CN109206600A - A kind of preparation method of phosphorous copolymerization flame-proof polylactic acid fiber - Google Patents
A kind of preparation method of phosphorous copolymerization flame-proof polylactic acid fiber Download PDFInfo
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- CN109206600A CN109206600A CN201710532652.3A CN201710532652A CN109206600A CN 109206600 A CN109206600 A CN 109206600A CN 201710532652 A CN201710532652 A CN 201710532652A CN 109206600 A CN109206600 A CN 109206600A
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- flame
- polylactic acid
- lactide
- proof
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- 239000004626 polylactic acid Substances 0.000 title claims abstract description 127
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 126
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 84
- 239000000835 fiber Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000011347 resin Substances 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 53
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000012545 processing Methods 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 14
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 10
- 230000005855 radiation Effects 0.000 claims description 9
- -1 organic acid rare earth compound Chemical class 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 235000010233 benzoic acid Nutrition 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000002506 iron compounds Chemical class 0.000 claims description 3
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 2
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims 2
- 125000005842 heteroatom Chemical group 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 49
- 238000000034 method Methods 0.000 abstract description 27
- 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 abstract description 19
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 22
- 150000003384 small molecules Chemical class 0.000 description 20
- 238000012360 testing method Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 14
- 238000009987 spinning Methods 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 239000004753 textile Substances 0.000 description 12
- 238000011056 performance test Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6922—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/88—Post-polymerisation treatment
- C08G63/90—Purification; Drying
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of preparation methods of phosphorous copolymerization flame-proof polylactic acid fiber comprising following steps: under the effect of the catalyst, reaction product is made through melt polymerization in lactide, wherein the conversion ratio of lactide is 10%-45%；Phosphorous copolymerization flame-proof polylactic acid resin is made through ring-opening polymerisation in reaction product and phosphor-containing flame-proof monomer, wherein conversion ratio >=92% of lactide；By phosphorous copolymerization flame-proof polylactic acid resin after the processing of removing lactide and devolatilization processing, phosphorous copolymerization flame-proof polylactic acid fiber is made through melt-spun molding, wherein, through removing lactide treated it is phosphorous copolymerization flame-proof polylactic acid resin in lactide content≤0.5wt%.The present invention prepares fire-retardant PLA using copolymerization process, effectively prevents the problems such as fire retardant is migrated and is precipitated with matrix poor compatibility, fire retardant, multiple melt-processed thermostability is poor, obtained flame-retardant PLA has both good spinnability, flame retardant property and mechanical property.
Description
Technical field
The invention belongs to flame-proof polylactic acid and its fibre technology fields, and in particular to a kind of phosphorous copolymerization flame-proof polylactic acid is fine
The preparation method of dimension.
Background technique
Polylactic acid (PLA) be it is a kind of from renewable resource and can it is degradable for carbon dioxide and water it is " green
Color macromolecule " material.It is nonirritant since its is nontoxic, there is excellent biocompatibility, bioresorbable, complete biology
Degradability, while also there is excellent physics, mechanical performance, thus widely paid close attention to.The anti-flammability of polylactic acid itself
Can only UL94HB grade, limit oxygen index (LOI) is 21%, and when burning only forms one layer of just visible carburization zone, then very
It liquefies, drip fastly and burn, which greatly limits its applications in the fields such as aviation, electronic apparatus, automobile.Therefore, having must
Its anti-flammability is modified and then improved to polylactic acid.
Therefore, presently, there are the problem of be the preparation side for being badly in need of researching and developing a kind of phosphorous copolymerization flame-proof polylactic acid fiber
Method.
Summary of the invention
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide a kind of phosphorous copolymerization is fire-retardant
The preparation method of acid fiber by polylactic.Preparation method provided by the invention is simple, on the one hand solves existing fire retardant and polylactic acid
Poor compatibility causes to be difficult into fine and gained fibrous mechanical property difference problem, on the other hand alleviates polylactic acid easy firing and melts
Drip the serious problem of phenomenon.
For this purpose, first aspect present invention provides a kind of preparation method of phosphorous copolymerization flame-proof polylactic acid fiber comprising
Following steps:
Under the effect of the catalyst reaction product is made through melt polymerization, wherein the conversion of lactide in lactide by S1
Rate is 10%-45%, and the reaction product includes unreacted lactide and polylactic acid prepolymer；
Phosphorous copolymerization flame-proof polylactic acid resin is made through ring-opening polymerisation in reaction product and phosphor-containing flame-proof monomer by S2, wherein
Conversion ratio >=92% of lactide；
S3 is formed by phosphorous copolymerization flame-proof polylactic acid resin after the processing of removing lactide and devolatilization processing through melt-spun
Phosphorous copolymerization flame-proof polylactic acid fiber is made, wherein through in removing lactide treated phosphorous copolymerization flame-proof polylactic acid resin
Content≤0.5wt% of lactide.
