CN109629038A

CN109629038A - Flame-proof polylactic acid fiber and preparation method thereof containing metal-modified cross carboxylate

Info

Publication number: CN109629038A
Application number: CN201811527152.1A
Authority: CN
Inventors: 李东华; 陆育明; 冯忠耀; 陈辉华; 孙宾; 朱美芳; 李忠; 顾惠琴
Original assignee: SHANGHAI DEFULUN CHEMICAL FIBER CO Ltd; Donghua University
Current assignee: Shanghai defulun New Material Technology Co.,Ltd.; Donghua University
Priority date: 2018-12-13
Filing date: 2018-12-13
Publication date: 2019-04-16
Anticipated expiration: 2038-12-13
Also published as: CN109629038B

Abstract

The present invention relates to a kind of flame-proof polylactic acid fiber and preparation method thereof containing metal-modified cross carboxylate, l-lactic acid is sliced, dextrorotation polylactic acid slice and function polylactic acid master batch containing modifier A and modifying agent B use melt spinning method that the flame-proof polylactic acid fiber containing metal-modified cross carboxylate is made after mixing, wherein, l-lactic acid slice and the mass ratio of dextrorotation polylactic acid slice are 1:1, modifier A is aluminum benzoate, the mixture that hydrated magnesium silicate and silica are mixed to get by the mass ratio of 2:1:1, modifying agent B is insoluble insoluble metal-modified cross carboxylate, metal-modified cross carboxylate is at 80 DEG C or less insoluble in most organic solvents, it is not melted in room temperature to T range, T >=380 DEG C.The method of the present invention is simple and easy, at low cost, and final acid fiber by polylactic fusing point obtained is high and has excellent flame retardant property, there is fabulous promotional value.

Description

Flame-proof polylactic acid fiber and preparation method thereof containing metal-modified cross carboxylate

Technical field

The invention belongs to fibre modification technical fields, are related to a kind of flame-proof polylactic acid containing metal-modified cross carboxylate Fiber and preparation method thereof.

Background technique

Currently, common synthetic fibers such as polyester, nylon etc., physics and chemical property are stablized, but there is using after The problem of waste can not decompose.In order to realize sustainable development, field of textiles needs new alternative materials, especially to ring The polymer of border close friend, polylactic acid (PLA) belong to linear aliphatic race thermoplastic polyester, have good biocompatibility and can drop Performance is solved, can be analyzed to water and carbon dioxide under certain condition.

Penetrability is good, elastic recovery is high, the combustion heat relative to having for petroleum-based PET fiber for PLA fiber It is small, burning fuming is few, ultra-violet resistance is good and the advantages such as refractive index is low, and rich in gloss, fabric feeling it is good and can biology Degradation.But there is also some defects for PLA fiber, for example its linear aliphatic race thermoplastic poly ester structure makes its hydrolysis resistance Difference, fusing point is low, poor heat resistance, this limits its use environment to a certain extent, also fundamentally limits acid fiber by polylactic Scale use.

In addition, in daily life, due to textile combustion caused by fire incident can bring injures and deaths and property Loss has become people's demand urgent at present using fire-retardant tooling and household textiles.

For carboxylate due to similar with the polymer architectures such as polyester, compatibility is good, is often used as functional modification carrier.To ester After compound carries out functional modification, the modification that can be realized to polymer is blended with polymer meltings such as polyester in it.Wherein ten For font carboxylate since its molecular structure is complex, the group of linkage function particle is more, is a kind of ideal functionalization Modified support.However, the fusing point of functional cross carboxylate is not high, generally at 60~70 DEG C, this stores it and transports Certain requirement is proposed, use cost is increased.Simultaneously as the addition of low molecule carboxylate type auxiliary agent can be improved greatly The rheological property of polymer, the too high levels of cross carboxylate can bring difficulty to the machine-shaping of polymer in polymer, Its additive amount when in use is typically not greater than 6~8wt%, and the functional form master batch of so low additive amount be difficult to meet it is corresponding Functional requirements.Therefore in the preparation process of current functional form master batch, cross carboxylate is used to add as functionality The master batch of agent is actually rare.

Therefore, overcome the defect of cross carboxylate itself to be modified using it to PLA fiber, and then develop one kind Flame-proof polylactic acid fiber containing metal-modified cross carboxylate has a very important significance.

Summary of the invention

The purpose of the present invention is overcoming the defect of cross carboxylate itself, prepared using it a kind of containing metal-modified cross Flame-proof polylactic acid fiber of type carboxylate and preparation method thereof.The present invention is first modified cross carboxylate and one kind has been made Metal-modified cross carboxylate with insoluble not molten characteristic, the fusing point of metal-modified cross carboxylate are higher than the overwhelming majority The melting temperature of polymer will not be melted when being blended with polymer melting, because of the blend machine-shaping without caused by Difficulty recycles metal-modified cross carboxylate to be modified PLA, metal-modified cross carboxylate load have metal from Son, metal ion can be improved the crystallinity and thermal stability of material, thus its fusing point that can improve PLA fiber and anti-flammability Energy.

In order to achieve the above object, the technical solution adopted by the present invention are as follows:

Flame-proof polylactic acid fiber containing metal-modified cross carboxylate mainly divides by acid fiber by polylactic matrix and uniformly Modifier A and modifying agent the B composition being dispersed in acid fiber by polylactic matrix；

The acid fiber by polylactic matrix by etc. quality l-lactic acid and dextrorotation polylactic acid form, the modifier A is The mixture that aluminum benzoate, hydrated magnesium silicate and silica are mixed to get by the mass ratio of 2:1:1, the modifying agent B are not The network polymerization that molten insoluble metal-modified cross carboxylate, specially cross carboxylate and metal ion crosslinked are formed Object, metal-modified cross carboxylate have insoluble insoluble characteristic, organic solvent I are not dissolved at 80 DEG C or less, in room temperature to T It is not melted in range, T >=380 DEG C；

The structural formula of the cross carboxylate is as follows:

In formula,The segment between the quaternary carbon C and carboxyl end group of cross carboxylate molecular center is represented,In contain Double bond with oxygen atom, cross carboxylate used in the present invention can carry out in cross carboxylate disclosed in the prior art Selection, structural formula herein is only symbolically depicted its structure, as long as the cross esterification that end group is carboxyl, central atom is C Object is all within the scope of the present invention,Specific structure can be selected in the prior art；

The crosslinking is to pass through coordinate bond with metal ion by the oxygen atom in cross carboxylate intramolecule double bond Acid ion and metal ion in connection while cross carboxylate molecule pass through what ion key connection was realized；It is described organic molten Agent I is aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon solvent, alcohols solvent, esters solvent, ketone Class solvent, acetonitrile, pyridine, phenol, N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.Metal-modified cross of the invention Type carboxylate does not dissolve in most organic solvents, is only simply to enumerate some common solvents herein.

