CN115960443A - Polylactic acid blending composition and preparation method thereof - Google Patents
Polylactic acid blending composition and preparation method thereof Download PDFInfo
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- CN115960443A CN115960443A CN202111187419.9A CN202111187419A CN115960443A CN 115960443 A CN115960443 A CN 115960443A CN 202111187419 A CN202111187419 A CN 202111187419A CN 115960443 A CN115960443 A CN 115960443A
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- 239000000203 mixture Substances 0.000 title claims abstract description 136
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 99
- 238000009987 spinning Methods 0.000 claims abstract description 63
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 43
- 239000011574 phosphorus Substances 0.000 claims abstract description 43
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- 238000000034 method Methods 0.000 claims description 24
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- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- OHRVBDRGLIWLPA-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] dihydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(O)=O OHRVBDRGLIWLPA-UHFFFAOYSA-N 0.000 claims description 6
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 claims description 3
- OJUVOJCIHNPHSA-UHFFFAOYSA-N bis(2,6-dimethylphenyl) (3-hydroxyphenyl) phosphate Chemical compound CC1=CC=CC(C)=C1OP(=O)(OC=1C(=CC=CC=1C)C)OC1=CC=CC(O)=C1 OJUVOJCIHNPHSA-UHFFFAOYSA-N 0.000 claims description 3
- 238000012360 testing method Methods 0.000 description 34
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- MORLYCDUFHDZKO-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]propanoic acid Chemical compound OC(=O)CCP(O)(=O)C1=CC=CC=C1 MORLYCDUFHDZKO-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
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- 239000000779 smoke Substances 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- 229920000742 Cotton Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004786 cone calorimetry Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 2
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- 230000001737 promoting effect Effects 0.000 description 2
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- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- YZBOZNXACBQJHI-UHFFFAOYSA-N 1-dichlorophosphoryloxyethane Chemical compound CCOP(Cl)(Cl)=O YZBOZNXACBQJHI-UHFFFAOYSA-N 0.000 description 1
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 description 1
- 101710130081 Aspergillopepsin-1 Proteins 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
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- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention provides a polylactic acid blending composition, a preparation method thereof and a flame-retardant polylactic acid fiber prepared by spinning the composition, wherein the polylactic acid blending composition is prepared by blending raw materials comprising polylactic acid and a phosphorus-containing flame retardant, the phosphorus-containing flame retardant is added, so that the polylactic acid is endowed with good flame-retardant property, the fluidity of a polylactic acid melt is improved, the spinning temperature and the fineness of the polylactic acid are greatly reduced, and the prepared polylactic acid fiber still has good mechanical property.
Description
Technical Field
The invention belongs to the technical field of polylactic acid materials, and particularly relates to a polylactic acid blending composition, a heat-resistant flame-retardant polylactic acid fiber and a preparation method thereof.
Background
The application field of poly (L-lactic acid) (PLLA), a bio-based polymer, is very wide, and at the beginning of its discovery, PLLA is applied to biodegradable fields such as disposable medical supplies, disposable tableware, personal care sanitary materials, textile clothing, agriculture and packaging materials, etc., and particularly, the amount of use is rapidly increasing after the use of non-degradable garbage bags and packaging materials is prohibited in the country. PLLA has a Limiting Oxygen Index (LOI) of about 19, which is flammable, and the flammability problem of products thereof as a material is related to storage safety, production and living safety, and human health, so there is a need to solve the flame retardancy problem of PLLA.
In recent years, researchers have tried various methods to improve the flame retardant performance of PLLA, such as nano inorganic flame retardants, phosphorus-based flame retardants, and intumescent flame retardants are often used as flame retardant modifiers for PLLA, and some new effective flame retardant systems have also been developed. Gregory Stoclet et al added 17wt% halloysite to PLLA reduced the heat release rate peak (pHRR) of the PLLA by 40%. Lei Song et al found a synergistic effect of intumescent flame retardants (pentaerythritol phosphate (PEPA) and Melamine Phosphate (MP)) and polyhedral oligomeric silsesquioxanes (POSS) on PLLA substrates. A PLLA with 25wt% IFR material achieved only a V-1 rating, while a PLLA with 20wt% IFR plus 5wt% POSS passed a UL94V-0 rating. The addition of 5wt% sulfuric acid intercalation-modified expanded graphite to PLLA by Ping Wei et al passed the PLLA/CEPPA through UL94V-0 rating. Qian Yong et Al added 0.5wt% of flame retardant (Al-SBA-15) to PLLA passed the UL94V-0 rating with an LOI of 30%. Wang et al synthesized flame retardant PPLA by a chain extension reaction of a dihydroxy terminated prepolymer (lactic acid) using ethyl dichlorophosphate as a chain extender. An LOI value of 25% and a UL94V-0 rating can be obtained for PLLA by adding 5wt% PPLA.
However, the addition of large amounts of flame retardants has a major impact on the mechanical and processability properties of the polymers. Therefore, it is a problem to be solved how to balance the flame retardancy and processability of PLLA so that the flame retardancy is improved without lowering the processability.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: the polylactic acid blending composition obtained by adding the phosphorus-containing flame retardant into the polylactic acid has good flame retardance, and the melt fluidity of the polylactic acid blending composition is better than that of the polylactic acid melt without the phosphorus-containing flame retardant, so that the spinning temperature of the polylactic acid blending composition is lower than that of the polylactic acid, and the mechanical properties of the polylactic acid blending composition and the flame-retardant polylactic acid fiber prepared from the polylactic acid blending composition are not obviously changed compared with that of the polylactic acid, so that the polylactic acid blending composition has good titer and mechanical properties, and the invention is completed.