According to the method for the present invention, in step sl, based on the poidometer of lactide, the dosage of the catalyst is
0.01wt%-0.1wt%.
In certain embodiments of the present invention, in step sl, the melt polymerization uses microwave radiation polymerization；It is preferred that
The reaction temperature of the melt polymerization is 130-160 DEG C, and the reaction time of the melt polymerization is 2-15min；It is preferred that described poly-
The weight average molecular weight of lactic acid prepolymer is 100-40000, more preferably 500-20000.
According to the method for the present invention, the catalyst is selected from glass putty, stannous chloride, stannous octoate, benzoic acid stannous, three oxidations
One of two antimony, organic acid rare earth compound and iron compound are a variety of.
According to the method for the present invention, in step s 2, the total weight based on reaction product Yu phosphor-containing flame-proof monomer, it is described to contain
The dosage of phosphorus flame-retardant monomer is 1wt%-5wt%, preferably 1wt%-3wt%.
According to the method for the present invention, the phosphor-containing flame-proof monomer is the reactive functional groups that main chain includes hydroxyl and/or amido
Compound；It is preferred that the phosphor-containing flame-proof monomer selected from organophosphorus ester, the structure containing phospho hetero phenanthrene phosphonate ester and phosphine oxide in
It is one or more；The more preferable phosphor-containing flame-proof monomer is selected from one or more in lower formula (I)-(X) compound represented；
In certain embodiments of the present invention, in step s 2, the ring-opening polymerisation uses microwave radiation polymerization；It is preferred that
The reaction temperature of the ring-opening polymerisation is 140-200 DEG C, and the reaction time of the ring-opening polymerisation is 5-30min.
According to the method for the present invention, in step s 2, the weight average molecular weight of the phosphorous copolymerization flame-proof polylactic acid resin is 15
Ten thousand -40 ten thousand, preferably 15.1 ten thousand -25 ten thousand.
In certain embodiments of the present invention, in step s3, removing lactide processing -0.07 to
It is carried out under the pressure of 0.095MPa；The melt-spun carries out at a temperature of being molded over 200-240 DEG C.
Second aspect of the present invention provides a kind of the phosphorous total of the preparation method preparation according to a first aspect of the present invention
Poly- flame-proof polylactic acid fiber.
Specific embodiment
To keep the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiments are only
Serve illustrative, it is not limited to application range of the invention.
Polylactic acid blend modification in view of the prior art causes to be difficult into fine, institute there are fire retardant and polylactic acid poor compatibility
Fibrous mechanical property difference and polylactic acid poor fire the technical issues of, the present inventor has found after study, this
Polylactic acid obtained by inventive method has low-down lactide content, can be directly used for spinning, and effectively prevent fire-retardant list
The technical problem of body and matrix poor compatibility, the migration of flame-retardant monomer and precipitation and multiple melt-processed thermal stability difference, institute
It obtains polylactic acid and has both good spinnability, flame retardant property and mechanical property.The present invention is based on what above-mentioned discovery was made.
Therefore, the preparation method of phosphorous copolymerization flame-proof polylactic acid fiber involved in first aspect present invention, including it is as follows
Step:
Under the effect of the catalyst reaction product is made through melt polymerization, wherein the conversion of lactide in lactide by S1
Rate is 10%-45%, and the reaction product includes unreacted lactide and polylactic acid prepolymer；
Phosphorous copolymerization flame-proof polylactic acid resin is made through ring-opening polymerisation in reaction product and phosphor-containing flame-proof monomer by S2, wherein
Conversion ratio >=92% of lactide；
S3 is formed by phosphorous copolymerization flame-proof polylactic acid resin after the processing of removing lactide and devolatilization processing through melt-spun
Phosphorous copolymerization flame-proof polylactic acid fiber is made, wherein through in removing lactide treated phosphorous copolymerization flame-proof polylactic acid resin
Content≤0.5wt% of lactide.
Term " conversion ratio of lactide " of the present invention refers to the quality and lactide raw material of the lactide reacted
The percentage of gross mass.For example, in step sl, the conversion ratio of lactide is 10%-45%, i.e., have in lactide raw material
The lactide of 10%-45% occurs melt polymerization and forms polylactic acid prepolymer, therefore, comprising unreacted in reaction product
Lactide.In step s 2, with phosphor-containing flame-proof monomer and polylactic acid prepolymer ring-opening reaction can occur for unreacted lactide,
So that the content of lactide is further reduced in reaction system, i.e., so that the conversion ratio of lactide is further increased to >=92%.
In the preparation method of above-mentioned phosphorous copolymerization flame-proof polylactic acid fiber, in step sl, the poidometer based on lactide,
The dosage of the catalyst is 0.01wt%-0.1wt%, preferably 0.02wt%-0.06wt%.Using lower in the present invention
Catalyst amount can obtain the higher polylactic acid of weight average molecular weight.