As a preferred technical scheme:

Flame-proof polylactic acid fiber as described above containing metal-modified cross carboxylate contains metal-modified cross esterification The filament number of the flame-proof polylactic acid fiber of object is 3.0~4.4dtex, and breaking strength >=3.70cN/dtex, elongation at break is 45~55%, line density deviation ratio is -8.0~8.0%；

The fusing point of the flame-proof polylactic acid fiber containing metal-modified cross carboxylate is 200~210 DEG C；The prior art In acid fiber by polylactic fusing point be 180~190 DEG C, illustrate that the fusing point of acid fiber by polylactic of the invention has compared with the prior art Significant raising；

Contain P elements in the flame-proof polylactic acid fiber containing metal-modified cross carboxylate, phosphorus content > 6500ppm, limit oxygen index are that 30~38%, UL-94 reaches V-0 grades.

Flame-proof polylactic acid fiber as described above containing metal-modified cross carboxylate, the aromatic hydrocarbon solvent are Benzene,toluene,xylene, styrene, butyl toluene or vinyltoluene；The fat hydrocarbon solvent is n-hexane, pentane, hexane Or octane；The alicyclic hydrocarbon type solvent is hexamethylene, cyclohexanone or toluene cyclohexanone；The halogenated hydrocarbon solvent is chlorobenzene, two Chlorobenzene, methylene chloride, chloroform, carbon tetrachloride, trichloro ethylene, tetrachloro-ethylene, trichloropropane or dichloroethanes；The alcohols solvent For methanol, ethyl alcohol, isopropanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol or propylene glycol；The esters solvent is tumer Ester, ethyl acetate or propyl acetate；The ketones solvent is acetone, espeleton, methylisobutylketone, cyclohexanone or toluene hexamethylene Ketone.

Flame-proof polylactic acid fiber as described above containing metal-modified cross carboxylate, the metal-modified cross ester The aerial initial decomposition temperature of compound is 300~400 DEG C, and the metal-modified cross carboxylate is dispersed in polymer-based Partial size in body is 40~500nm.

Flame-proof polylactic acid fiber as described above containing metal-modified cross carboxylate, the system of the cross carboxylate It is standby that steps are as follows:

(a) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is stirred in nitrogen or inert gas shielding and machinery Fusion esterification reaction is carried out under conditions of mixing, and collects product, it is post-treated to obtain DAPER；

(b) by dicarboxylic acids B₂It is mixed with dihydric alcohol with the molar ratio of 1:1, catalyst is added, in nitrogen or inert gas Melt condensation reaction is carried out under conditions of protection and mechanical stirring, obtains DADA；

(c) DAPER is added in the system of step (b), the molar ratio of DAPER and DADA are 1:4, keep the temperature of system It spends constant, is continually fed into nitrogen or inert gas, fusion esterification reaction is carried out under conditions of mechanical stirring, collect product, warp Post-processing obtains cross carboxylate；

In step (a), the inert gas be argon gas, helium or neon, the churned mechanically mixing speed be 50~ 500rpm, the temperature of fusion esterification reaction are 180~200 DEG C, and the reaction time is 1~4h, the post-processing include dissolution, Filtering and drying；

In step (b), the catalyst is 4- toluenesulfonic acid, the B₂Molar ratio with catalyst is 1:0.01, institute Stating inert gas is argon gas, helium or neon, and the churned mechanically mixing speed is 50~500rpm, and the melt condensation is anti- The temperature answered is 180~200 DEG C, and the reaction time is 1~3h；

In step (c), the inert gas be argon gas, helium or neon, the churned mechanically mixing speed be 50~ The time of 500rpm, the fusion esterification reaction are 1~4h, and the post-processing includes crushing, dissolving, being filtered, washed and dried, Wherein, drying refers to 6~18h of vacuum drying at 25~50 DEG C；

A₂And B₂It is independently selected from the following compound of structural formula:

The dihydric alcohol is ethylene glycol, propylene glycol or 1,4- butanediol.

Flame-proof polylactic acid fiber as described above containing metal-modified cross carboxylate, the metal ion are Co²⁺、 Ni²⁺、Cu²⁺Or Zn²⁺, the metal ion is provided by its corresponding mol ratio of metal acetate, in the metal-modified cross carboxylate The content of metal ion is 10~20wt%.In metal-modified cross carboxylate of the invention the content of metal ion include but Be not limited only to this, can adjust in the appropriate range, but should not too, metal ion content is too low will lead to it is obtained metal-modified The functionality of cross carboxylate is poor, and can impact to its insoluble insoluble characteristic.The present invention can be according to modified reality Border demand selects different metal ions, and the present invention only enumerates the feasible metal ion in part, if other metal ions its have Corresponding metal acetate salting liquid is equally applicable to the present invention.

The present invention also provides a kind of flame-proof polylactic acid fibers prepared as described above containing metal-modified cross carboxylate Method, l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are used into melt spinning after mixing The flame-proof polylactic acid fiber containing metal-modified cross carboxylate is made in method, and the l-lactic acid slice and dextrorotation polylactic acid are cut The mass ratio of piece is 1:1, contains modifier A and modifying agent B in the function polylactic acid master batch.

As a preferred technical scheme:

Method as described above, steps are as follows:

(1) l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are dried after mixing Mixture is made, wherein the mass fraction of function polylactic acid master batch is 10~30%, and dry temperature is 110~125 DEG C, when Between be 13~16h；

(2) mixture is melted, measure pump-metered, spinneret extrusion, winding, molding, boundling, drawing-off, thermal finalization, Obtain the flame-proof polylactic acid fiber containing metal-modified cross carboxylate after curling and cutting, wherein metering pump for amount for 780~ 1000g/min, the temperature that spinneret squeezes out are 225~260 DEG C, and the speed that spinneret squeezes out is 980~1100m/min, drawing-off Multiple be 3.1~3.6 times.

