) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), more preferably one or two of diethyl zinc hypophosphite and diethyl aluminum hypophosphite.
The inventor discovers that the addition of the organic hypophosphite flame retardant to the polylactic acid can further improve the thermal deformation temperature and the Vicat softening temperature of the polylactic acid, greatly improve the heat resistance and the use temperature of the polylactic acid material, improve the flame retardant property of the polylactic acid material and endow the polylactic acid material with good application prospect.
In the present invention, the mass ratio of the organic hypophosphite flame retardant to the polylactic acid is (0.01 to 0.5): 1, preferably (0.03 to 0.4): 1, and more preferably (0.05 to 0.25): 1.
The limiting oxygen index and the anti-dripping performance of the polylactic acid material can be further improved by adding the organic hypophosphite flame retardant into the polylactic acid material, the carbon residue rate of the polylactic acid material is increased along with the increase of the organic hypophosphite flame retardant, the good high Wen Chengtan property is very beneficial to the flame retardant modification of the polymer, meanwhile, the limiting oxygen index and the heat deformation temperature of the polylactic acid material are gradually improved along with the increase of the organic hypophosphite flame retardant, but the mass ratio of the organic hypophosphite flame retardant to the polylactic acid exceeds 0.25 along with the further increase of the organic hypophosphite flame retardant: 1, the heat distortion temperature is reduced.
The limiting oxygen index of the heat-resistant flame-retardant polylactic acid material is 22-27%, the thermal deformation temperature is 160-180 ℃, the Vicat softening temperature is 145-170 ℃, and the anti-dripping performance is excellent.
The second aspect of the invention provides a preparation method of the heat-resistant flame-retardant polylactic acid material according to the first aspect of the invention, which comprises the following steps:
step 1, drying polylactic acid and an organic hypophosphite flame retardant;
and 2, placing the dried material in the step 1 into an internal mixer for blending.
This step is specifically described and illustrated below.
Step 1, drying polylactic acid and an organic hypophosphite flame retardant.
The polylactic acid is one or two selected from L-polylactic acid and D-polylactic acid, and is preferably a mixture of L-polylactic acid and D-polylactic acid.
The mass ratio of the L-polylactic acid to the D-polylactic acid is (0.1-5): 1, preferably (0.5-2): 1, more preferably 1:1.
The organic hypophosphite flame retardant is one or more selected from organic hypophosphite halogen-free flame retardants, preferably one or more selected from diethyl aluminum hypophosphite, diethyl zinc hypophosphite (ZDP), ammonium polyphosphate (APP), [ (6-oxo-6H-dibenzo- (c, e) (1, 2) -oxaphosphorin-6-one) -methyl ] -succinic acid (DDP) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)), more preferably one or two selected from diethyl zinc hypophosphite and diethyl aluminum hypophosphite.
The mass ratio of the organic hypophosphite flame retardant to the polylactic acid is (0.01-0.5): 1, preferably (0.03-0.4): 1, more preferably (0.05-0.25): 1.
The addition of the organic hypophosphite can improve the limiting oxygen index of the polylactic acid material and improve the flame retardant property of the polylactic acid material, and is particularly beneficial to improving the service temperature and the anti-dripping property of the polylactic acid material, and the higher the service temperature of the polylactic acid material is, the better the dimensional stability is when heated, and the smaller the thermal deformation is. The better the flame retardant property and the anti-dripping property are, the less easy the ignition, the spread and the scald are caused in the fire disaster, and the application prospect of the polylactic acid material can be effectively improved by adding the organic hypophosphite into the polylactic acid material.
The drying is carried out in a vacuum oven at a drying temperature of 40-80 ℃, preferably 50-70 ℃, more preferably 60 ℃.
The drying time is 10 to 20 hours, preferably 11 to 15 hours, more preferably 12 hours.
The crystallization water in the polylactic acid can be removed by drying before blending, so that the degradation of the polylactic acid in the blending process is weakened, and the performance of the prepared heat-resistant flame-retardant polylactic acid material is improved.
And 2, placing the dried material in the step 1 into an internal mixer for blending.
The blending temperature is 160 to 220 ℃, preferably 170 to 210 ℃, more preferably 180 to 200 ℃.
The blending is carried out in a molten state, so that the blending is more uniform in material mixing, and meanwhile, the blending is carried out at a high temperature, the content of SC-crystals is improved, and experiments show that the formation of SC stereocrystal is favorable for improving the limiting oxygen index of the material and improving the heat resistance and the flame retardant property, but the content of SC-crystals is excessive, so that the mechanical property of the polylactic acid is reduced.
The blending time is 2 to 10 minutes, preferably 3 to 7 minutes, more preferably 4 to 6 minutes.