In the preparation method of above-mentioned phosphorous copolymerization flame-proof polylactic acid fiber, in step sl, the melt polymerization is using micro-
Wave radiation polymerization；It is preferred that the reaction temperature of the melt polymerization is 130-160 DEG C, the reaction time of the melt polymerization is 2-
15min；It is preferred that the weight average molecular weight of the polylactic acid prepolymer is 100-40000, preferably 500-20000.
The energy and time can effectively be saved using microwave radiation polymerization in the present invention, reduce the life of flame-proof polylactic acid fiber
Produce cost.
In the preparation method of above-mentioned phosphorous copolymerization flame-proof polylactic acid fiber, the catalyst is selected from glass putty, stannous chloride, pungent
Having in sour stannous, benzoic acid stannous, antimony oxide, organic acid rare earth compound and iron compound is one or more.It is preferred that
The catalyst is stannous octoate.
It is above-mentioned it is phosphorous copolymerization flame-proof polylactic acid fiber preparation method in, in step s 2, based on reaction product with it is phosphorous
The total weight of flame-retardant monomer, the dosage of the phosphor-containing flame-proof monomer are 1wt%-5wt%, preferably 1wt%-3wt%.
In the preparation method of above-mentioned phosphorous copolymerization flame-proof polylactic acid fiber, the phosphor-containing flame-proof monomer is that main chain includes hydroxyl
With the compound of the reactive functional groups of/amido.It is preferred that the phosphor-containing flame-proof monomer is selected from organophosphorus ester, structure containing phospho hetero phenanthrene
Phosphonate ester and one of phosphine oxide or a variety of.The more preferable phosphor-containing flame-proof monomer, which is selected from shown in lower formula (I)-(X), to be changed
It closes one or more in object；
In the preparation method of above-mentioned phosphorous copolymerization flame-proof polylactic acid fiber, in step s 2, the ring-opening polymerisation is using micro-
Wave radiation polymerization；It is preferred that the reaction temperature of the ring-opening polymerisation is 140-200 DEG C, the reaction time of the ring-opening polymerisation is 5-
30min。
Reaction rate can also be improved using microwave radiation polymerization in the present invention, reduce lactide ring-opening polymerisation side reaction
Occur, is conducive to the quality for improving product.
In the preparation method of above-mentioned phosphorous copolymerization flame-proof polylactic acid fiber, in step s 2, the phosphorous copolymerization is fire-retardant poly-
The weight average molecular weight of lactic acid resin is 150,000-40 ten thousand, preferably 15.1 ten thousand-25 ten thousand.
In the preparation method of above-mentioned phosphorous copolymerization flame-proof polylactic acid fiber, in step s3, the removing lactide processing
It is carried out under -0.07 to 0.095MPa pressure；The melt-spun carries out at a temperature of being molded over 200-240 DEG C.
In the preparation method of above-mentioned phosphorous copolymerization flame-proof polylactic acid fiber, in step s3, the phosphorous copolymerization of synthesis is hindered
Combustion polylactic resin enters Devolatilization device and double screw extruder carries out devolatilization, and small point in melt is removed with the mode vacuumized
Son and oligomer obtain the resin for meeting into fine requirement, to spinning equipment after double screw extruder.
Second aspect of the present invention is related to a kind of phosphorous copolymerization of preparation method preparation according to a first aspect of the present invention
Flame-proof polylactic acid fiber.
The present invention prepare phosphorous reaction-type flame-retarding monomer using existing method, then by lactide and phosphor-containing flame-proof monomer into
Row ring-opening polymerisation obtains phosphorous copolymerization flame-proof polylactic acid resin, and melt-spun molding is directly carried out after devolatilization and prepares excellent fireproof performance
Phosphorous copolymerization flame-proof polylactic acid fiber.
Compared with prior art, the beneficial effects of the present invention are:
(1) lactide remaining in polylactic resin is removed in the present invention by removed under reduced pressure method, this method can protect
It holds and removes lactide on the basis of polylactic acid performance, obtained polylactic acid has low-down lactide content, can directly use
In spinning；
(2) the method for the present invention is in the preparation process of acid fiber by polylactic, using microwave radiation polymerization, effectively save the energy and
Time reduces the production cost of flame-proof polylactic acid fiber；
(3) present invention prepares flame-proof polylactic acid using the method for copolymerization, effectively prevent fire retardant and matrix poor compatibility,
The problems such as fire retardant is migrated and is precipitated, multiple melt-processed thermal stability is poor, gained polylactic acid has both good spinnability and resistance
Fire performance；The flame-proof polylactic acid fiber of preparation has both excellent flame retardant property and mechanical property, can be used for automobile interior decoration, decoration material
The fields more demanding to flame retardant property such as material, clothes home textile, wide market.
Characterization test method of the present invention is as follows:
(1) flame retardant property: referring to GB/T 5454-1997 (textile combustion performance test oxygen index method) standard；
(2) fibre strength: referring to GB/T 14344-2008 standard.