The first aspect of the invention provides a polylactic acid blending composition, which comprises polylactic acid and a phosphorus-containing flame retardant;
the mass ratio of the phosphorus-containing flame retardant to the polylactic acid is (0.1-30): (70-200).
The second aspect of the present invention provides a method for preparing the flame retardant polylactic acid fiber according to the first aspect of the present invention, the method comprising the steps of:
step 1, blending polylactic acid and a phosphorus-containing flame retardant to prepare flame-retardant polylactic acid master batch;
and 2, mixing the flame-retardant polylactic acid master batch, the PLLA/ZnO master batch and the PLLA to obtain the polylactic acid blending composition.
The third aspect of the present invention provides a flame retardant polylactic acid fiber, wherein the flame retardant polylactic acid fiber is prepared by spinning the polylactic acid blend composition according to the first aspect of the present invention or the polylactic acid blend composition prepared by the preparation method according to the second aspect of the present invention.
The polylactic acid blending composition, the heat-resistant flame-retardant polylactic acid fiber and the preparation method thereof provided by the invention have the following advantages:
(1) According to the invention, the phosphorus-containing flame retardant is blended with the polylactic acid, so that the flame retardance of the polylactic acid is improved, the fluidity of a polylactic acid melt is improved, and the spinning temperature of the polylactic acid is reduced;
(2) The heat-resistant flame-retardant polylactic acid fiber prepared from the polylactic acid blending composition has low titer and excellent antibacterial performance.
Drawings
FIG. 1 shows DSC spectra of temperature rising process of PLLA, CEPPA and polylactic acid blend compositions prepared in examples 1-7;
FIG. 2 shows DSC spectra of the cooling process of PLLA, CEPPA and the polylactic acid blend compositions prepared in examples 1-7;
FIG. 3 shows DSC spectra of warming process of PLLA, CEPPA, example 8 and example 12 fibers;
FIG. 4 shows DSC spectra of temperature reduction process for PLLA, CEPPA, example 8 and example 12 fibers;
FIG. 5 shows TGA test spectra of CEPPA, PLLA, example 2, example 4 and example 6;
FIG. 6 shows a plot of heat release rate versus time for PLLA, example 5 and example 7 resulting in polylactic acid blend compositions;
FIG. 7 shows a plot of total heat release over time for the polylactic acid blend compositions made from PLLA, example 5 and example 7;
FIG. 8 shows plots of total smoke release over time for PLLA, example 5 and example 7 resulting in polylactic acid blend compositions;
fig. 9 shows a photograph of a conical calorimetric residue of PLLA;
FIG. 10 shows a photograph of cone shaped hot residue of polylactic acid blend composition made in example 5;
FIG. 11 shows a photograph of cone calorimetric residue of polylactic acid blend composition made in example 7.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent with reference to the following description.
The first aspect of the invention provides a polylactic acid blending composition, which comprises polylactic acid and a phosphorus-containing flame retardant.
In the present invention, the polylactic acid is L-type polylactic acid.
The phosphorus-containing flame retardant is selected from one or more of diethyl ethylphosphate, resorcinol bis (2, 6-dimethylphenyl) phosphate, pentaerythritol phosphate, 2-carboxyethylphenyl hypophosphorous acid (CEPPA) and tris (2, 3-dibromopropyl) phosphate, and tests show that the addition of the phosphorus-containing flame retardant not only can improve the flame retardance of polylactic acid, but also has a plasticizing effect on the polylactic acid, improves the fluidity of a polylactic acid melt, reduces the spinning temperature of the polylactic acid, reduces energy consumption, is beneficial to improving the spinning speed, increases the productivity in unit time and saves cost, and meanwhile, the addition of the phosphorus-containing flame retardant does not reduce the mechanical property of the polylactic acid fiber obtained by spinning and has a good application prospect.
Preferably, the phosphorus-containing flame retardant is selected from one or more of diethyl ethylphosphate, pentaerythritol phosphate and 2-carboxyethylphenylhypophosphorous acid, more preferably 2-carboxyethylphenylhypophosphorous acid.
In the combustion process of the polylactic acid, the 2-carboxyethyl phenyl hypophosphorous acid (CEPPA) can play a role in a gas phase and a condensed phase at the same time, a free radical scavenger is generated in the gas phase to inhibit the further occurrence of combustion, the carbonization is promoted in the condensed phase to form a closed carbon layer, the mass and heat transfer between flame and a polylactic acid matrix is slowed down, and the purpose of inhibiting the combustion is achieved. Particularly, the CEPPA is added, so that the flame retardant effect is improved, the mechanical property of the polylactic acid fiber is not reduced, the polylactic acid has a good plasticizing effect, and the spinning temperature of the polylactic acid can be effectively reduced.
The mass ratio of the phosphorus-containing flame retardant to the polylactic acid is (0.1-30): (70-200), preferably the mass ratio is (0.15-20): (80-150), and more preferably the mass ratio is (0.2-10): (90-100).
Tests show that when the addition amount of the phosphorus-containing flame retardant exceeds the range, the breaking strength and the breaking elongation of the polylactic acid are reduced, and in the range, the crystallinity of the polylactic acid is increased due to the crystallization promoting effect of the phosphorus-containing flame retardant, so that the flame retardance of the polylactic acid fiber can be improved on the premise of not reducing the mechanical property of the polylactic acid fiber, and the spinning temperature is reduced, and tests show that when the addition amount of the phosphorus-containing flame retardant is within the range, the spinning temperature of the polylactic acid can be reduced by 5-30 ℃.