The blending time is short, the compatibility and uniformity of the polylactic acid and the flame retardant after blending are poor, the flame retardant effect of the flame retardant on the polylactic acid is poor, and if the blending time is too long, the degradation of the polylactic acid material can be caused, and the heat resistance, flame retardance, mechanical property and other properties of the material are affected. The rotation speed of the internal mixer is 30 to 100rpm, preferably 40 to 80rpm, more preferably 50 to 70rpm.
The compatibility and uniformity of the polylactic acid and the flame retardant can influence the flame retardant property of the flame retardant to improve, the compatibility is closely related to the processing technology, and the adoption of a larger rotating speed is beneficial to improving the compatibility of the polylactic acid and the flame retardant in the melt mixing process, so that the flame retardant effect is beneficial to improving.
Isothermal treatment is carried out after the blending is finished, the temperature is 160-180 ℃, preferably 170 ℃, and the isothermal time is 1-5 min, preferably 1-2 min.
The isothermal treatment can remove the bound water in the heat-resistant flame-retardant polylactic acid material, thereby facilitating the use of injection molding and the like in the later stage.
The third aspect of the invention provides a molten drop resistant heat resistant flame retardant polylactic acid material, which is prepared by blending raw materials comprising polylactic acid and melamine based flame retardant.
The polylactic acid is selected from one or two of L-polylactic acid and D-polylactic acid, and is preferably a mixture of L-polylactic acid and D-polylactic acid.
The limiting oxygen index of the L-polylactic acid is lower, and the L-polylactic acid is a non-flame-retardant material, and the inventor discovers that the addition of the D-polylactic acid into the L-polylactic acid can not only improve the limiting oxygen index of the polylactic acid material, but also improve the heat resistance of the polylactic acid material.
In a preferred embodiment of the present invention, the mass ratio of the L-polylactic acid to the D-polylactic acid is (0.1 to 5): 1, preferably the mass ratio is (0.5 to 2): 1, more preferably the mass ratio is 1:1.
In the invention, the melamine-based flame retardant is one or more selected from melamine phthalate, melamine phytate, melamine cyanurate and melamine thiocyanate, preferably one or two selected from melamine phthalate and melamine cyanurate, and more preferably melamine cyanurate.
The inventor finds out through a large number of experiments that the heat resistance and the flame retardance of the polylactic acid can be improved by adding the melamine-based flame retardant into the polylactic acid.
The mass ratio of the melamine flame retardant to the polylactic acid is (0.02-0.5): 1, preferably (0.04-0.3): 1, and more preferably (0.05-0.25): 1.
According to a preferred embodiment of the invention, the raw material further comprises an organic hypophosphite flame retardant.
Experiments show that the limiting oxygen index, the anti-molten drop and the heat resistance of the polylactic acid material can be greatly improved by further adding the organic hypophosphite flame retardant into the polylactic acid material, the co-addition of the organic hypophosphite flame retardant and the melamine-based flame retardant has a synergistic effect, and the improvement effect on the flame retardance and the heat resistance of the polylactic acid is more remarkable than the single addition of the organic hypophosphite or the melamine-based flame retardant.
The organic hypophosphite flame retardant is one or more selected from organic hypophosphite halogen-free flame retardants, preferably one or more selected from diethyl aluminum hypophosphite (ADP), diethyl zinc hypophosphite (ZDP), ammonium polyphosphate (APP), [ (6-oxo-6H-dibenzo- (c, e) (1, 2) -oxaphosphorin-6-one) -methyl ] -succinic acid (DDP) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)), more preferably one or two selected from diethyl zinc hypophosphite and diethyl aluminum hypophosphite.
The inventor discovers that the combined action of the organic hypophosphite halogen-free flame retardant and the melamine-based flame retardant has more obvious effect of improving the polylactic acid, not only can greatly improve the heat resistance of the polylactic acid, but also can greatly improve the limiting oxygen index and the molten drop resistance of the polylactic acid, and meanwhile, the melamine-based flame retardant and the organic hypophosphite are added simultaneously to have the effect of promoting carbon, so that an expansion layer is formed on the surface of the polylactic acid after combustion, the total heat release amount is reduced, the combustion time is greatly shortened, and excellent flame retardance is shown.
The mass ratio of the melamine flame retardant to the organic hypophosphite is (0.5-5) 1, and the mass ratio is (0.7-4): 1, more preferably the mass ratio is (0.8 to 3): 1.
The mass ratio of the melamine-based flame retardant to the organic hypophosphite can influence the synergistic effect of the two flame retardants, so that the heat resistance and the flame retardance of the polylactic acid material are improved.
The limiting oxygen index of the anti-molten-drop heat-resistant flame-retardant polylactic acid material is 23% -33%, the thermal deformation temperature is 170-210 ℃, the Vicat softening temperature is 160-200 ℃, and the UL-94 vertical burning grade reaches V-0 grade.