Embodiment
Embodiment 1
It is before reaction that lactide and phosphor-containing flame-proof monomer is true at 60 DEG C using Formulas I compound represented as phosphor-containing flame-proof monomer
The lower dry 3h of sky removes moisture.Under an inert atmosphere, microwave reaction kettle is warming up to 140 DEG C, lactide and stannous octoate is added
Sn(Oct)2, catalyst amount is the 0.05wt% of lactide quality, carries out melt polymerization 5min, controls turning for lactide
Rate is 41%, obtains reaction product.It comprising unreacted lactide and weight average molecular weight is 6000 in the reaction product
Polylactic acid prepolymer.The phosphor-containing flame-proof monomer of 1wt% is added into above-mentioned reaction product, microwave tube type is entered after stirring and is reacted
Device carries out ring-opening polymerization time 15min at being 190 DEG C in temperature, the phosphorous copolymerization that weight average molecular weight is 170000 is made
Flame-proof polylactic acid resin.Under -0.07MPa pressure condition remaining third in the removed under reduced pressure phosphorous copolymerization flame-proof polylactic acid resin
After lactide, devolatilization is carried out into Devolatilization device, small molecule and oligomer in melt is removed with the mode vacuumized, is met
The resin required at fibre.Then by above-mentioned resin enter spinning equipment form to obtain through melt-spun directly at 220 DEG C it is phosphorous total
Poly- flame-proof polylactic acid fiber.Temperature is 205 DEG C when melt conveying, and small molecule (i.e. lactide) content in final material is
0.4wt%.
It is fire-retardant that the phosphorous copolymerization is tested referring to GB/T 5454-1997 standard (textile combustion performance test oxygen index method)
The LOI value of acid fiber by polylactic is 29.2, and the fire-retardant rank for testing the sample through UL-94 is V-1 grades.With (the identical survey of pure polylactic acid
The LOI value of pure acid fiber by polylactic is 23.7) to compare under test-object is quasi-, and flame retardant property significantly improves.
Referring to GB/T 14344-2008 standard testing, the intensity of the phosphorous copolymerization flame-proof polylactic acid fiber reaches 4.5cN/
dtex。
Embodiment 2
It is before reaction that lactide and phosphor-containing flame-proof monomer is true at 60 DEG C using Formulas I compound represented as phosphor-containing flame-proof monomer
The lower dry 3h of sky removes moisture.Under an inert atmosphere, microwave reaction kettle is warming up to 140 DEG C, lactide and stannous octoate is added
Sn(Oct)2, catalyst amount is the 0.05wt% of lactide quality, carries out melt polymerization 5min, controls turning for lactide
Rate is 41%, obtains reaction product.It comprising unreacted lactide and weight average molecular weight is 6000 in the reaction product
Polylactic acid prepolymer.The phosphor-containing flame-proof monomer of 3wt% is added into above-mentioned reaction product, microwave tube type is entered after stirring and is reacted
Device carries out ring-opening polymerization time 15min at being 190 DEG C in temperature, the phosphorous copolymerization that weight average molecular weight is 156000 is made
Flame-proof polylactic acid resin.Under -0.07MPa pressure condition remaining third in the removed under reduced pressure phosphorous copolymerization flame-proof polylactic acid resin
After lactide, devolatilization is carried out into Devolatilization device, small molecule and oligomer in melt is removed with the mode vacuumized, is met
The resin required at fibre.Then by above-mentioned resin enter spinning equipment form to obtain through melt-spun directly at 220 DEG C it is phosphorous total
Poly- flame-proof polylactic acid fiber.Temperature is 205 DEG C when melt conveying, and small molecule (i.e. lactide) content in final material is
0.3wt%.
It is fire-retardant that the phosphorous copolymerization is tested referring to GB/T 5454-1997 standard (textile combustion performance test oxygen index method)
The LOI value of acid fiber by polylactic is 29.7, and the fire-retardant rank for testing the sample through UL-94 is V-1 grades.With (the identical survey of pure polylactic acid
The LOI value of pure acid fiber by polylactic is 23.7) to compare under test-object is quasi-, and flame retardant property significantly improves.
Referring to GB/T 14344-2008 standard testing, the intensity of the phosphorous copolymerization flame-proof polylactic acid fiber reaches 4.0cN/
dtex。
Embodiment 3
It is before reaction that lactide and phosphor-containing flame-proof monomer is true at 60 DEG C using Formulas I compound represented as phosphor-containing flame-proof monomer
The lower dry 3h of sky removes moisture.Under an inert atmosphere, microwave reaction kettle is warming up to 140 DEG C, lactide and stannous octoate is added
Sn(Oct)2, catalyst amount is the 0.05wt% of lactide quality, carries out melt polymerization 5min, controls turning for lactide
Rate is 41%, obtains reaction product.It comprising unreacted lactide and weight average molecular weight is 6000 in the reaction product
Polylactic acid prepolymer.The phosphor-containing flame-proof monomer of 5wt% is added into above-mentioned reaction product, microwave tube type is entered after stirring and is reacted
Device carries out ring-opening polymerization time 15min at being 190 DEG C in temperature, the phosphorous copolymerization that weight average molecular weight is 151000 is made
Flame-proof polylactic acid resin.Under -0.07MPa pressure condition remaining third in the removed under reduced pressure phosphorous copolymerization flame-proof polylactic acid resin
After lactide, devolatilization is carried out into Devolatilization device, small molecule and oligomer in melt is removed with the mode vacuumized, is met
The resin required at fibre.Then by above-mentioned resin enter spinning equipment form to obtain through melt-spun directly at 220 DEG C it is phosphorous total
Poly- flame-proof polylactic acid fiber.Temperature is 205 DEG C when melt conveying, and small molecule (i.e. lactide) content in final material is
0.3wt%.