According to the invention, the raw materials also comprise zinc oxide, and a proper amount of zinc oxide is added into the polylactic acid, so that the mechanical property of the polylactic acid can be improved, the antibacterial property of the prepared polylactic acid textile material can be improved, and the antibacterial rate of the polylactic acid textile material to escherichia coli and staphylococcus aureus can reach more than 90% after the zinc oxide is added.
The mass ratio of the zinc oxide to the polylactic acid is 1: (500 to 700), preferably 1: (550 to 650), more preferably 1: (570-600).
The polylactic acid blending composition is prepared by blending raw materials comprising polylactic acid and a phosphorus-containing flame retardant.
According to a preferred embodiment of the invention, the polylactic acid blend composition is prepared by blending polylactic acid and a phosphorus-containing flame retardant to prepare master batches, and then mixing the master batches with PLLA/ZnO master batches and PLLA. The phosphorus-containing flame retardant and the polylactic acid can be mixed more uniformly and have better compatibility by adopting a mode of firstly blending the phosphorus-containing flame retardant and then mixing the mixture with the PLLA/ZnO master batch and the PLLA.
The blending of the polylactic acid and the phosphorus-containing flame retardant is preferably carried out in a double screw extruder, and the temperature of each blending area is (180-220) ° C- (170-210) ° C- (160-200) ° C- (150-190) ° C- (150-170) ° C- (140-160 ℃).
According to the invention, the mixing is preferably carried out in a single-screw extruder in which the temperatures in the individual zones are (140-200) DEG C- (170-210) DEG C- (170-220) DEG C- (180-220).
The polylactic acid blending composition has the limiting oxygen index of 22-35 percent and the UL-94 can reach V0 level at most. Compared with the spinning temperature of polylactic acid, the spinning temperature of the polylactic acid blending composition is reduced by 5-30 ℃. And the mechanical properties of the fiber obtained by spinning the polylactic acid blending composition are equivalent to those of the polylactic acid fiber, so that the preparation cost and the energy consumption of the polylactic acid fiber are greatly reduced.
In a second aspect of the present invention, there is provided a method for preparing the flame retardant polylactic acid fiber according to the first aspect of the present invention, the method comprising the steps of:
step 1, blending polylactic acid and a phosphorus-containing flame retardant to prepare flame-retardant polylactic acid master batches;
and 2, mixing the flame-retardant polylactic acid master batch, the PLLA/ZnO master batch and the PLLA to obtain the polylactic acid blending composition.
This step is specifically described and illustrated below.
Step 1, blending polylactic acid and a phosphorus-containing flame retardant to prepare the flame-retardant polylactic acid master batch.
The phosphorus-containing flame retardant is selected from one or more of diethyl ethylphosphate, resorcinol bis (2, 6-dimethylphenyl) phosphate, pentaerythritol phosphate, 2-carboxyethylphenylphosphinic acid (CEPPA) and tris (2, 3-dibromopropyl) phosphate, preferably from one or more of diethyl ethylphosphate, pentaerythritol phosphate and 2-carboxyethylphenylphosphinic acid, and more preferably is 2-carboxyethylphenylphosphinic acid.
The addition of the phosphorus-containing flame retardant can improve the flame retardance of the polylactic acid, improve the fluidity of the polylactic acid melt and play a role of a plasticizer. Among them, CEPPA is most excellent in flame retardancy and plasticization of polylactic acid.
The mass ratio of the phosphorus-containing flame retardant to the polylactic acid is (0.1-0.6): 1, preferably the mass ratio of (0.2-0.5): 1, and more preferably 1 to 0.3 mass ratio.
With the increase of the addition amount of the phosphorus-containing flame retardant, the fluidity of the polylactic acid melt is gradually increased, the spinning temperature is gradually reduced, the spinning speed is increased, the limiting oxygen index of the polylactic acid is increased, the vertical combustion performance is improved, and the mechanical performance of the polylactic acid is reduced by further increasing the use amount of the phosphorus-containing flame retardant.
In the invention, the blending is carried out in a double-screw extruder, experiments show that CEPPA is liquid and cannot be conveyed by a single screw to carry out spinning processing under the processing condition of polylactic acid, the CEPPA liquid and polylactic acid slices are difficult to be uniformly mixed, so that the CEPPA liquid and the polylactic acid slices are difficult to be uniformly dispersed in PLLA, and the problems that the single screw cannot be processed and the dispersion is not uniform are solved by adopting the double-screw extruder to prepare the flame-retardant polylactic acid master batch.
The temperature of each zone in the double-screw extruder is (180-220) DEG C- (170-210) DEG C- (160-200) DEG C- (150-190) DEG C- (150-170) DEG C- (140-160) DEG C, preferably (190-210) DEG C- (180-200) DEG C- (170-190) DEG C- (160-180) DEG C- (155-165) DEG C- (145-155) DEG C, more preferably 200-190-180-170-150 ℃.
The blending time is 1 to 10min, preferably 1 to 5min, and more preferably 1 to 3min.
The screw rotation speed is 20-70 r/min, preferably 40-60 r/min, and more preferably 50r/min.
The mixing uniformity and compatibility of the phosphorus-containing flame retardant and the polylactic acid can be influenced by the rotating speed of the screw and the blending time, so that the flame retardant and plasticizing effects of the phosphorus-containing flame retardant are influenced.
And 2, mixing the flame-retardant polylactic acid master batch, the PLLA/ZnO master batch and the PLLA to obtain the polylactic acid blending composition.