The fourth aspect of the present invention provides a method for preparing the anti-droplet heat-resistant flame-retardant polylactic acid material according to the third aspect of the present invention, wherein the method comprises: and (5) putting the dried raw materials into an internal mixer for blending.
In the present invention, the raw materials include polylactic acid and melamine-based flame retardant
The polylactic acid is selected from one or two of L-polylactic acid and D-polylactic acid, and is preferably a mixture of L-polylactic acid and D-polylactic acid.
The mass ratio of the L-polylactic acid to the D-polylactic acid is (0.1-5): 1, preferably the mass ratio is (0.5-2): 1, more preferably a mass ratio of 1:1.
The melamine-based flame retardant is one or more selected from melamine phthalate, melamine phytate, melamine cyanurate and melamine thiocyanate, preferably one or two selected from melamine phthalate and melamine cyanurate, more preferably melamine cyanurate.
The mass ratio of the melamine-based flame retardant to the polylactic acid is (0.02 to 0.5): 1, preferably (0.04 to 0.3): 1, more preferably (0.05 to 0.25): 1.
According to a preferred embodiment of the invention, the raw material further comprises an organic hypophosphite flame retardant.
The organic hypophosphite flame retardant is one or more selected from organic hypophosphite halogen-free flame retardants, preferably one or more selected from diethyl aluminum hypophosphite (ADP), diethyl zinc hypophosphite (ZDP), ammonium polyphosphate (APP), [ (6-oxo-6H-dibenzo- (c, e) (1, 2) -oxaphosphorin-6-one) -methyl ] -succinic acid (DDP) and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)), more preferably one or two selected from diethyl zinc hypophosphite and diethyl aluminum hypophosphite.
The mass ratio of the melamine-based flame retardant to the organic hypophosphite flame retardant is (0.5-5): 1, preferably the mass ratio is (0.7-4): 1, more preferably the mass ratio is (0.8 to 3): 1.
The drying is carried out in a vacuum oven at a temperature of 60 to 120 ℃, preferably 80 to 110 ℃, more preferably 100 ℃.
The crystallization water in the polylactic acid can be removed by drying before blending, so that the degradation of the polylactic acid in the blending process is weakened, and the heat resistance and flame retardance of the heat-resistant flame-retardant polylactic acid material are improved.
The drying time is 5 to 20 hours, preferably 10 to 15 hours, more preferably 12 hours.
The blending temperature is 160 to 220 ℃, preferably 170 to 210 ℃, more preferably 180 to 200 ℃.
The blending in the temperature range can ensure that the polylactic acid material is in a molten state during the blending, thereby being beneficial to more uniform material mixing, improving the content of SC crystal, and improving the heat resistance and flame retardance of the polylactic acid material.
The blending time is 2 to 10 minutes, preferably 3 to 7 minutes, more preferably 4 to 6 minutes.
The blending time length can influence the uniformity of mixing the polylactic acid and the flame retardant, and further influence the flame retardance and the heat resistance improvement effect of the flame retardant on the polylactic acid, but the blending time is too long, the polylactic acid material can be degraded, and experiments show that the polylactic acid can not be degraded when the blending time is in the range, and the flame retardant has good improvement effect on the heat resistance and the flame retardance of the polylactic acid.
The rotation speed of the internal mixer is 30 to 100rpm, preferably 40 to 80rpm, more preferably 50 to 70rpm.
If the stirring speed of the blending is too low under stirring at a high speed, the mixing uniformity is small, which is not beneficial to improving the effect of the flame retardant on the polylactic acid.
And carrying out isothermal treatment after the blending is finished, wherein the isothermal treatment temperature is 160-180 ℃, preferably 170 ℃, and the isothermal treatment time is 1-5 min, preferably 1-2 min.
The combined water in the anti-dripping heat-resistant flame-retardant polylactic acid material can be further removed by carrying out isothermal treatment after blending, so that the later use is convenient.
The invention has the beneficial effects that:
(1) The heat-resistant flame-retardant polylactic acid material has good flame retardant property, and the limiting oxygen index is more than 22%;
(2) The heat-resistant flame-retardant polylactic acid material has the heat deformation temperature reaching 170.4 ℃, the Vicat softening temperature reaching 165 ℃, good dimensional stability when heated, small heat deformation, excellent heat resistance and good application prospect;
(3) The heat-resistant flame-retardant polylactic acid material disclosed by the invention has excellent anti-dripping performance, obvious char formation effect when being heated and burnt, and the sample can keep the shape for a long time;
(4) The limiting oxygen index of the anti-molten-drop heat-resistant flame-retardant polylactic acid material can reach 33%, the thermal deformation temperature can reach 209.8 ℃, the Vicat softening temperature can reach 189.9 ℃, the anti-molten-drop performance is excellent, and the UL-94 vertical burning grade can reach V-0 grade;
(5) The polylactic acid material prepared by the method has wide sources of raw materials, can be prepared by simple one-step blending, has low preparation cost, and is suitable for large-scale industrial production.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
Placing L-polylactic acid (marine biological material, REVODE) (PLLA), D-polylactic acid (TOTAL, D120) (PDLA) and diethyl aluminum hypophosphite (ADP) into a vacuum oven for vacuum drying for 12 hours, mixing PLLA and PDLA with the ADP accounting for 5% of the TOTAL mass of the polylactic acid in a ratio of 1:1 uniformly, adding into an internal mixer for blending at 190 ℃ at a speed of 60rpm/min for 5min, and carrying out isothermal treatment at 170 ℃ for 2min after the blending is finished to finally obtain the PLLA/PDLA/ADP5 heat-resistant flame-retardant polylactic acid material.