It is fire-retardant that the phosphorous copolymerization is tested referring to GB/T 5454-1997 standard (textile combustion performance test oxygen index method)
The LOI value of acid fiber by polylactic is 32.0, and the fire-retardant rank for testing the sample through UL-94 is V-1 grades.With (the identical survey of pure polylactic acid
The LOI value of pure acid fiber by polylactic is 23.7) to compare under test-object is quasi-, and flame retardant property significantly improves.
Referring to GB/T 14344-2008 standard testing, the intensity of the phosphorous copolymerization flame-proof polylactic acid fiber reaches 3.9cN/
dtex。
Embodiment 4
It is before reaction that lactide and phosphor-containing flame-proof monomer is true at 60 DEG C using Formulas I compound represented as phosphor-containing flame-proof monomer
The lower dry 3h of sky removes moisture.Under an inert atmosphere, microwave reaction kettle is warming up to 140 DEG C, lactide and stannous octoate is added
Sn(Oct)2, catalyst amount is the 0.05wt% of lactide quality, carries out melt polymerization 6min, controls turning for lactide
Rate is 45%, obtains reaction product.It comprising unreacted lactide and weight average molecular weight is 10500 in the reaction product
Polylactic acid prepolymer.The phosphor-containing flame-proof monomer of 1wt% is added into above-mentioned reaction product, microwave tube type is entered after stirring and is reacted
Device carries out ring-opening polymerization time 15min at being 190 DEG C in temperature, the phosphorous copolymerization that weight average molecular weight is 185000 is made
Flame-proof polylactic acid resin.Under -0.07MPa pressure condition remaining third in the removed under reduced pressure phosphorous copolymerization flame-proof polylactic acid resin
After lactide, devolatilization is carried out into Devolatilization device, small molecule and oligomer in melt is removed with the mode vacuumized, is met
The resin required at fibre.Then by above-mentioned resin enter spinning equipment form to obtain through melt-spun directly at 220 DEG C it is phosphorous total
Poly- flame-proof polylactic acid fiber.Temperature is 205 DEG C when melt conveying, and small molecule (i.e. lactide) content in final material is
0.5wt%.
It is fire-retardant that the phosphorous copolymerization is tested referring to GB/T 5454-1997 standard (textile combustion performance test oxygen index method)
The LOI value of acid fiber by polylactic is 29.4, and the fire-retardant rank for testing the sample through UL-94 is V-1 grades.With (the identical survey of pure polylactic acid
The LOI value of pure acid fiber by polylactic is 23.7) to compare under test-object is quasi-, and flame retardant property significantly improves.
Referring to GB/T 14344-2008 standard testing, the intensity of the phosphorous copolymerization flame-proof polylactic acid fiber reaches 4.7cN/
dtex。
Embodiment 5
Using formula III compound represented as phosphor-containing flame-proof monomer, by lactide and phosphor-containing flame-proof monomer at 60 DEG C before reaction
Dry 3h removes moisture under vacuum.Under an inert atmosphere, microwave reaction kettle is warming up to 130 DEG C, lactide is added and octanoic acid is sub-
Tin Sn (Oct)2, catalyst amount is the 0.06wt% of lactide quality, carries out melt polymerization 8min, controls lactide
Conversion ratio is 35%, obtains reaction product.It comprising unreacted lactide and weight average molecular weight is 7800 in the reaction product
Polylactic acid prepolymer.The phosphor-containing flame-proof monomer of 3wt% is added into above-mentioned reaction product, microwave tube type is entered after stirring and is reacted
Device carries out ring-opening polymerization time 18min at being 190 DEG C in temperature, the phosphorous copolymerization that weight average molecular weight is 152000 is made
Flame-proof polylactic acid resin.Under -0.07MPa pressure condition remaining third in the removed under reduced pressure phosphorous copolymerization flame-proof polylactic acid resin
After lactide, devolatilization is carried out into Devolatilization device, small molecule and oligomer in melt is removed with the mode vacuumized, is met
The resin required at fibre.Then by above-mentioned resin enter spinning equipment form to obtain through melt-spun directly at 220 DEG C it is phosphorous total
Poly- flame-proof polylactic acid fiber.Temperature is 205 DEG C when melt conveying, the small molecule content 0.5wt% in final material.