The PLLA/ZnO master batch is purchased from Siam Mingbo chemical technology Co., ltd, and the content of zinc oxide is 17%. The proper amount of zinc oxide is added into the polylactic acid, so that the bacteriostasis rate of the polylactic acid fiber obtained by spinning the blended composition can be improved on the premise of not reducing other properties of the polylactic acid.
The mass ratio of the flame-retardant polylactic acid master batch to the PLLA/ZnO master batch to the PLLA is (0.01-30): (0.5-10): (60-100), preferably the mass ratio is (0.05-10): (0.5 to 7): (83 to 99.9), and more preferably (0.1 to 5): (0.5-5): (90-99.9).
In the present invention, the mixing is preferably carried out in a single-screw extruder in which the temperatures of the respective zones are (140 to 200) ° c- (170 to 210) ° c- (170 to 220) ° c- (180 to 220) ° c, preferably in the respective zones (150 to 180) ° c- (180 to 200) ° c- (190 to 210) ° c, and more preferably in the respective zones at 160 ℃ -190 ℃ -200 ℃.
The mixing time is 1 to 10min, preferably 1 to 5min, more preferably 1 to 3min.
The mixing temperature and the mixing time can influence the uniformity of the mixture of the substances, and further influence the compatibility of the substances, the compatibility is better, and the phosphorus-containing flame retardant has better flame retardant and plasticizing effects on the polylactic acid.
The screw rotation speed is 20-100 r/min, preferably 30-70 r/min, and more preferably 40-50 r/min.
The third aspect of the present invention provides a flame-retardant polylactic acid fiber, wherein the flame-retardant polylactic acid fiber is prepared by spinning the polylactic acid blend composition according to the first aspect of the present invention or the polylactic acid blend composition prepared by the preparation method according to the second aspect of the present invention.
The blend composition is preferably dried before spinning, the drying temperature is preferably 80 to 120, more preferably 100, and the drying time is preferably 500 to 700min, more preferably 600min.
The spinning is preferably carried out in a single-screw spinning machine, and the temperature of each region in the single-screw spinning machine is (140-180) ° c- (170-210) ° c- (180-220) ° c, preferably (150-170) ° c- (180-200) ° c- (190-210) ° c, and more preferably 160 ℃ -190 ℃ -200 ℃ - (190-200) ° c.
The temperature of the pipeline is 170 to 210 ℃, preferably 180 to 205 ℃, and more preferably 185 to 205 ℃.
The temperature of the spinning pack is 170 to 220 ℃, preferably 180 to 215 ℃, more preferably 181 to 210 ℃.
The inventor finds that the phosphorus-containing flame retardant, particularly CEPPA, added into the polylactic acid has a melting point close to that of the polylactic acid and has certain compatibility with the polylactic acid, the addition of CEPPA can improve the flame retardance of the polylactic acid, and the CEPPA can be used as a plasticizer of a polylactic acid melt in the spinning process to reduce the spinning temperature of the polylactic acid by 5-30 ℃.
The pressure in the spin pack is 5.5 to 7MPa, preferably 6 to 7MPa, more preferably 6.5MPa. The spinning temperature is adjusted during the spinning process to ensure that the pressure of the spinning assembly is about the above range.
The winding speed is 800 to 1200m/min, preferably 900 to 1100m/min, more preferably 1000m/min.
After spinning, the nascent fiber is preferably drafted by a parallel drafting machine, the drafting temperature and speed are kept unchanged during drafting, and the elongation at break is kept about 30% by adjusting the drafting multiple.
The draft winding speed is 300 to 500m/min, preferably 350 to 450m/min, and more preferably 400m/min.
The temperature of the first drafting roller, the temperature of the two rollers and the temperature of the shaping box are respectively (60-90) DEG C (90-110) DEG C (120-150) DEG C, preferably (70-80) DEG C (95-105) DEG C (130-145) DEG C, and more preferably 75-100-140 ℃.
The draft ratio is 2 to 3.5, preferably 2.5 to 3.1.
The titer of the flame-retardant polylactic acid fiber is 110 to 135dtex/96f, the breaking strength is 2.7 to 3.1cN/dtex, and the elongation at break is 28 to 35 percent.
The invention has the following beneficial effects:
(1) The LOI value of the polylactic acid blending composition can reach 32, the flame combustion time of UL-94 is obviously shortened, the flame retardant level reaches V-0 level, the ignition time is prolonged, and the heat release rate and the total amount are both obviously reduced;
(2) The addition of the flame retardant has little influence on the thermal stability of PLLA and the residual amount at 700 ℃, the glass transition temperature, the cold crystallization temperature and the hot crystallization temperature of the PLLA have little change after the flame retardant is added, the flame retardant has the melting induction effect, and the melting point of the flame retardant is slightly reduced;
(3) The PLLA blending composition added with the flame retardant has good spinnability and drawability, the prepared fiber has good mechanical property, the flame retardant has a certain plasticizing effect on the PLLA, the spinning temperature of the polylactic acid fiber is gradually reduced along with the increase of the addition amount of the flame retardant, the drawability multiple is gradually increased, and the preparation of the fine PLLA fiber with certain flame retardance is facilitated;
(4) The addition of the phosphorus-containing flame retardant is beneficial to improving the thermal crystallization performance of the PLLA, and can be used for solving the problem of nonwoven fabric shrinkage caused by slow crystallization speed in the melt-blowing process of the PLLA;
(5) The bacteriostasis rate of the added zinc oxide on escherichia coli and staphylococcus aureus reaches 99%, and the addition amount of the phosphorus-containing flame retardant has no influence on the antibacterial property of the phosphorus-containing flame retardant.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1
70 parts by weight of PLLA and 30 parts by weight of CEPPA are placed in a DZF-6050 type vacuum drying oven to be dried for 12 hours in vacuum at 100 ℃, and then the materials are placed in a double-screw extruder (Poly OS, HAAKE, germany) to be melted and blended, the rotating speed of a screw is 50r/min, the temperatures of all regions of the screw are 200 ℃, 190 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃ in sequence, and the blending time is 3min, so that the PLLA/CEPPA master batch is prepared.