Example 2
The preparation of the heat-resistant flame-retardant polylactic acid material was carried out in a similar manner to example 1, except that: and (3) uniformly mixing PLLA and PDLA with ADP accounting for 10 percent of the total mass of the polylactic acid in a ratio of 1:1, and adding the mixture into an internal mixer for blending to finally prepare the PLLA/PDLA/ADP10 heat-resistant flame-retardant polylactic acid material.
Example 3
The preparation of the heat-resistant flame-retardant polylactic acid material was carried out in a similar manner to example 1, except that: and (3) uniformly mixing PLLA and PDLA with ADP accounting for 15% of the total mass of the polylactic acid in a ratio of 1:1, and adding the mixture into an internal mixer for blending to finally prepare the PLLA/PDLA/ADP15 heat-resistant flame-retardant polylactic acid material.
Example 4
The preparation of the heat-resistant flame-retardant polylactic acid material was carried out in a similar manner to example 1, except that: and (3) uniformly mixing PLLA and PDLA with ADP accounting for 20% of the total mass of the polylactic acid in a ratio of 1:1, and adding the mixture into an internal mixer for blending to finally prepare the PLLA/PDLA/ADP20 heat-resistant flame-retardant polylactic acid material.
Example 5
Placing L-polylactic acid (marine biological material, REVODE) (PLLA), D-polylactic acid (TOTAL, D120) (PDLA) and Melamine Cyanurate (MCA) into a vacuum oven for vacuum drying for 12 hours, mixing PLLA and PDLA with MCA accounting for 15 percent of the TOTAL mass of the polylactic acid in a ratio of 1:1 uniformly, adding into an internal mixer for blending, wherein the blending temperature is 190 ℃, the rotating speed is 60rpm/min, the blending time is 5min, and carrying out isothermal treatment for 2min at 170 ℃ after the blending is finished, thus obtaining the PLLA/PDLA/MCA15 heat-resistant flame-retardant polylactic acid material.
Example 6
Placing L-polylactic acid (marine biological material, REVODE) (PLLA), D-polylactic acid (TOTAL, D120) (PDLA), diethyl aluminum hypophosphite (ADP) and Melamine Cyanurate (MCA) into a vacuum oven for vacuum drying for 12 hours, wherein the drying temperature is 100 ℃, mixing PLLA and PDLA with MCA accounting for 15 percent of the TOTAL mass of the polylactic acid and ADP accounting for 15 percent of the TOTAL mass of the polylactic acid uniformly in a ratio of 1:1, adding the mixture into an internal mixer for blending, wherein the blending temperature is 190 ℃, the rotating speed is 60rpm/min, the blending time is 5min, and carrying out isothermal treatment at 170 ℃ for 2min after the blending is finished, thus obtaining the PLLA/PDLA/MCA15/ADP15 heat-resistant flame-retardant polylactic acid material.
Example 7
Placing L-polylactic acid (marine biological material, REVODE) (PLLA), D-polylactic acid (TOTAL, D120) (PDLA), diethyl aluminum hypophosphite (ADP) and Melamine Cyanurate (MCA) into a vacuum oven for vacuum drying for 12 hours, wherein the drying temperature is 100 ℃, mixing PLLA and PDLA with MCA accounting for 20 percent of the TOTAL mass of the polylactic acid and ADP accounting for 10 percent of the TOTAL mass of the polylactic acid uniformly in a ratio of 1:1, adding into an internal mixer for blending, wherein the blending temperature is 190 ℃, the rotating speed is 60rpm/min, the blending time is 5min, and carrying out isothermal treatment at 170 ℃ for 2min after the blending is finished, thus obtaining the PLLA/PDLA/MCA20/ADP10 heat-resistant flame-retardant polylactic acid material.
Comparative example
Comparative example 1
And (3) placing the L-polylactic acid (marine biological material, REVODE) (PLLA) into a vacuum oven for vacuum drying for 24 hours, wherein the drying temperature is 80 ℃, adding the PLLA into an internal mixer for blending, and the blending temperature is 190 ℃, the rotating speed is 60rpm/min and the blending time is 5min to obtain the PLLA polylactic acid material.