It is fire-retardant that the phosphorous copolymerization is tested referring to GB/T 5454-1997 standard (textile combustion performance test oxygen index method)
The LOI value of acid fiber by polylactic is 30.4, and the fire-retardant rank for testing the sample through UL-94 is V-1 grades.With (the identical survey of pure polylactic acid
The LOI value of pure acid fiber by polylactic is 23.7) to compare under test-object is quasi-, and flame retardant property significantly improves.
Referring to GB/T 14344-2008 standard testing, the intensity of the phosphorous copolymerization flame-proof polylactic acid fiber reaches 4.0cN/
dtex。
Embodiment 6
It is before reaction that lactide and phosphor-containing flame-proof monomer is true at 60 DEG C using formula IV compound represented as phosphor-containing flame-proof monomer
The lower dry 3h of sky removes moisture.Under an inert atmosphere, microwave reaction kettle is warming up to 130 DEG C, lactide and stannous octoate is added
Sn(Oct)2, catalyst amount is the 0.06wt% of lactide quality, carries out melt polymerization 8min, controls turning for lactide
Rate is 35%, obtains reaction product.It comprising unreacted lactide and weight average molecular weight is 7800 in the reaction product
Polylactic acid prepolymer.The phosphor-containing flame-proof monomer of 3wt% is added into above-mentioned reaction product, microwave tube type is entered after stirring and is reacted
Device carries out ring-opening polymerization time 18min at being 190 DEG C in temperature, the phosphorous copolymerization that weight average molecular weight is 157000 is made
Flame-proof polylactic acid resin.Under -0.07MPa pressure condition remaining third in the removed under reduced pressure phosphorous copolymerization flame-proof polylactic acid resin
After lactide, devolatilization is carried out into Devolatilization device, small molecule and oligomer in melt is removed with the mode vacuumized, is met
The resin required at fibre.Then by above-mentioned resin enter spinning equipment form to obtain through melt-spun directly at 220 DEG C it is phosphorous total
Poly- flame-proof polylactic acid fiber.Temperature is 205 DEG C when melt conveying, the small molecule content 0.3wt% in final material.
It is fire-retardant that the phosphorous copolymerization is tested referring to GB/T 5454-1997 standard (textile combustion performance test oxygen index method)
The LOI value of acid fiber by polylactic is 29.1, and the fire-retardant rank for testing the sample through UL-94 is V-1 grades.With (the identical survey of pure polylactic acid
The LOI value of pure acid fiber by polylactic is 23.7) to compare under test-object is quasi-, and flame retardant property significantly improves.
Referring to GB/T 14344-2008 standard testing, the intensity of the phosphorous copolymerization flame-proof polylactic acid fiber reaches 4.0cN/
dtex。
Embodiment 7
It is before reaction that lactide and phosphor-containing flame-proof monomer is true at 60 DEG C using Formula V compound represented as phosphor-containing flame-proof monomer
The lower dry 3h of sky removes moisture.Under an inert atmosphere, microwave reaction kettle is warming up to 130 DEG C, lactide and stannous octoate is added
Sn(Oct)2, catalyst amount is the 0.06wt% of lactide quality, carries out melt polymerization 8min, controls turning for lactide
Rate is 35%, obtains reaction product.It comprising unreacted lactide and weight average molecular weight is 7800 in the reaction product
Polylactic acid prepolymer.The phosphor-containing flame-proof monomer of 3wt% is added into above-mentioned reaction product, microwave tube type is entered after stirring and is reacted
Device carries out ring-opening polymerization time 18min at being 190 DEG C in temperature, the phosphorous copolymerization that weight average molecular weight is 155000 is made
Flame-proof polylactic acid resin.Under -0.07MPa pressure condition remaining third in the removed under reduced pressure phosphorous copolymerization flame-proof polylactic acid resin
After lactide, devolatilization is carried out into Devolatilization device, small molecule and oligomer in melt is removed with the mode vacuumized, is met
The resin required at fibre.Then by above-mentioned resin enter spinning equipment form to obtain through melt-spun directly at 220 DEG C it is phosphorous total
Poly- flame-proof polylactic acid fiber.Temperature is 205 DEG C when melt conveying, the small molecule content 0.4wt% in final material.
It is fire-retardant that the phosphorous copolymerization is tested referring to GB/T 5454-1997 standard (textile combustion performance test oxygen index method)
The LOI value of acid fiber by polylactic is 32.4, and the fire-retardant rank for testing the sample through UL-94 is V-1 grades.With (the identical survey of pure polylactic acid
The LOI value of pure acid fiber by polylactic is 23.7) to compare under test-object is quasi-, and flame retardant property significantly improves.