Method as described above, the function polylactic acid master batch is by the polylactic acid powder of 63~83wt%, 5~15wt% The auxiliary material composition of colorant, the modifying agent B of 10~30wt%, the modifier A of 1~3wt% and 1~5wt%, modifying agent B, that is, insoluble Insoluble metal-modified cross carboxylate is able to ascend the fusing point and flame retardant property of fiber, road after colorant can be such that fiber exempts Dyeing, modifier A can be improved the crystal property of polymeric system, further increase the fusing point of polymer, and auxiliary material can Improve processing performance；

The function polylactic acid master batch the preparation method comprises the following steps: by polylactic acid powder, colorant, modifier A, modifying agent B and auxiliary Material is made after being uniformly mixed through melt blending, extrusion, cooling, tie rod, pelletizing and drying, and the temperature of melt blending is 150~180 ℃；

The polylactic acid powder is ground after being mixed by l-lactic acid slice and dextrorotation polylactic acid slice by the mass ratio of 1:1 It is made；

The colorant is C.I. Pigment white 6, white 18:1, C.I paratonere 101 of C.I. face, C.I pigment red 4 9:1, C.I pigment Red 68, C.I pigment yellow 32, C.I. pigment yellow 16, C.I. pigment black 11, C.I. pigment black 15, C.I. solvent yellow 19, C.I. pigment It is orange 24, C.I pigment violet 3, C.I. pigment blue 10, phthalocyanine blue b, C.I. pigment blue 29, C.I pigment blue 1 7:1, C.I naphthol green 8, resistance to Shine one or more of emerald green color lake, environmentally-friecarbon carbon black FR8150 and environmentally-friecarbon carbon black FR5200；

The auxiliary material is the mixture of polyethylene wax and nanometer calcium carbonate, in mixture the content of polyethylene wax be 40~ 60wt%.

The preparation step of method as described above, the modifying agent B is as follows:

(1) cross carboxylate and mol ratio of metal acetate are dissolved in organic solvent II and deionized water respectively and obtain cross Type carboxylate solution and metal acetate salting liquid；After metal acetate salting liquid is added dropwise in cross carboxylate solution, metal from Son can be reacted with the carboxyl end group of cross carboxylate rapidly, and then under the conditions of sonic oscillation, metal ion enters metal Inside modified cross carboxylate, oxygen atom and metal ion in cross carboxylate intramolecule double bond are connected by coordinate bond It connects；

(2) in stirring and under the conditions of sonic oscillation, by metal acetate salting liquid be added drop-wise in cross carboxylate solution into Row reaction obtains suspension；

(3) suspension after reaction is post-processed to obtain modifying agent B；

After metal acetate salting liquid of the invention is added dropwise into cross carboxylate solution, metal ion is simultaneously by acetic acid Metal salt ionizes the electrostatic attraction of the electrostatic attraction for the acetate ion to be formed and the carboxyl end group of cross carboxylate, by In both electrostatic attractions approximation, metal ion will not be rapidly by the carboxyl total overall reaction on cross carboxylate surface, metal Ion is slow release in the whole process, can be deep into the inside of cross carboxylate molecule, with cross carboxylate Oxygen atom in internal double bond establishes more stable coordinate bond, and the metal-modified cross carboxylate because prepared by has not Molten insoluble characteristic；

In step (1), the organic solvent II be chloroform, acetone, n,N-Dimethylformamide or tetrahydrofuran, described ten The concentration of font carboxylate solution is 0.7~1.25mol/L, and the concentration of the metal acetate salting liquid is 0.1~0.3mol/L；

In step (2), the stirring is mechanical stirring or magnetic agitation, and the rate of stirring is 50~500rpm, described super The power of sound oscillation is 600~1200W, and the power of sonic oscillation of the invention includes but are not limited to this, can be in proper range Interior adjustment, but should not too, the power of sonic oscillation is higher, and obtained metal-modified cross carboxylate structure is more uniform, mistake Low power, which may result in, cannot form enough coordination structures；

The speed of the dropwise addition is 0.5~2 drop/sec, and the volume of every drop is 0.05~0.1mL, reactant after completion of dropwise addition The molar ratio of cross carboxylate and metal ion is 1:2~9 in system；Cross carboxylate and metal ion rubs in the present invention You include but are not limited to this by ratio, can adjust in the appropriate range, but should not too, the additive amount of metal ion is too low to be unable to shape At enough coordination structures, it is impacted to will lead to the insoluble insoluble property of the cross carboxylate of to be formed metal-modified；

In step (3), the post-processing, which refers to, to be filtered, washed and dried, wherein drying is to carry out under vacuum conditions , vacuum degree is -0.1MPa, and drying time is 8~12h, and drying temperature is 25 DEG C.

Invention mechanism:

After metal salt ionizes in aqueous solution, there is interactions for interionic, and cation is by anion around it Electrostatic attraction, the anion also electrostatic attraction by surrounding cation.Ion by with xenogenesis charge from It, will also be by the mutual expelling force of the ion with like charges while sub mutually attraction.Therefore, the behavior of ion in the solution is not Be it is entirely free on his, metal ion solution (metal acetate salting liquid) concentration is bigger, and interionic interaction force is stronger.And ten Font carboxylate can be swollen in organic solvent II, when to be slowly dropped to cross carboxylate molten for metal acetate salting liquid When in liquid, metal ion may be loaded in two forms on cross carboxylate: (1) the cross carboxylate surface after being swollen The acidic-groups such as-COOH can dissociate H⁺, then it is keyed with metal ion by ion；(2) cross carboxylate structure Oxygen and metal ion on internal carbonyl and/or other double bonds pass through coordination key connection.

After metal acetate salting liquid is added drop-wise to cross carboxylate solution by the present invention, due to acetate ion to metal from The electrostatic attraction of son is approximate with carboxyl, therefore metal ion will not be complete by the carboxyl on the cross carboxylate surface of swelling rapidly Portion's reaction forms the structure of one " outer close interior thin " (i.e. surface engagement is intensive, and internal engagement is sparse), in ultrasonic concussion condition of shaking Under, a part of metal ion can enter from the gap on the cross carboxylate surface being keyed with metal ion by ion In the internal structure of cross carboxylate after swelling, and it is abundant with the carbonyl of cross carboxylate inside configuration or other double bonds It is coordination cross-linked, uniform cross-linked structure is formed, so that metal-modified cross carboxylate obtained is with insoluble insoluble Property avoids the defect that general electrification complex ion complex is soluble in organic solvent, solves functional cross esterification Object solubility when processing is blended is excessively high and lower melting-point problem.

After the present invention is by being prepared function polylactic acid master batch using insoluble insoluble metal-modified cross carboxylate Then function polylactic acid master batch and l-lactic acid are sliced and dextrorotation polylactic acid slice are mixed with acid fiber by polylactic, wherein Metal-modified cross carboxylate can play the role of nucleating agent as hybrid inorganic-organic materials in polylactic acid matrix, It can be improved the crystallinity of polylactic acid and then improve the fusing point of polylactic acid；Metal-modified cross carboxylate is rich in metal ion, It can also can be cooperateed with simultaneously individually or with ignition-proof elements such as P, N containing the ignition-proof elements such as P, N, metal ion and play change polymerization Object burning, the effect of the physics in pyroprocess, chemical change achieve the purpose that hinder mass transfer, heat transfer, and then improve polylactic acid Flame retardant property.