Comparative example 2
Placing L-polylactic acid (marine biological material, REVODE) (PLLA) and D-polylactic acid (TOTAL, D120) (PDLA) into a vacuum oven, vacuum drying for 24 hours at 80 ℃, uniformly mixing PLLA and PDLA according to the proportion of 1:1, adding into an internal mixer for blending, wherein the blending temperature is 190 ℃, the rotating speed is 60rpm/min, and the blending time is 5min, and finally obtaining the PLLA/PDLA polylactic acid material.
Experimental example
Experimental example 1DSC test
Examples 1-7 and comparative examples 1-2 were tested using a differential scanning calorimeter (DSC Q2000, TA Instruments) from the company TA of America, and the mass of the samples was approximately 5-9 mg. Under the protection of nitrogen atmosphere, the temperature of the sample is raised to 250 ℃ at the speed of 30 ℃/min, the temperature is kept constant for 5min, the temperature is lowered to 30 ℃ at the temperature lowering speed of 10 ℃/min, the temperature is raised to 250 ℃ at the temperature raising speed of 10 ℃/min, and the temperature lowering curve and the second temperature raising curve of the sample are recorded. The test results of examples 1 to 4 and comparative examples 1 to 2 are shown in fig. 1 and 2, respectively. The test results of example 3, examples 5 to 7 and comparative examples 1 to 2 are shown in fig. 14 and 15, respectively.
As can be seen from fig. 1 and 14, the PLLA polylactic acid material obtained in comparative example 1 shows almost no thermal crystallization during the cooling process, and in fig. 2 and 15 (during the second heating process), a sharp cold crystallization peak appears near 105 ℃, a sharp melting peak appears near 175 ℃, the PLLA/PDLA polylactic acid material obtained in comparative example 2 shows a small thermal crystallization peak near 105 ℃ during the cooling process, a more gentle cold crystallization peak appears near 105 ℃ than the PLLA polylactic acid material during the second heating process, a sharp melting peak appears near 175 ℃, and a more gentle melting peak appears near 225 ℃, which means that the PLLA/PDLA polylactic acid material has a small amount of SC crystal forms.
The ADP added samples have sharp thermal crystallization peaks near 175 ℃ and milder crystallization peaks near 125 ℃ in the cooling process, small melting peaks near 175 ℃ and large melting peaks near 225 ℃ in the second heating process, the thermal crystallization peaks near 105 ℃ are judged to be crystallization peaks of SC crystal forms, the melting peaks near 175 ℃ are crystallization peaks of alpha crystal forms, and the melting peaks near 225 ℃ are melting peaks of SC crystal forms in the second heating process. It was found that the addition of PDLA can promote the formation of a small amount of SC crystal forms and that the addition of ADP can promote the formation of a large amount of SC crystal forms. And the PLLA/PDLA/ADP10 samples have the best effect, namely the SC crystal content is the largest.
As can be seen from fig. 14 and 15, the PLLA/PDLA/MCA15 shows a more gentle crystallization peak of SC crystals around 190 ℃ during the first cooling process, a smaller crystallization peak of α -crystal form around 128 ℃, and in the second temperature rising curve, the PLLA/PDLA/MCA15 shows a small melting peak of α -crystal at 175 ℃ and a larger melting peak of SC crystals around 225 ℃, which means that adding 15% MCA to polylactic acid is beneficial to the formation of SC crystals, and the crystallization rate is accelerated.
In the sample added with ADP and MCA, PLLA/PDLA/MCA15/ADP15 and PLLA/PDLA/MCA20/ADP10 have a sharp SC crystal crystallization peak near 190 ℃ in the first cooling process, have a melting peak near 175 ℃ in the second heating process and have a large SC crystal melting peak near 225 ℃, which means that the simultaneous addition of ADP and MCA to polylactic acid not only promotes the formation of SC crystal and improves the crystallization rate, but also can inhibit the formation of alpha crystal.
Experimental example 2TG test
Examples 1 to 4 and comparative examples 1 to 2 were tested for thermal stability of the samples and ADP using a Netzsch TG 209F1 type thermogravimetric analyzer from the German relaxation company. Test conditions: n 2 atmosphere, the temperature range is 30-700 ℃, and the temperature rising rate is 20 ℃/min. The TG curve and DTG curve are shown in fig. 3a, 3b, 4a and 4b, respectively, fig. 3b is an enlarged view of the black box in fig. 3a, and fig. 4b is an enlarged view of the black box in fig. 4 a.