Referring to GB/T 14344-2008 standard testing, the intensity of the phosphorous copolymerization flame-proof polylactic acid fiber reaches 4.1cN/
dtex。
Embodiment 8
Using Formula VII compound represented as phosphor-containing flame-proof monomer, by lactide and phosphor-containing flame-proof monomer at 60 DEG C before reaction
Dry 3h removes moisture under vacuum.Under an inert atmosphere, microwave reaction kettle is warming up to 130 DEG C, lactide is added and octanoic acid is sub-
Tin Sn (Oct)2, catalyst amount is the 0.06wt% of lactide quality, carries out melt polymerization 8min, controls lactide
Conversion ratio is 35%, obtains reaction product.It comprising unreacted lactide and weight average molecular weight is 7800 in the reaction product
Polylactic acid prepolymer.The phosphor-containing flame-proof monomer of 3wt% is added into above-mentioned reaction product, microwave tube type is entered after stirring and is reacted
Device carries out ring-opening polymerization time 18min at being 190 DEG C in temperature, the phosphorous copolymerization that weight average molecular weight is 159000 is made
Flame-proof polylactic acid resin.Under -0.07MPa pressure condition remaining third in the removed under reduced pressure phosphorous copolymerization flame-proof polylactic acid resin
After lactide, devolatilization is carried out into Devolatilization device, small molecule and oligomer in melt is removed with the mode vacuumized, is met
The resin required at fibre.Then by above-mentioned resin enter spinning equipment form to obtain through melt-spun directly at 220 DEG C it is phosphorous total
Poly- flame-proof polylactic acid fiber.Temperature is 205 DEG C when melt conveying, the small molecule content 0.4wt% in final material.
It is fire-retardant that the phosphorous copolymerization is tested referring to GB/T 5454-1997 standard (textile combustion performance test oxygen index method)
The LOI value of acid fiber by polylactic is 31.7, and the fire-retardant rank for testing the sample through UL-94 is V-1 grades.With (the identical survey of pure polylactic acid
The LOI value of pure acid fiber by polylactic is 23.7) to compare under test-object is quasi-, and flame retardant property significantly improves.
Referring to GB/T 14344-2008 standard testing, the intensity of the phosphorous copolymerization flame-proof polylactic acid fiber reaches 4.2cN/
dtex。
Embodiment 9
It is before reaction that lactide and phosphor-containing flame-proof monomer is true at 60 DEG C using Formula X compound represented as phosphor-containing flame-proof monomer
The lower dry 3h of sky removes moisture.Under an inert atmosphere, microwave reaction kettle is warming up to 130 DEG C, lactide and stannous octoate is added
Sn(Oct)2, catalyst amount is the 0.06wt% of lactide quality, carries out melt polymerization 8min, controls turning for lactide
Rate is 35%, obtains reaction product.It comprising unreacted lactide and weight average molecular weight is 7800 in the reaction product
Polylactic acid prepolymer.The phosphor-containing flame-proof monomer of 3wt% is added into above-mentioned reaction product, microwave tube type is entered after stirring and is reacted
Device carries out ring-opening polymerization time 18min at being 190 DEG C in temperature, the phosphorous copolymerization that weight average molecular weight is 161000 is made
Flame-proof polylactic acid resin.Under -0.07MPa pressure condition remaining third in the removed under reduced pressure phosphorous copolymerization flame-proof polylactic acid resin
After lactide, devolatilization is carried out into Devolatilization device, small molecule and oligomer in melt is removed with the mode vacuumized, is met
The resin required at fibre.Then by above-mentioned resin enter spinning equipment form to obtain through melt-spun directly at 220 DEG C it is phosphorous total
Poly- flame-proof polylactic acid fiber.Temperature is 205 DEG C when melt conveying, the small molecule content 0.5wt% in final material.
It is fire-retardant that the phosphorous copolymerization is tested referring to GB/T 5454-1997 standard (textile combustion performance test oxygen index method)
The LOI value of acid fiber by polylactic is 30.6, and the fire-retardant rank for testing the sample through UL-94 is V-1 grades.With (the identical survey of pure polylactic acid
The LOI value of pure acid fiber by polylactic is 23.7) to compare under test-object is quasi-, and flame retardant property significantly improves.