The utility model has the advantages that

(1) preparation method of the flame-proof polylactic acid fiber of the invention containing metal-modified cross carboxylate, it is simple and easy, At low cost, insoluble insoluble metal-modified cross carboxylate obtained, which has to be insoluble in common organic solvents and heat, not to be melted The characteristics of, with other polymers be blended process when approximate can be considered as inorganic particle, do not lose its it is functional under the premise of, subtract The small influence to blend rheological property, it is ensured that the rheological behavior of blend is conducive to product machine-shaping；

(2) the flame-proof polylactic acid fiber of the invention containing metal-modified cross carboxylate, acid fiber by polylactic obtained are molten Point is high and has excellent flame retardant property.

Specific embodiment

The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Fixed range.

In formula (I),The segment between the quaternary carbon C and carboxyl end group of cross carboxylate molecular center is represented,In contain There is the double bond with oxygen atom.

Embodiment 1

A kind of preparation method of the flame-proof polylactic acid fiber containing metal-modified cross carboxylate, the specific steps are as follows:

(1) cross carboxylate is prepared；

(a) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is 300rpm in nitrogen protection and mixing speed Mechanical stirring under conditions of carry out fusion esterification reaction, collect product, through dissolution, DAPER is filtered and is dried to obtain, wherein melting The temperature for melting esterification is 200 DEG C, reaction time 3h, A₂Structural formula are as follows:

(b) by dicarboxylic acids B₂It is mixed with ethylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, in nitrogen protection With mixing speed to carry out melt condensation reaction under conditions of the mechanical stirring of 500rpm, DADA is obtained, wherein B₂With 4- methyl The molar ratio of benzene sulfonic acid is 1:0.01, and the temperature of melt condensation reaction is 180 DEG C, reaction time 2.5h, B₂Structural formula are as follows:

(c) DAPER is added in the system of step (b), the molar ratio of DAPER and DADA are 1:4, keep the temperature of system It spends constant, is continually fed into neon, carries out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 500rpm, collect Product through crushing, dissolves, is filtered, washed and dried to obtain cross carboxylate, and wherein the time of fusion esterification reaction is 1h, It is dry to refer to the vacuum drying 11h in 30 DEG C of vacuum drying oven, shown in the structural formula such as formula (I) of cross carboxylate obtained；

(2) cross carboxylate is dissolved in the cross carboxylate solution for obtaining that concentration is 0.7mol/L in chloroform, it will Cobalt acetate dissolution obtains the cobalt acetate solution that concentration is 0.1mol/L in deionized water；

(3) under the conditions of stirring and sonic oscillation, cobalt acetate solution is added drop-wise in cross carboxylate solution and is carried out instead Should obtain suspension, wherein the rate of stirring is 350rpm, and the power of sonic oscillation is 800W, the speed of dropwise addition be 0.5 drop/ Second, the volume of every drop is 0.07mL, cross carboxylate and Co in reaction system after completion of dropwise addition²⁺Molar ratio be 1:2；

(4) insoluble insoluble metal-modified cross is filtered, washs and is dried to obtain to suspension after reaction Type carboxylate, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 11h, drying temperature It is 25 DEG C；

Co in final metal-modified cross carboxylate obtained²⁺Content be 11wt%.It is insoluble insoluble metal-modified Cross carboxylate is cross carboxylate and Co²⁺It is former by the oxygen in cross carboxylate intramolecule C=O and P=O double bond Son and Co²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Co²⁺It is even formed by ionic bond Network polymer, have insoluble insoluble characteristic, 80 DEG C or less do not dissolve in organic solvent I, organic solvent I include benzene, first Benzene, dimethylbenzene, styrene, butyl toluene, vinyltoluene, n-hexane, pentane, hexane, octane, hexamethylene, cyclohexanone, toluene Cyclohexanone, chlorobenzene, dichloro-benzenes, methylene chloride, chloroform, carbon tetrachloride, trichloro ethylene, tetrachloro-ethylene, trichloropropane, two chloroethenes Alkane, methanol, ethyl alcohol, isopropanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, methyl acetate, ethyl acetate, acetic acid Propyl ester, acetone, espeleton, methylisobutylketone, cyclohexanone, toluene cyclohexanone, acetonitrile, pyridine, phenol, N, N- dimethyl formyl Amine and n,N-dimethylacetamide, in room temperature to not melting within the scope of 380 DEG C, metal-modified cross carboxylate is aerial Initial decomposition temperature is 340 DEG C, and partial size when being dispersed in PET is 40~50nm；

(5) function polylactic acid master batch is prepared；

(5.1) function polylactic acid master batch each component is prepared；

(5.1.1) grinds after mixing l-lactic acid slice and dextrorotation polylactic acid slice by the mass ratio of 1:1 and is made poly- Lactic acid powder；

Aluminum benzoate, hydrated magnesium silicate and silica are mixed to get modifier A by the mass ratio of 2:1:1 by (5.1.2)；

Polyethylene wax and nanometer calcium carbonate 60:40 in mass ratio are mixed to prepare auxiliary material by (5.1.3)；

(5.2) by polylactic acid powder, C.I. Pigment white 6, insoluble insoluble metal-modified cross carboxylate, modifier A With auxiliary material after mixing first through 170 DEG C of temperature melt blending again through extrusion, cooling, tie rod, pelletizing and dry obtained function Polylactic acid master batch, each component content in function polylactic acid master batch are as follows: the C.I. Pigment white of the polylactic acid powder of 70wt%, 10wt% 6, the insoluble insoluble metal-modified cross carboxylate of 15wt%, the modifier A of 3wt% and the auxiliary material of 2wt%；

(6) the flame-proof polylactic acid fiber containing metal-modified cross carboxylate is prepared；

(6.1) l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are done after mixing Dry obtained mixture, wherein dry temperature is 115 DEG C, time 15h, l-lactic acid slice and dextrorotation polylactic acid slice Mass ratio be 1:1, the mass fraction of function polylactic acid master batch is 20% in mixture；

(6.2) mixture melted, measure pump-metered, spinneret extrusion, winding, molding, boundling, drawing-off, heat calmly The flame-proof polylactic acid fiber containing metal-modified cross carboxylate is obtained after type, curling and cutting, wherein metering pump for amount be 900g/min, the temperature that spinneret squeezes out are 250 DEG C, and the speed that spinneret squeezes out is 1000m/min, and the multiple of drawing-off is 3.4 Times.

The filament number of flame-proof polylactic acid fiber obtained containing metal-modified cross carboxylate is 3.4dtex, fracture Intensity is 4.1cN/dtex, and elongation at break 50%, line density deviation ratio is -6.0%.

The fusing point of flame-proof polylactic acid fiber containing metal-modified cross carboxylate is 205 DEG C, phosphorus content 7500ppm, Limit oxygen index is that 36%, UL-94 reaches V-0 grades.