Mixing 0.2 weight part of PLLA/CEPPA master batch, 1 weight part of PLLA/ZnO master batch (purchased from the chemical and scientific Co., ltd., zinc oxide content of 17%, the same below) and 99.8 weight parts of PLLA, wherein the temperature of each zone of a single-screw extruder is 160-190-200 ℃, the mixing time is 3min, and the screw rotation speed is 50r/min to obtain the polylactic acid blending composition named as PLLA/CEPPA0.2.
Example 2
The preparation of polylactic acid blend composition was carried out in a similar manner to example 1, except that: putting 1 weight part of PLLA/ZnO master batch, 99.6 weight parts of PLLA and 0.4 weight part of PLLA/CEPPA master batch into a DZF-6050 type vacuum drying oven, and carrying out vacuum drying for 12h at 100 ℃, wherein the product is named as PLLA/CEPPA0.4.
Example 3
The preparation of polylactic acid blend composition was carried out in a similar manner to example 1, except that: putting 1 weight part of PLLA/ZnO master batch, 99.4 weight parts of PLLA and 0.6 weight part of PLLA/CEPPA master batch into a DZF-6050 type vacuum drying oven, and carrying out vacuum drying for 12h at 100 ℃, wherein the product is named as PLLA/CEPPA0.6.
Example 4
The preparation of polylactic acid blend composition was carried out in a similar manner to example 1, except that: putting 1 weight part of PLLA/ZnO master batch, 99.2 weight parts of PLLA and 0.8 weight part of PLLA/CEPPA master batch into a DZF-6050 type vacuum drying oven, and carrying out vacuum drying for 12h at 100 ℃, wherein the product is named as PLLA/CEPPA0.8.
Example 5
The preparation of polylactic acid blend composition was carried out in a similar manner to example 1, except that: putting 1 weight part of PLLA/ZnO master batch, 99.0 weight parts of PLLA and 1.0 weight part of PLLA/CEPPA master batch into a DZF-6050 type vacuum dryer, and carrying out vacuum drying for 12 hours at 100 ℃, wherein the product is named as PLLA/CEPPA1.0.
Example 6
The preparation of polylactic acid blend composition was carried out in a similar manner to example 1, except that: putting 1 weight part of PLLA/ZnO master batch, 98.5 weight parts of PLLA and 1.5 weight parts of PLLA/CEPPA master batch into a DZF-6050 type vacuum dryer, and carrying out vacuum drying for 12 hours at 100 ℃, wherein the product is named as PLLA/CEPPA1.5.
Example 7
The preparation of polylactic acid blend composition was carried out in a similar manner to example 1, except that: putting 1 weight part of PLLA/ZnO master batch, 98 weight parts of PLLA and 2 weight parts of PLLA/CEPPA master batch into a DZF-6050 type vacuum dryer to be dried for 12 hours in vacuum at 100 ℃, and naming the product as PLLA/CEPPA2.0.
Experimental example 8
Drying the polylactic acid blending composition prepared in the embodiment 1 at 100 ℃ for 600min, putting the dried polylactic acid blending composition into a single-screw spinning machine for spinning, and adjusting a zone I in the spinning process,
Spinning temperatures of the II area, the III area, the IV area, the pipeline and the assembly are respectively 160 ℃, 190 ℃, 200 ℃, 205 ℃ and 210 ℃, the pressure of the assembly is adjusted to be 6.5MPa, the winding speed is 1000m/min, a parallel drafting machine is adopted to draft the nascent fiber, the drafting temperature and the speed are kept unchanged in the drafting process, the drafting and winding speed is 400m/min, the temperature of a drafting roller, the temperature of two rollers and the temperature of a shaping box are respectively 75 ℃, 100 ℃ and 140 ℃, and the drafting multiple is 2.7.
Example 9
The preparation of a flame retardant polylactic acid fiber was carried out in a similar manner to example 8 except that: the polylactic acid blending composition prepared in example 2 is adopted for spinning, the spinning temperatures of the area I, the area II, the area III, the area IV, the pipeline and the assembly are respectively adjusted to 160 ℃, 190 ℃, 200 ℃, 205 ℃ and 203 ℃ in the spinning process, and the drawing multiple is 2.7.
Example 10
The preparation of a flame retardant polylactic acid fiber was carried out in a similar manner to example 8 except that: the polylactic acid blending composition prepared in example 3 was used for spinning, and the spinning temperatures of zone I, zone II, zone III, zone IV, the pipeline and the assembly were adjusted to 160 ℃, 190 ℃, 200 ℃ and 200 ℃ respectively, and the draft ratio was 2.9.
Example 11
The preparation of a flame retardant polylactic acid fiber was carried out in a similar manner to example 8 except that: the polylactic acid blending composition prepared in example 4 was used for spinning, and the spinning temperatures of zone i, zone ii, zone iii, zone iv, the pipeline, and the assembly were adjusted to 160 ℃, 190 ℃, 200 ℃, 195 ℃, and 198 ℃, respectively, during the spinning process, and the draft ratio was 2.9.