Referring to GB/T 14344-2008 standard testing, the intensity of the phosphorous copolymerization flame-proof polylactic acid fiber reaches 4.2cN/
dtex。
Comparative example 1
It is before reaction that lactide and phosphor-containing flame-proof monomer is true at 60 DEG C using Formulas I compound represented as phosphor-containing flame-proof monomer
The lower dry 3h of sky removes moisture.Under an inert atmosphere, microwave reaction kettle is warming up to 140 DEG C, lactide and stannous octoate is added
Sn(Oct)2, catalyst amount is the 0.3wt% of lactide quality, carries out melt polymerization 2min, controls turning for lactide
Rate is 41%, obtains reaction product.It comprising unreacted lactide and weight average molecular weight is 3600 in the reaction product
Polylactic acid prepolymer.The phosphor-containing flame-proof monomer of 5wt% is added into above-mentioned reaction product, microwave tube type is entered after stirring and is reacted
Device carries out ring-opening polymerization time 8min at being 190 DEG C in temperature, and the phosphorous copolymerization that weight average molecular weight is 71000 is made and hinders
Fire polylactic resin.The third friendship remaining in the removed under reduced pressure phosphorous copolymerization flame-proof polylactic acid resin under -0.07MPa pressure condition
After ester, devolatilization is carried out into Devolatilization device, small molecule and oligomer in melt is removed with the mode vacuumized, obtains meeting into
The resin that fibre requires.Then above-mentioned resin spinning equipment is entered directly to form to obtain phosphorous copolymerization through melt-spun at 220 DEG C
Flame-proof polylactic acid fiber.Temperature is 205 DEG C when melt conveying, and small molecule (i.e. lactide) content in final material is
0.3wt%.
It is fire-retardant that the phosphorous copolymerization is tested referring to GB/T 5454-1997 standard (textile combustion performance test oxygen index method)
The LOI value of acid fiber by polylactic is 30.7, and the fire-retardant rank for testing the sample through UL-94 is V-1 grades.With (the identical survey of pure polylactic acid
The LOI value of pure acid fiber by polylactic is 23.7) to compare under test-object is quasi-, and flame retardant property significantly improves.
Referring to GB/T 14344-2008 standard testing, the intensity of the phosphorous copolymerization flame-proof polylactic acid fiber reaches 2.1cN/
dtex。
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (10)
1. a kind of preparation method of phosphorous copolymerization flame-proof polylactic acid fiber comprising following steps:
Under the effect of the catalyst reaction product is made through melt polymerization in lactide by S1, wherein the conversion ratio of lactide is
10%-45%, the reaction product include unreacted lactide and polylactic acid prepolymer；
Phosphorous copolymerization flame-proof polylactic acid resin is made through ring-opening polymerisation, wherein third hands in reaction product and phosphor-containing flame-proof monomer by S2
Conversion ratio >=92% of ester；
S3 is formed through melt-spun and is made by phosphorous copolymerization flame-proof polylactic acid resin after the processing of removing lactide and devolatilization processing
Phosphorous copolymerization flame-proof polylactic acid fiber, wherein through the third friendship in removing lactide treated phosphorous copolymerization flame-proof polylactic acid resin
Content≤0.5wt% of ester.
2. preparation method according to claim 1, which is characterized in that in step sl, the poidometer based on lactide, institute
The dosage for stating catalyst is 0.01wt%-0.1wt%.
3. preparation method according to claim 1 or 2, which is characterized in that in step sl, the melt polymerization is using micro-
Wave radiation polymerization；It is preferred that the reaction temperature of the melt polymerization is 130-160 DEG C, the reaction time of the melt polymerization is 2-
15min；It is preferred that the weight average molecular weight of the polylactic acid prepolymer is 100-40000, more preferably 500-20000.
4. preparation method described in any one of -3 according to claim 1, which is characterized in that the catalyst be selected from glass putty,
One of stannous chloride, stannous octoate, benzoic acid stannous, antimony oxide, organic acid rare earth compound and iron compound or
It is a variety of.
5. preparation method described in any one of -4 according to claim 1, which is characterized in that in step s 2, based on reaction
The total weight of product and phosphor-containing flame-proof monomer, the dosage of the phosphor-containing flame-proof monomer are 1wt%-5wt%, preferably 1wt%-
3wt%.
6. preparation method described in any one of -5 according to claim 1, which is characterized in that based on the phosphor-containing flame-proof monomer
Chain includes the compound of the reactive functional groups of hydroxyl and/or amido；It is preferred that the phosphor-containing flame-proof monomer be selected from organophosphorus ester,
One of the phosphonate ester of the structure containing phospho hetero phenanthrene and phosphine oxide are a variety of；The more preferable phosphor-containing flame-proof monomer is selected from lower formula (I)-
(X) one or more in compound represented；
7. preparation method described in any one of -6 according to claim 1, which is characterized in that in step s 2, the open loop
Polymerization uses microwave radiation polymerization；It is preferred that the reaction temperature of the ring-opening polymerisation is 140-200 DEG C, the reaction of the ring-opening polymerisation
Time is 5-30min.
8. preparation method according to any one of claims 1-7, which is characterized in that in step s 2, described phosphorous
The weight average molecular weight for being copolymerized flame-proof polylactic acid resin is 150,000-40 ten thousand, preferably 15.1 ten thousand-25 ten thousand.
9. preparation method described in any one of -8 according to claim 1, which is characterized in that in step s3, the removing
Lactide processing carries out under -0.07 to 0.095MPa pressure；The melt-spun carries out at a temperature of being molded over 200-240 DEG C.
10. the phosphorous copolymerization flame-proof polylactic acid fiber of the preparation of preparation method described in any one of -9 according to claim 1.
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