As can be seen from fig. 3a, 3b, 4a and 4b, the TG curve and DTG curve of the samples prepared in comparative example 1 and comparative example 2 almost coincide, the thermal decomposition temperature is about 318 ℃, the maximum thermal decomposition temperature is about 363 ℃, the decomposition of ADP is started at 406 ℃, the thermal decomposition rate of ADP reaches maximum when the temperature reaches 471 ℃, two platforms are present for the samples added with ADP, the first platform drop process is the thermal decomposition process of PLLA/PDLA, and the second platform drop is the thermal decomposition process of ADP.
The PLLA/PDLA/ADP5 sample first plateau drops at 284℃and the maximum thermal decomposition temperature at 344℃and the second plateau starts to drop at 406℃and the thermal decomposition rate of ADP reaches a maximum when the temperature reaches 430 ℃.
PLLA/PDLA/ADP 10 samples the first plateau drops at 279℃and the maximum thermal decomposition temperature at 337℃and the second plateau starts to drop at 406℃because ADP starts to decompose and the thermal decomposition rate of ADP reaches a maximum when the temperature reaches 431 ℃.
The PLLA/PDLA/ADP15 sample first plateau drops at 277℃and the maximum thermal decomposition temperature at 338℃and the second plateau also starts to drop at 406℃and the thermal decomposition rate of ADP reaches a maximum when the temperature reaches 451 ℃.
The PLLA/PDLA/ADP20 sample first plateau drops at 267℃and the maximum thermal decomposition temperature at 338℃and the second plateau also starts to drop at 406℃and the thermal decomposition rate of ADP reaches a maximum when the temperature reaches 456 ℃.
From the above, it can be seen that the thermal decomposition of PLLA/PDLA is accelerated after adding ADP, the higher the ADP addition amount, the lower the thermal decomposition temperature of the sample, the less obvious change of the maximum heat release rate of the sample, the ADP starts to decompose after 406 ℃, the maximum decomposition rate of ADP in the sample gradually increases with the increase of the ADP content, and the maximum thermal decomposition temperature also increases with the increase of the ADP content.
Experimental example 3LOI test
LOI values of the samples prepared in examples 1 to 7 and comparative examples 1 to 2 were measured by using a Dynasco oxygen index tester in the United states, the spline size was 80mm by 6.5mm by 3mm, and the test standard was used for measuring the combustion behavior according to GB/T2406.2-2009 oxygen index method for plastics. The test results of examples 1 to 4 and comparative examples 1 to 2 are shown in Table 1. The test results of example 3, examples 5 to 7 and comparative examples 1 to 2 are shown in FIG. 16.
TABLE 1 flame retardant Property test results
| Sample name | LOI(％) |
| Comparative example 1 | 19 |
| Comparative example 2 | 21 |
| Example 1 | 22 |
| Example 2 | 22 |
| Example 3 | 26 |
| Example 4 | 27 |
As can be seen from table 1, the limiting oxygen index of PLLA polylactic acid of comparative example 1 is only 19%, which belongs to non-flame retardant materials, and the limiting oxygen index of the sample prepared in comparative example 2 is 21%, which shows that the formation of SC stereocrystal helps to improve the limiting oxygen index of the material, but the flame retardant effect is smaller, and the limiting oxygen index of the prepared sample gradually increases with the increase of the flame retardant, and when the addition amount of the flame retardant is 20%, the limiting oxygen index can reach 27%, which shows that the flame retardant performance of the polylactic acid can be improved by adding the flame retardant of the invention.
As can be seen from FIG. 16, the limiting oxygen index of the PLLA/PDLA/MCA15 sample is 23%, the limiting oxygen index of the PLLA/PDLA/ADP15 sample is 26%, and the limiting oxygen indexes of the PLLA/PDLA/MCA15/ADP15 and PLLA/PDLA/MCA20/ADP10 obtained by adding MCA and ADP are 33%, so that the flame retardant property is greatly improved, and the simultaneous addition of MCA and ADP can greatly improve the flame retardant property of polylactic acid.
Experimental example 4 vertical Combustion Performance test
The samples prepared in examples 1 to 7 and comparative examples 1 to 2 were tested for vertical burning performance by using a horizontal vertical burner of analytical instrumentation CZF-3 in Nanjing's Jiang Ning, the spline size was 130 mm. Times.13 mm. Times.3 mm, and the test standards were according to GB/T2408-2008 "horizontal and vertical methods for testing Plastic burning Performance". The test results of examples 1 to 4 and comparative examples 1 to 2 are shown in Table 2 and FIG. 5. The test results of example 3, examples 5 to 7 and comparative examples 1 to 2 are shown in Table 2 and FIG. 17.