Embodiment 2

(1) cross carboxylate is prepared；

(a) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is 350rpm in argon gas protection and mixing speed Mechanical stirring under conditions of carry out fusion esterification reaction, collect product, through dissolution, DAPER is filtered and is dried to obtain, wherein melting The temperature for melting esterification is 185 DEG C, reaction time 1h, A₂Structural formula are as follows:

(b) by dicarboxylic acids B₂It is mixed with propylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, in nitrogen protection With mixing speed to carry out melt condensation reaction under conditions of the mechanical stirring of 300rpm, DADA is obtained, wherein B₂With 4- methyl The molar ratio of benzene sulfonic acid is 1:0.01, and the temperature of melt condensation reaction is 185 DEG C, reaction time 1h, B₂Structural formula are as follows:

(c) DAPER is added in the system of step (b), the molar ratio of DAPER and DADA are 1:4, keep the temperature of system It spends constant, is continually fed into nitrogen, carries out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 450rpm, collect Product through crushing, dissolves, is filtered, washed and dried to obtain cross carboxylate, wherein the time of fusion esterification reaction be 3.5h, drying refer to the vacuum drying 8h in 25 DEG C of vacuum drying oven, structural formula such as formula (I) institute of cross carboxylate obtained Show；

(2) dissolution of cross carboxylate is obtained into the cross carboxylate solution that concentration is 1.25mol/L in acetone, it will Nickel acetate dissolution obtains the nickel acetate solution that concentration is 0.2mol/L in deionized water；

(3) under the conditions of stirring and sonic oscillation, nickel acetate solution is added drop-wise in cross carboxylate solution and is carried out instead Should obtain suspension, wherein the rate of stirring is 280rpm, and the power of sonic oscillation is 700W, the speed of dropwise addition be 0.5 drop/ Second, the volume of every drop is 0.06mL, cross carboxylate and Ni in reaction system after completion of dropwise addition²⁺Molar ratio be 1:5；

(4) insoluble insoluble metal-modified cross is filtered, washs and is dried to obtain to suspension after reaction Type carboxylate, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 9h, and drying temperature is 25℃；

Ni in final metal-modified cross carboxylate obtained²⁺Content be 15wt%.It is insoluble insoluble metal-modified Cross carboxylate is cross carboxylate and Ni²⁺Pass through the oxygen atom and Ni of cross carboxylate intramolecule C=O double bond²⁺ Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Ni²⁺The network even formed by ionic bond Polymer has insoluble insoluble characteristic, does not dissolve in organic solvent I, the specific type of organic solvent I and embodiment at 80 DEG C or less 1 is consistent, and in room temperature to not melting within the scope of 395 DEG C, the metal-modified cross aerial initial decomposition temperature of carboxylate is 388 DEG C, partial size when being dispersed in PBT is 80~120nm；

(5) function polylactic acid master batch is prepared；

(5.1) function polylactic acid master batch each component is prepared；

Polyethylene wax and nanometer calcium carbonate 40:60 in mass ratio are mixed to prepare auxiliary material by (5.1.3)；

(5.2) by polylactic acid powder, the white 18:1 of C.I. face, insoluble insoluble metal-modified cross carboxylate, modifier A With auxiliary material after mixing first through 150 DEG C of temperature melt blending again through extrusion, cooling, tie rod, pelletizing and dry obtained function Polylactic acid master batch, each component content in function polylactic acid master batch are as follows: the C.I. face white 18 of the polylactic acid powder of 83wt%, 5wt%: 1, the insoluble insoluble metal-modified cross carboxylate of 10wt%, the modifier A of 1wt% and the auxiliary material of 1wt%；

(6.1) l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are done after mixing Dry obtained mixture, wherein dry temperature is 110 DEG C, time 13h, l-lactic acid slice and dextrorotation polylactic acid slice Mass ratio be 1:1, the mass fraction of function polylactic acid master batch is 10% in mixture；

(6.2) mixture melted, measure pump-metered, spinneret extrusion, winding, molding, boundling, drawing-off, heat calmly The flame-proof polylactic acid fiber containing metal-modified cross carboxylate is obtained after type, curling and cutting, wherein metering pump for amount be 780g/min, the temperature that spinneret squeezes out are 225 DEG C, and the speed that spinneret squeezes out is 980m/min, and the multiple of drawing-off is 3.1 Times.

The filament number of flame-proof polylactic acid fiber obtained containing metal-modified cross carboxylate is 3.0dtex, fracture Intensity is 3.70cN/dtex, and elongation at break 45%, line density deviation ratio is -8.0%.

The fusing point of flame-proof polylactic acid fiber containing metal-modified cross carboxylate is 200 DEG C, limit oxygen index 30, UL-94 reaches V-0 grades.

Embodiment 3

(1) cross carboxylate is prepared；

(a) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is 400rpm in helium protection and mixing speed Mechanical stirring under conditions of carry out fusion esterification reaction, collect product, through dissolution, DAPER is filtered and is dried to obtain, wherein melting The temperature for melting esterification is 180 DEG C, reaction time 2h, A₂Structural formula are as follows:

(b) by dicarboxylic acids B₂It is mixed with 1,4-butanediol with the molar ratio of 1:1,4- toluenesulfonic acid is added, in argon gas Melt condensation reaction is carried out under conditions of the mechanical stirring that protection and mixing speed are 500rpm, obtains DADA, wherein B₂With 4- The molar ratio of toluenesulfonic acid is 1:0.01, and the temperature of melt condensation reaction is 180 DEG C, reaction time 1h, B₂Structural formula Are as follows:

(c) DAPER is added in the system of step (b), the molar ratio of DAPER and DADA are 1:4, keep the temperature of system It spends constant, is continually fed into neon, carries out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 330rpm, collect Product through crushing, dissolves, is filtered, washed and dried to obtain cross carboxylate, wherein the time of fusion esterification reaction be 1.5h, drying refer to the vacuum drying 8h in 50 DEG C of vacuum drying oven, structural formula such as formula (I) institute of cross carboxylate obtained Show；

(2) being dissolved in cross carboxylate and obtaining concentration in N,N-dimethylformamide is the cross of 1.05mol/L Copper acetate dissolution is obtained the acetic acid copper solution that concentration is 0.15mol/L by carboxylate solution in deionized water；

(3) under the conditions of stirring and sonic oscillation, acetic acid copper solution is added drop-wise in cross carboxylate solution and is carried out instead It should obtain suspension, wherein the rate of stirring is 200pm, and the power of sonic oscillation is 600W, and the speed of dropwise addition is 2 drops/sec, The volume of every drop is 0.05mL, cross carboxylate and Cu in reaction system after completion of dropwise addition²⁺Molar ratio be 1:8；

(4) insoluble insoluble metal-modified cross is filtered, washs and is dried to obtain to suspension after reaction Type carboxylate, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 10h, drying temperature It is 25 DEG C.