Example 12
The preparation of a flame retardant polylactic acid fiber was carried out in a similar manner to example 8 except that: the polylactic acid blending composition prepared in example 5 was used for spinning, and the spinning temperatures of zone i, zone ii, zone iii, zone iv, the pipeline, and the assembly were adjusted to 160 ℃, 190 ℃, 200 ℃, 190 ℃, and 190 ℃, respectively, during the spinning process, and the draft ratio was 2.9.
Example 13
The preparation of a flame retardant polylactic acid fiber was carried out in a similar manner to example 8 except that: the polylactic acid blending composition prepared in example 6 is used for spinning, the spinning temperatures of the area I, the area II, the area III, the area IV, the pipeline and the assembly are respectively adjusted to 160 ℃, 190 ℃, 200 ℃, 190 ℃ and 186 ℃ in the spinning process, and the draft ratio is 3.1.
Example 14
The preparation of a flame retardant polylactic acid fiber was carried out in a similar manner to example 8 except that: the polylactic acid blending composition prepared in example 7 is used for spinning, the spinning temperatures of the area I, the area II, the area III, the area IV, the pipeline and the assembly are respectively adjusted to 160 ℃, 190 ℃, 200 ℃, 190 ℃, 185 ℃ and 181 ℃ in the spinning process, and the draft ratio is 3.1.
Comparative example
Comparative example 1
Placing PLLA in a DZF-6050 type vacuum drying oven, vacuum drying at 100 ℃ for 12h, then placing the mixture in a double-screw extruder (Poly OS, HAAKE, germany) for melt blending at the screw rotation speed of 50r/min, wherein the temperatures of all regions of the screw are 200 ℃, 190 ℃, 180 ℃, 170 ℃, 160 ℃ and 150 ℃ in sequence, and the blending time is 3min, thus obtaining the PLLA master batch.
Mixing 1 part by weight of PLLA/ZnO master batch with 100 parts by weight of PLLA, wherein the mixing temperature is 160-190-200 ℃, the mixing time is 3min, and the screw rotation speed is 50r/min to obtain the blending composition.
And (2) putting the blended composition into a single-screw spinning machine for spinning, wherein the spinning temperatures of an area I, an area II, an area III, an area IV, a pipeline and a component are adjusted to be 160 ℃, 190 ℃, 200 ℃, 205 ℃ and 210 ℃ respectively in the spinning process, the pressure of the component is adjusted to be 6.5MPa, the winding speed is 1000m/min, a parallel drafting machine is adopted for drafting the as-spun fibers, the drafting temperature and the speed are kept unchanged in the drafting process, the drafting winding speed is 400m/min, the temperature of a drafting roller, the temperature of two rollers and the temperature of a shaping box are 75 ℃, 100 ℃ and 140 ℃, and the drafting multiple is 2.1.
Examples of the experiments
The polylactic acid blend compositions obtained in examples 1 to 7 and the blend composition obtained in comparative example 1 were used to prepare a flame retardant test specimen for flame retardant property test using a JPH30 type injection molding machine (screw diameter 25mm, guangdong Hongli machine Co., ltd.).
Experimental example 1DSC test
The sample is heated, quenched and subjected to thermal history elimination (the fiber sample is not subjected to thermal history elimination treatment) on a hot table, DSC (dynamic stability testing) is carried out by adopting a company Q2000 of American TA, the temperature range is 0-200 ℃, the temperature rising speed is 20 ℃/min, and the temperature is in a nitrogen atmosphere.
DSC test spectrograms of PLLA, CEPPA and polylactic acid blend compositions prepared in examples 1-7 are respectively shown in figure 1 (temperature rising process) and figure 2 (temperature lowering process), and DSC test spectrograms of fiber products prepared in PLLA, CEPPA, examples 8 and example 12 are respectively shown in figure 3 (temperature rising process) and figure 4 (temperature lowering process).
As can be seen from fig. 1 and fig. 2, when part of CEPPA is molecularly dispersed between PLLA molecular chains, PLLA crystallization is hindered, and the influence on PLLA molecular movement is reduced, so that when the PLLA/CEPPA addition amount is not more than 2%, the glass transition temperature of the polylactic acid blend composition is slightly reduced along with the increase of the PLLA/CEPPA addition amount, which is beneficial to improving the drawability of the polylactic acid blend composition. In the cooling process, the thermal crystallization peak of CEPPA is about 120 ℃, PLLA does not have the thermal crystallization peak when being cooled at the speed of 20 ℃/min, and with the increase of the addition amount of PLLA/CEPPA, the PLLA molecular chain takes the crystallization of CEPPA as a crystal nucleus for crystallization under the induction action of CEPPA crystallization, so the thermal crystallization peak area of the polylactic acid blend composition is gradually increased, which is shown as promoting the thermal crystallization of PLLA.
As can be seen from FIGS. 3 and 4, the glass transition temperature of the flame-retardant polylactic acid fibers prepared in examples 8 and 12 disappeared, and the melting point of the polylactic acid fibers was not significantly affected when the PLLA/CEPPA was added in an amount of 0.2%, and was decreased to 168 ℃ due to the melt-induction effect of CEPPA when the PLLA/CEPPA was added in an amount of 1%. It can be seen from the cooling process that PLLA does not have a thermal crystallization phenomenon, and the flame retardant polylactic acid fibers prepared in examples 8 and 12 have a thermal crystallization peak, which indicates that the addition of 0.2% of CEPPA can promote the thermal crystallization of PLLA, which can be used for preparing melt-blown polylactic acid nonwoven fabrics, and solve the problem of fabric surface shrinkage caused by the slow crystallization speed of PLLA in the melt-blown process.