Table 2 vertical burn Performance test
| Sample name | Whether or not to drip | Whether or not to ignite absorbent cotton | Grade |
| Comparative example 1 | Is that | Is that | V-2 |
| Comparative example 2 | Is that | Is that | V-2 |
| Example 1 | Is that | Is that | V-2 |
| Example 2 | Is that | Is that | V-2 |
| Example 3 | Whether or not | Whether or not | V-2 |
| Example 4 | Whether or not | Whether or not | V-2 |
| Example 5 | Is that | Is that | V-2 |
| Example 6 | Whether or not | Whether or not | V-0 |
| Example 7 | Whether or not | Whether or not | V-0 |
As can be seen from Table 2, the heat-resistant flame-retardant polylactic acid prepared in example 3 and example 4 has better anti-dripping performance, which indicates that the addition of the flame retardant can improve the anti-dripping performance of the polylactic acid material. As can be seen from fig. 5, the samples prepared in example 3 and example 4 can maintain the shape more permanently, and the char formation effect is remarkable with the increase of the flame retardant, the more permanently the shape of the samples can be maintained.
The vertical burning test result shows that the PLLA/PDLA/ADP15 sample can keep the shape temporarily, but the burning time is long, still only V-2 grade, the PLLA/PDLA/MCA15/ADP15 and PLLA/PDLA/MCA20/ADP10 samples prepared by adding MCA and ADP simultaneously have no molten drop phenomenon, the burning time is short, the flame extinction is faster, and the sample can keep the shape permanently, and has more excellent molten drop resistance and flame retardance as can be seen from the figure 17.
Experimental example 5CONE test
Examples 1 to 7 and comparative examples 1 to 2 were tested using a standard cone calorimeter (FTT STANDARD Corn Calorimeter) of the British FIRE TESTING Technology Ltd, with a heat radiation power of 35kW/m 2, a sample size of 100mm x 3mm, test standards according to ISO 5660-1 section 1 "heat release, smoke yield and Mass loss Rate for fire reaction test: heat release rate (cone calorimeter method), heat release, total heat release and total smoke release amounts of examples 1 to 4 and comparative examples 1 to 2 are shown in fig. 6, fig. 7 and fig. 8, respectively. The heat release rates and total heat release amounts of example 3, examples 6 to 7, and comparative examples 1 to 2 are shown in fig. 18 and 19, respectively.
As is clear from fig. 6 and 7, the addition of ADP has a certain effect on the reduction of HRR (heat release), and as the HRR gradually decreases with the increase of the ADP addition amount, the HRR value of the sample with 20% ADP content decreases to about 300KW/m 2. The total heat release amount is effectively improved, and the THR (total heat release) value decreases with an increase in ADP content. PLA is a degradable material with very little smoke release, and as can be seen from fig. 8, the TSR (total smoke release) of the sample gradually increases as the ADP content in the sample increases.
As shown in fig. 9, PLLA and PLLA/PDLA had almost no residue after combustion, but samples with ADP added had different degrees of residue, which indicated that ADP added was helpful for char formation, and further indicated that ADP contributed to the char-promoting effect of polylactic acid. The good high Wen Chengtan property is very beneficial to the flame retardant modification of the polymer, on one hand, the high char formation property can enhance the flame retardance of the polymer, and on the other hand, the high char formation property is beneficial to reducing the smoke release amount and the heat release amount in the combustion process.
As can be seen from fig. 18 and 19, the difference between the heat release rate and the total heat release amount of the pure PLLA and PLLA/PDLA is not large, the peak value of the heat release rate is about 500KW/m 2, the total heat release amount is about 86m 2/m2, the addition of ADP has a certain effect on reducing HRR and THR, and the HRR peak value of the PLLA/PDLA/MCA15/ADP15 and PLLA/PDLA/MCA20/ADP10 samples added with two flame retardants of MCA and ADP is further reduced, as low as 360KW/m 2, the total heat release is reduced by 28% relative to the pure PLLA sample, the total heat release is reduced by about 70m 2/m2, and the flame retardant property is effectively improved in terms of heat release relative to the pure PLLA sample.
As shown in fig. 20 and 21, the burnt carbon residue has more residues after the MCA and ADP are added, and as can be seen from fig. 21, the residues after the combustion of the samples of example 6 and example 7 have a high-rise expansion morphology, which indicates that the addition of MCA and ADP simultaneously plays a role in retarding the condensed phase.
Experimental example 6 thermal deformation Performance test
Adopts a GTS-III type thermal deformation performance measuring instrument of Shanghai Kai Di New material science and technology Co., ltd. Taking out the powder sample prepared in the example 1 after being kept in a die at 120 ℃ for 30min, taking out the powder sample prepared in the comparative example 2 after being kept in a die at 130 ℃ for 10min, taking out the powder samples prepared in the example 3 and the examples 6-7 after being kept in a die at 170 ℃ for 2min, cutting out a small section of sample for thermal deformation temperature test, and measuring the thickness of a spline: 3-4mm, test conditions: the temperature ranges from room temperature to 235 ℃, the temperature rising rate is 10 ℃/min, and the pressure is 200Mpa. The test results of comparative examples 1 to 2, example 3 and examples 6 to 7 are shown in FIG. 10.