Cu in final metal-modified cross carboxylate obtained²⁺Content be 20wt%.It is insoluble insoluble metal-modified Cross carboxylate is cross carboxylate and Cu²⁺By in cross carboxylate intramolecule C=O double bond and P=O double bond Oxygen atom and Cu²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Cu²⁺Connected by ionic bond The network polymer of formation has insoluble insoluble characteristic, at 80 DEG C or less insoluble in organic solvent I, I specific kind of organic solvent Class and embodiment 1 are consistent, in room temperature to not melting within the scope of 380 DEG C, the metal-modified cross aerial starting of carboxylate Decomposition temperature is 360 DEG C, and partial size when being dispersed in PP is 400~500nm；

(5) function polylactic acid master batch is prepared；

(5.1) function polylactic acid master batch each component is prepared；

Polyethylene wax and nanometer calcium carbonate 50:50 in mass ratio are mixed to prepare auxiliary material by (5.1.3)；

(5.2) by polylactic acid powder, C.I paratonere 101, insoluble insoluble metal-modified cross carboxylate, modifier A With auxiliary material after mixing first through 160 DEG C of temperature melt blending again through extrusion, cooling, tie rod, pelletizing and dry obtained function Polylactic acid master batch, each component content in function polylactic acid master batch are as follows: the C.I paratonere of the polylactic acid powder of 63wt%, 5wt% 101, the insoluble insoluble metal-modified cross carboxylate of 30wt%, the modifier A of 1wt% and the auxiliary material of 1wt%；

(6.1) l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are done after mixing Dry obtained mixture, wherein dry temperature is 125 DEG C, time 16h, l-lactic acid slice and dextrorotation polylactic acid slice Mass ratio be 1:1, the mass fraction of function polylactic acid master batch is 30% in mixture；

(6.2) mixture melted, measure pump-metered, spinneret extrusion, winding, molding, boundling, drawing-off, heat calmly The flame-proof polylactic acid fiber containing metal-modified cross carboxylate is obtained after type, curling and cutting, wherein metering pump for amount be 1000g/min, the temperature that spinneret squeezes out are 260 DEG C, and the speed that spinneret squeezes out is 1100m/min, and the multiple of drawing-off is 3.6 Times.

The filament number of flame-proof polylactic acid fiber obtained containing metal-modified cross carboxylate is 4.4dtex, fracture Intensity is 4.50cN/dtex, and elongation at break 55%, line density deviation ratio is 5.5%.

The fusing point of flame-proof polylactic acid fiber containing metal-modified cross carboxylate is 210 DEG C, phosphorus content 7600ppm, Limit oxygen index is that 38%, UL-94 reaches V-0 grades.

Embodiment 4

(1) cross carboxylate is prepared；

(a) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is 450rpm in neon protection and mixing speed Mechanical stirring under conditions of carry out fusion esterification reaction, collect product, through dissolution, DAPER is filtered and is dried to obtain, wherein melting The temperature for melting esterification is 195 DEG C, reaction time 4h, A₂Structural formula are as follows:

(b) by dicarboxylic acids B₂It is mixed with propylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, protected in helium With mixing speed to carry out melt condensation reaction under conditions of the mechanical stirring of 300rpm, DADA is obtained, wherein B₂With 4- methyl The molar ratio of benzene sulfonic acid is 1:0.01, and the temperature of melt condensation reaction is 200 DEG C, reaction time 3h, B₂Structural formula are as follows:

(c) DAPER is added in the system of step (b), the molar ratio of DAPER and DADA are 1:4, keep the temperature of system It spends constant, is continually fed into nitrogen, carries out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 500rpm, collect Product through crushing, dissolves, is filtered, washed and dried to obtain cross carboxylate, and wherein the time of fusion esterification reaction is 4h, It is dry to refer to the vacuum drying 6h in 35 DEG C of vacuum drying oven, shown in the structural formula such as formula (I) of cross carboxylate obtained；

(2) cross carboxylate is dissolved in obtained in tetrahydrofuran concentration be 0.8mol/L cross carboxylate it is molten Zinc acetate dissolution is obtained the zinc acetate solution that concentration is 0.3mol/L by liquid in deionized water；

(3) under the conditions of stirring and sonic oscillation, zinc acetate solution, which is added drop-wise in cross carboxylate solution, to be reacted Obtaining suspension, wherein the rate of stirring is 250rpm, and the power of sonic oscillation is 1000W, and the speed of dropwise addition is 1 drop/sec, The volume of every drop is 0.05mL, cross carboxylate and Zn in reaction system after completion of dropwise addition²⁺Molar ratio be 1；9；

(4) insoluble insoluble metal-modified cross is filtered, washs and is dried to obtain to suspension after reaction Type carboxylate, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 12h, drying temperature It is 25 DEG C.

Zn in final metal-modified cross carboxylate obtained²⁺Content be 16wt%.It is insoluble insoluble metal-modified Cross carboxylate is cross carboxylate and Zn²⁺By in cross carboxylate intramolecule C=O double bond and P=O double bond Oxygen atom and Zn²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Zn²⁺Connected by ionic bond The network polymer of formation has insoluble insoluble characteristic, at 80 DEG C or less insoluble in organic solvent I, I specific kind of organic solvent Class and embodiment 1 are consistent, in room temperature to not melting within the scope of 390 DEG C, the metal-modified cross aerial starting of carboxylate Decomposition temperature is 371 DEG C, and partial size when being dispersed in PP is 460~500nm；

(5) function polylactic acid master batch is prepared；

(5.1) function polylactic acid master batch each component is prepared；

Polyethylene wax and nanometer calcium carbonate 55:45 in mass ratio are mixed to prepare auxiliary material by (5.1.3)；

(5.2) by polylactic acid powder, colorant (C.I pigment red 4 9:1), insoluble insoluble metal-modified cross carboxylate, Modifier A and auxiliary material are after mixing first through 180 DEG C of temperature melt blending again through extrusion, cooling, tie rod, pelletizing and dry system Function polylactic acid master batch, each component content in function polylactic acid master batch are as follows: the color of the polylactic acid powder of 67wt%, 10wt% Material, the insoluble insoluble metal-modified cross carboxylate of 15wt%, the modifier A of 3wt% and the auxiliary material of 5wt%；

(6.1) l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are done after mixing Dry obtained mixture, wherein dry temperature is 115 DEG C, time 14h, l-lactic acid slice and dextrorotation polylactic acid slice Mass ratio be 1:1, the mass fraction of function polylactic acid master batch is 20% in mixture；

(6.2) mixture melted, measure pump-metered, spinneret extrusion, winding, molding, boundling, drawing-off, heat calmly The flame-proof polylactic acid fiber containing metal-modified cross carboxylate is obtained after type, curling and cutting, wherein metering pump for amount be 900g/min, the temperature that spinneret squeezes out are 240 DEG C, and the speed that spinneret squeezes out is 1100m/min, and the multiple of drawing-off is 3.3 Times.