Experimental example 2TGA test
The method adopts German Netzsch TG 209F1 for testing, and adopts a nitrogen atmosphere, the testing temperature range is room temperature-600 ℃, and the heating rate is 10 ℃/min.
The results of the tests for CEPPA, PLLA, example 2, example 4 and example 6 are shown in FIG. 5.
As can be seen from FIG. 5, the thermal decomposition temperatures of CEPPA and PLLA are 185 ℃ and 300 ℃ respectively, and the thermal decomposition temperature of the polylactic acid blend composition prepared by adding the flame retardant CEPPA is reduced to about 260 ℃, which is related to the low decomposition temperature of the flame retardant CEPPA, but the processing temperature of PLLA is generally not more than 220 ℃, so that the polylactic acid blend composition prepared by the invention meets the requirement of thermal processing.
Experimental example 3 limiting oxygen index test
The specimens obtained in examples 1 to 7 and comparative example 1 were subjected to a limiting oxygen index test using an oxygen index tester of Dynisco type, USA, and the specimens were 100 mm. Times.6.5 mm. Times.4 mm in size, according to GB/T2406.2-2009. The test results are shown in table 1.
TABLE 1
As can be seen from Table 1, when the PLLA/CEPPA content is not more than 1wt%, the LOI value of the polylactic acid blend composition increases from 19% to 32% with the increase of the CEPPA content, which shows that CEPPA has the effect of improving the flame retardant property of PLLA, and the LOI value is not significantly improved with the further addition of CEPPA.
Experimental example 4 vertical Combustion Performance test
The test specimens obtained in examples 1 to 7 and comparative example 1 were subjected to a vertical burning test using a CZF-3 type horizontal vertical burner, nanjing Jiangning Analyzer Co., ltd., test Standard GB/T2408-2008, and the dimensions of the specimens were 100 mm. Times.13 mm. Times.4 mm. The test results are shown in table 1.
In Table 1, the time t for self-extinguishing of the polylactic acid blend composition from fire 1 And t 2 As the CEPPA addition amount is increased and reduced, the melting drop phenomenon exists during the ignition process, but the absorbent cotton is not ignited, and the absorbent cotton does not drop after leaving the ignition source, the V0 grade of UL-94 can be reached by adding the polylactic acid blend composition which is 1wt% PLLA/CEPPA, and the vertical burning performance is not obviously improved by further adding the CEPPA.
Experimental example 5 Cone calorimetry test
The test is carried out by adopting a British FTT Standard Corn Calorimeter cone Calorimeter, and the heat radiation power is 35kW/m 2 Sample size 100X 3mm, test standard ISO 5660-1. The Heat Release Rate (HRR), total Heat Release (THR), and Total Smoke Release (TSR) profiles over time for PLLA, the polylactic acid blend compositions prepared in example 5 and example 7 are shown in fig. 6, fig. 7, and fig. 8, respectively. The cone-shaped calorimetric residues are shown in FIGS. 9 to 11, respectively.
The cone calorimetry test is to evaluate 35kW/m in atmospheric environment 2 An effective method for the resistance of materials to thermal radiation under heat irradiation conditions, as can be seen from FIG. 6, the ignition time of the polylactic acid blend composition prepared in example 5 was delayed from 68s to 76s, extended by 8s, and the maximum heat release rate was increased from 440kW/m compared to polylactic acid without CEPPA 2 Reduced to 343kW/m 2 The maximum heat release rate is reduced by 22%, the ignition time of the polylactic acid blend composition prepared in example 7 is prolonged to 85s and 17s, and the maximum heat release rate is 440kW/m 2 Reduced to 325kW/m 2 The maximum heat release rate is reduced by 26%.
In FIG. 7, the total heat release amount of the polylactic acid blend compositions of example 5 and example 7 was 60.4MJ/m, respectively 2 And 63.1MJ/m 2 Compared with polylactic acid without CEPPA, the content of the polylactic acid is reduced by 22.6 percent and 19.1 percent.
As can be seen from FIG. 8, the smoke emissions of the polylactic acid blend composition after the addition of 1% and 2% PLLA/CEPPA were 148.2m 2 /m 2 Increased to 416.5m 2 /m 2 And 769.0m 2 /m 2 But still has the smoke release amount (2092.7 m) which is higher than that of the PET material containing benzene rings in molecular chains which is commonly used at present 2 /m 2 ) Much smaller.
As can be seen from fig. 9 to 11, compared with PLLA, the polylactic acid blend composition has a certain char-forming property, which indicates that CEPPA promotes PLLA char formation during combustion, and expands the surface of the blend during combustion to form a carbon layer which is difficult to combust, and simultaneously reduces the contact of the blend with oxygen and the total amount of heat release.
Experimental example 6 fiber denier and Strength testing
The fiber titer test was carried out using a YG086 strand yarn length measuring machine (first textile equipment Co., ltd., changzhou city) to test Standard GB/T14343-2008. An HD021N type electronic single yarn strength instrument (Nantong Honda laboratory instruments Co., ltd.) is adopted to carry out fiber strength test, and the test standard GB/T14344-2008 is adopted. The titer and strength test results are shown in table 2.
TABLE 2
As can be seen from Table 2, the fineness of the polylactic acid fiber was decreased from 168.3dtex/96f to 122-133 dtex/96f after CEPPA was added, which indicates that the drawability of the polylactic acid fiber was increased and the fineness was decreased after CEPPA was added.
As can be seen from Table 2, the breaking strength of the fiber was reduced from 3.11cN/dtex to 2.78cN/dtex after adding 1% PLLA/CEPPA compared with PLLA fiber, which is probably because the PLLA/CEPPA masterbatch is subjected to a certain degradation after one thermal processing, resulting in a slight decrease in breaking strength, but the fiber still can meet the requirement of textile processing.