As can be seen from fig. 10, the HDT (heat distortion) temperature of the pure PLLA is only 65.1 ℃, the HTD temperature of the PLLA/PDLA sample can be increased to 156.8 ℃, the HDT temperature of the sample of PLLA/PDLA/ADP15 can be up to 170.4 ℃, which is 161.8% higher than that of the pure PLLA sample, and the heat resistance is excellent, and the use temperature of polylactic acid is increased.
The HDT of the PLLA/PDLA/MCA20/ADP10 sample reaches 176.9 ℃, the HDT of the PLLA/PDLA/MCA15/ADP15 sample can reach 209.8 ℃, and compared with the pure PLLA sample, the HDT is improved by 222.27%, and the heat resistance is excellent.
Experimental example 7 Vicat softening temperature test
Vicat softening temperature is the temperature at which a sample is pressed 1mm by a 1mm square pin under a constant load and a constant temperature rise by placing a thermoplastic into a liquid heat transfer medium. The softening temperature of the micro card is one of indexes for evaluating heat resistance of materials and reflecting physical and mechanical properties of products under the heated condition. The vicat softening temperature of a material cannot be used directly to evaluate the actual use temperature of the material, but can be used to guide the quality control of the material. The higher the Vicat softening temperature, the better the dimensional stability of the material when heated, the less the thermal deformation, i.e. the better the heat distortion resistance, the greater the rigidity and the higher the modulus.
The powder sample prepared in example 1 was taken out after being kept at 120℃for 30min in a mold, the powder sample prepared in comparative example 2 was taken out after being kept at 130℃for 10min, the powder samples prepared in example 3 and examples 6 to 7 were taken out after being kept at 170℃for 2min in a mold, and a small sample was taken out for the Vicat softening temperature test. The test results of example 3, comparative examples 1 to 2 and examples 6 to 7 are shown in FIG. 11.
As can be seen from FIG. 11, the VST (Vicat softening temperature) of the pure PLLA sample is only 78.6 ℃, the VST of the PLLA/PDLA sample is increased to 163.7 ℃, the VST of the PLLA/PDLA/ADP15 sample can reach 165 ℃, and the VST is increased by 109.9%.
The VST of the PLLA/PDLA/MCA20/ADP10 sample can reach 174.3 ℃, the VST of the PLLA/PDLA/MCA15/ADP15 sample reaches 189.9 ℃, and the VST is 141.6 percent higher than that of the PLLA sample. Exhibits excellent heat resistance.
Experimental example 8 temperature deformation test
The powder sample prepared in example 1 was taken out after being kept at 120℃for 30min in a mold, the powder sample prepared in comparative example 2 was taken out after being kept at 130℃for 10min, the powder samples prepared in example 3 and examples 5 to 7 were taken out after being kept at 170℃for 2min in a mold, and a small section of the sample was taken out for temperature deformation curve test. The test results of example 3, examples 5 to 7 and comparative examples 1 to 2 are shown in fig. 12 and 13, respectively.
As can be seen from fig. 12, the PLLA sample showed an inflection point at 172.13 ℃, which is that the melting point of alpha crystals was reached, and only alpha crystals were present in the PLLA matrix. The PLLA/PDLA (comparative example 2) sample showed a small step at 63 ℃ compared to the other two samples, a first inflection point at 180.12 ℃ which is probably the melting of part of the alpha and beta crystals in the matrix, and a second inflection point at 214.95 ℃ which is the melting of the SC crystals. The glass transition of the PLLA (comparative example 1) sample and the PLLA/PDLA/ADP15 (example 3) sample in FIG. 13 was hardly noticeable, indicating that both samples were well crystallized. The PLLA/PDLA/ADP15 sample showed an inflection point around 187℃, which is the melting of the SC crystals. Therefore, the use temperature of the PLLA/PDLA/ADP15 sample is improved by 8.64 percent compared with that of the PLLA sample, and the PLLA/PDLA/ADP15 sample has good heat deformation resistance.
The curve inflection points of the PLLA/PDLA/ADP15 sample and the PLLA/PDLA/MCA15 sample are about 187 ℃, and the curve inflection points of the PLLA/PDLA/MCA20/ADP10 and the PLLA/PDLA/MCA15/ADP15 sample are about 220 ℃, which is improved by 27.81 percent compared with the pure PLLA sample. It is explained that isothermal treatment with proper temperature by adding PDLA, ADP, MCA to PLLA has a remarkable effect of improving the deformation temperature of the sample. Thus demonstrating the effective improvement of the heat resistance of the materials by the addition of ADP and MCA.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art 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, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (4)
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