The filament number of flame-proof polylactic acid fiber obtained containing metal-modified cross carboxylate is 3.4dtex, fracture Intensity is 4.10cN/dtex, and elongation at break 48%, line density deviation ratio is 6.5%.

The fusing point of flame-proof polylactic acid fiber containing metal-modified cross carboxylate is 204 DEG C, phosphorus content 7000ppm, Limit oxygen index is that 35%, UL-94 reaches V-0 grades.

Embodiment 5

(1) cross carboxylate is prepared；

(a) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is 500rpm in nitrogen protection and mixing speed Mechanical stirring under conditions of carry out fusion esterification reaction, collect product, through dissolution, DAPER is filtered and is dried to obtain, wherein melting The temperature for melting esterification is 180 DEG C, reaction time 1.5h, A₂Structural formula are as follows:

(b) by dicarboxylic acids B₂It is mixed with 1,4-butanediol with the molar ratio of 1:1,4- toluenesulfonic acid is added, in neon Melt condensation reaction is carried out under conditions of the mechanical stirring that protection and mixing speed are 500rpm, obtains DADA, wherein B₂With 4- The molar ratio of toluenesulfonic acid is 1:0.01, and the temperature of melt condensation reaction is 195 DEG C, reaction time 3h, B₂Structural formula Are as follows:

(c) DAPER is added in the system of step (b), the molar ratio of DAPER and DADA are 1:4, keep the temperature of system It spends constant, is continually fed into argon gas, carries out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 340rpm, collect Product through crushing, dissolves, is filtered, washed and dried to obtain cross carboxylate, and wherein the time of fusion esterification reaction is 3h, It is dry to refer to the vacuum drying 15h in 30 DEG C of vacuum drying oven, shown in the structural formula such as formula (I) of cross carboxylate obtained；

(2) cross carboxylate is dissolved in the cross carboxylate solution for obtaining that concentration is 1.0mol/L in chloroform, it will Cobalt acetate dissolution obtains the cobalt acetate solution that concentration is 0.1mol/L in deionized water；

(3) under the conditions of stirring and sonic oscillation, cobalt acetate solution is added drop-wise in cross carboxylate solution and is carried out instead Should obtain suspension, wherein the rate of stirring is 300rpm, and the power of sonic oscillation is 1200W, the speed of dropwise addition be 1.5 drops/ Second, the volume of every drop is 0.09mL, cross carboxylate and Co in reaction system after completion of dropwise addition²⁺Molar ratio be 1:2；

(4) insoluble insoluble metal-modified cross is filtered, washs and is dried to obtain to suspension after reaction Type carboxylate, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 8h, and drying temperature is 25℃。

Co in final metal-modified cross carboxylate obtained²⁺Content be 11wt%.It is insoluble insoluble metal-modified Cross carboxylate is cross carboxylate and Co²⁺By in cross carboxylate intramolecule C=O double bond and P=O double bond Oxygen atom and Co²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Co²⁺Connected by ionic bond The network polymer of formation has insoluble insoluble characteristic, at 80 DEG C or less insoluble in organic solvent I, I specific kind of organic solvent Class and embodiment 1 are consistent, in room temperature to not melting within the scope of 380 DEG C, the metal-modified cross aerial starting of carboxylate Decomposition temperature is 300 DEG C, and partial size when being dispersed in PP is 240~300nm；

(5) function polylactic acid master batch is prepared；

(5.1) function polylactic acid master batch each component is prepared；

Polyethylene wax and nanometer calcium carbonate 45:55 in mass ratio are mixed to prepare auxiliary material by (5.1.3)；

C.I. Pigment white 6 and the white 18:1 of C.I. face 1:1 in mass ratio are mixed to prepare colorant by (5.1.4)；

(5.2) polylactic acid powder, colorant, insoluble insoluble metal-modified cross carboxylate, modifier A and auxiliary material are mixed First the temperature melt blending through 170 DEG C is female through extrusion, cooling, tie rod, pelletizing and dry obtained function polylactic acid again after closing uniformly , each component content in function polylactic acid master batch are as follows: the polylactic acid powder of 65wt%, the colorant of 15wt%, 14wt% are insoluble not Molten metal-modified cross carboxylate, the modifier A of 2wt% and the auxiliary material of 4wt%；

(6.2) mixture melted, measure pump-metered, spinneret extrusion, winding, molding, boundling, drawing-off, heat calmly The flame-proof polylactic acid fiber containing metal-modified cross carboxylate is obtained after type, curling and cutting, wherein metering pump for amount be 800g/min, the temperature that spinneret squeezes out are 240 DEG C, and the speed that spinneret squeezes out is 1000m/min, and the multiple of drawing-off is 3.3 Times.

The filament number of flame-proof polylactic acid fiber obtained containing metal-modified cross carboxylate is 3.3dtex, fracture Intensity is 4.0cN/dtex, and elongation at break 48%, line density deviation ratio is 6.3%.

The fusing point of flame-proof polylactic acid fiber containing metal-modified cross carboxylate is 205 DEG C, phosphorus content 6800ppm, Limit oxygen index is that 32%, UL-94 reaches V-0 grades.

Embodiment 6

(1) cross carboxylate is prepared；

(a) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is 50rpm in helium protection and mixing speed Mechanical stirring under conditions of carry out fusion esterification reaction, collect product, through dissolution, DAPER is filtered and is dried to obtain, wherein melting The temperature for melting esterification is 190 DEG C, reaction time 2.5h, A₂Structural formula are as follows:

(b) by dicarboxylic acids B₂It is mixed with ethylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, in nitrogen protection With mixing speed to carry out melt condensation reaction under conditions of the mechanical stirring of 50rpm, DADA is obtained, wherein B₂With 4- methylbenzene The molar ratio of sulfonic acid is 1:0.01, and the temperature of melt condensation reaction is 190 DEG C, reaction time 1h, B₂Structural formula are as follows:

(c) DAPER is added in the system of step (b), the molar ratio of DAPER and DADA are 1:4, keep the temperature of system It spends constant, is continually fed into nitrogen, carries out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 50rpm, collect Product through crushing, dissolves, is filtered, washed and dried to obtain cross carboxylate, wherein the time of fusion esterification reaction be 2.5h, drying refer to the vacuum drying 18h in 45 DEG C of vacuum drying oven, the structural formula such as formula (I) of cross carboxylate obtained It is shown；