Experimental example 7 mechanical Property test
The polylactic acid blend compositions of example 1, example 3, example 5, and example 7 and PLLA in comparative example 1 were subjected to mechanical property tests, and the test results are shown in table 3.
TABLE 3
Sample name | Breaking strength/MPa | Elongation at break/% | Initial modulus/GPa |
PLLA | 64.51 | 6.25 | 1.209 |
Example 1 | 63.65 | 4.84 | 1.359 |
Example 3 | 60.93 | 3.99 | 1.638 |
Example 5 | 58.29 | 2.82 | 1.882 |
Example 7 | 56.24 | 2.91 | 2.078 |
As can be seen from Table 3, the breaking strength and elongation at break of the polylactic acid gradually decreased with the increase of the amount of CEPPA added, but the mechanical properties of the polylactic acid were not greatly affected when PLLA/CEPPA was added in an amount of not more than 1%.
Experimental example 8 antibacterial Property test
The flame retardant polylactic acid fibers prepared in examples 8 and 12 were woven into a leg of a sock on a hosiery knitting machine, and the antibacterial property was measured, and the results are shown in table 4.
TABLE 4
As can be seen from Table 4, the bacteriostatic rate of Escherichia coli and Staphylococcus aureus by adding 1% PLLA/ZnO reaches 99%, and the antibacterial performance of CEPPA is not affected by the addition of CEPPA.
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 embodiments and implementations of the invention without departing from the spirit and scope of the invention, and are within the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A polylactic acid blending composition is characterized by comprising polylactic acid and a phosphorus-containing flame retardant;
the mass ratio of the phosphorus-containing flame retardant to the polylactic acid is (0.1-30): (70-200).
2. The polylactic acid blend composition according to claim 1,
the polylactic acid is L-type polylactic acid;
the phosphorus-containing flame retardant is selected from one or more of diethyl ethylphosphate, resorcinol bis (2, 6-dimethylphenyl) phosphate, pentaerythritol phosphate, 2-carboxyethylphenyl hypophosphorous acid (CEPPA) and tris (2, 3-dibromopropyl) phosphate.
3. The polylactic acid blend composition according to claim 1,
the blending composition also comprises zinc oxide, and the mass ratio of the zinc oxide to the polylactic acid is 1: (500-700).
4. The polylactic acid blend composition according to claim 1, wherein the polylactic acid blend composition is prepared by blending raw materials comprising polylactic acid and a phosphorus-containing flame retardant.
5. The polylactic acid blend composition according to any one of claims 1 to 4,
compared with the spinning temperature of polylactic acid, the spinning temperature of the polylactic acid blending composition is reduced by 5-30 ℃;
the limiting oxygen index of the polylactic acid blending composition is 22-35%.
6. A preparation method of a polylactic acid blending composition is characterized by comprising the following steps:
step 1, blending polylactic acid and a phosphorus-containing flame retardant to prepare flame-retardant polylactic acid master batch;
and 2, mixing the flame-retardant polylactic acid master batch, the PLLA/ZnO master batch and the PLLA to obtain the polylactic acid blending composition.
7. The method according to claim 6, wherein, in step 1,
the mass ratio of the phosphorus-containing flame retardant to the polylactic acid is (0.1-0.6): 1.
8. the method according to claim 6, wherein, in step 1,
the blending is carried out in a double-screw extruder, the temperature of each zone in the double-screw extruder is (180-220) DEG C- (170-210) DEG C- (160-200) DEG C- (150-190) DEG C- (150-170) DEG C- (140-160) DEG C;
the blending time is 1-10 min, and the screw rotating speed is 20-70 r/min.
9. The method according to claim 6, wherein in step 2,
the mass ratio of the flame-retardant polylactic acid master batch to the PLLA/ZnO master batch is (0.01-30) to (0.5-10) to (60-100);
the mixing is preferably carried out in a single screw extruder, in which the temperature of each zone is (140-200) ° c- (170-210) ° c- (170-220) ° c- (180-220) ° c, and the mixing time is 1-10 min.
10. A flame-retardant polylactic acid fiber, wherein the flame-retardant polylactic acid fiber is prepared by spinning the polylactic acid blend composition according to any one of claims 1 to 5 or the polylactic acid blend composition prepared by the preparation method according to any one of claims 6 to 9;
the spinning is preferably carried out in a single-screw spinning machine, and the temperature of each area in the single-screw spinning machine is (140-180) DEG C- (170-210) DEG C- (180-220) DEG C;
the temperature of the pipeline is 170-210 ℃, and the temperature of the spinning assembly is 170-220 ℃;
the titer of the heat-resistant flame-retardant polylactic acid fiber is 110 to 135dtex/96f.
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CN112321996A (en) * | 2020-10-30 | 2021-02-05 | 今创景新材料科技(上海)有限公司 | Phosphorus-containing flame-retardant degradable polyester material and preparation method thereof |
CN113337092A (en) * | 2021-06-16 | 2021-09-03 | 西华大学 | Transparent heat-resistant full-degradable component polylactic acid composite material and preparation method thereof |
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CN105239194A (en) * | 2015-11-20 | 2016-01-13 | 王庆 | Method of preparing flame-retarding anti-microbial polylactic acid fibers, spinning fibers into yarn and making fabric |
CN112321996A (en) * | 2020-10-30 | 2021-02-05 | 今创景新材料科技(上海)有限公司 | Phosphorus-containing flame-retardant degradable polyester material and preparation method thereof |
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