(2) dissolution of cross carboxylate is obtained into the cross carboxylate solution that concentration is 0.75mol/L in acetone, it will Nickel acetate dissolution obtains the nickel acetate solution that concentration is 0.2mol/L in deionized water；

(3) under the conditions of stirring and sonic oscillation, nickel acetate solution is added drop-wise in cross carboxylate solution and is carried out instead It should obtain suspension, wherein the rate of stirring is 50rpm, and the power of sonic oscillation is 1100W, and the speed of dropwise addition is 1 drop/sec, The volume of every drop is 0.08mL, cross carboxylate and Ni in reaction system after completion of dropwise addition²⁺Molar ratio be 1:3；

(4) insoluble insoluble metal-modified cross is filtered, washs and is dried to obtain to suspension after reaction Type carboxylate, wherein drying carries out under vacuum conditions, vacuum degree is -0.1MPa, drying time 9h, and drying temperature is 25℃。

Ni in final metal-modified cross carboxylate obtained²⁺Content be 10wt%.It is insoluble insoluble metal-modified Cross carboxylate is cross carboxylate and Ni²⁺By oxygen atom in cross carboxylate intramolecule C=O double bond with Ni²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Ni²⁺The net even formed by ionic bond Network polymer has insoluble insoluble characteristic, and organic solvent I, the specific type of organic solvent I and implementation are not dissolved at 80 DEG C or less Example 1 is consistent, in room temperature to not melting within the scope of 390 DEG C, the metal-modified cross aerial initial decomposition temperature of carboxylate It is 330 DEG C, partial size when being dispersed in PP is 355~420nm；

(5) function polylactic acid master batch is prepared；

(5.1) function polylactic acid master batch each component is prepared；

C.I paratonere 101,68 1:1:1 in mass ratio of C.I pigment red 4 9:1 and C.I paratonere are mixed to prepare by (5.1.4) Colorant；

(5.2) polylactic acid powder, colorant, insoluble insoluble metal-modified cross carboxylate, modifier A and auxiliary material are mixed First the temperature melt blending through 180 DEG C is female through extrusion, cooling, tie rod, pelletizing and dry obtained function polylactic acid again after closing uniformly , each component content in function polylactic acid master batch are as follows: the polylactic acid powder of 72wt%, the colorant of 7wt%, 17wt% are insoluble not to be melted Metal-modified cross carboxylate, the modifier A of 2wt% and the auxiliary material of 2wt%；

(6.1) l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are done after mixing Dry obtained mixture, wherein dry temperature is 120 DEG C, time 16h, l-lactic acid slice and dextrorotation polylactic acid slice Mass ratio be 1:1, the mass fraction of function polylactic acid master batch is 16% in mixture；

(6.2) mixture melted, measure pump-metered, spinneret extrusion, winding, molding, boundling, drawing-off, heat calmly The flame-proof polylactic acid fiber containing metal-modified cross carboxylate is obtained after type, curling and cutting, wherein metering pump for amount be 900g/min, the temperature that spinneret squeezes out are 260 DEG C, and the speed that spinneret squeezes out is 1000m/min, and the multiple of drawing-off is 3.3 Times.

The filament number of flame-proof polylactic acid fiber obtained containing metal-modified cross carboxylate is 3.4dtex, fracture Intensity is 4.10cN/dtex, and elongation at break 49.8%, line density deviation ratio is 8.0%.

The fusing point of flame-proof polylactic acid fiber containing metal-modified cross carboxylate is 205 DEG C, limit oxygen index 35%, UL-94 reaches V-0 grades.

Embodiment 7

(1) cross carboxylate is prepared；

(a) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is 350rpm in nitrogen protection and mixing speed Mechanical stirring under conditions of carry out fusion esterification reaction, collect product, through dissolution, DAPER is filtered and is dried to obtain, wherein melting The temperature for melting esterification is 200 DEG C, reaction time 3.5h, A₂Structural formula are as follows:

(b) by dicarboxylic acids B₂It is mixed with ethylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, protected in argon gas With mixing speed to carry out melt condensation reaction under conditions of the mechanical stirring of 400rpm, DADA is obtained, wherein B₂With 4- methyl The molar ratio of benzene sulfonic acid is 1:0.01, and the temperature of melt condensation reaction is 200 DEG C, reaction time 1.5h, B₂Structural formula are as follows:

(c) DAPER is added in the system of step (b), the molar ratio of DAPER and DADA are 1:4, keep the temperature of system It spends constant, is continually fed into helium, carries out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 370rpm, collect Product through crushing, dissolves, is filtered, washed and dried to obtain cross carboxylate, and wherein the time of fusion esterification reaction is 1h, It is dry to refer to the vacuum drying 14h in 40 DEG C of vacuum drying oven, shown in the structural formula such as formula (I) of cross carboxylate obtained；

(2) cross carboxylate is dissolved in the cross ester for obtaining that concentration is 0.9mol/L in N,N-dimethylformamide Copper acetate dissolution is obtained the acetic acid copper solution that concentration is 0.2mol/L by compound solution in deionized water；

(3) under the conditions of stirring and sonic oscillation, acetic acid copper solution is added drop-wise in cross carboxylate solution and is carried out instead It should obtain suspension, wherein the rate of stirring is 400rpm, and the power of sonic oscillation is 600W, and the speed of dropwise addition is 2 drops/sec, The volume of every drop is 0.1mL, cross carboxylate and Cu in reaction system after completion of dropwise addition²⁺Molar ratio be 1:9；

Cu in final metal-modified cross carboxylate obtained²⁺Content be 16wt%.It is insoluble insoluble metal-modified Cross carboxylate is cross carboxylate and Cu²⁺By oxygen atom in cross carboxylate intramolecule C=O double bond with Cu²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Cu²⁺The net even formed by ionic bond Network polymer has insoluble insoluble characteristic, and organic solvent I, the specific type of organic solvent I and implementation are not dissolved at 80 DEG C or less Example 1 is consistent, in room temperature to not melting within the scope of 385 DEG C, the metal-modified cross aerial initial decomposition temperature of carboxylate It is 400 DEG C, partial size when being dispersed in PET is 50~95nm；

(5) function polylactic acid master batch is prepared；

(5.1) function polylactic acid master batch each component is prepared；

(5.2) by polylactic acid powder, C.I paratonere 68, insoluble insoluble metal-modified cross carboxylate, modifier A With auxiliary material after mixing first through 180 DEG C of temperature melt blending again through extrusion, cooling, tie rod, pelletizing and dry obtained function Polylactic acid master batch, each component content in function polylactic acid master batch are as follows: the C.I paratonere of the polylactic acid powder of 75wt%, 8wt% 68, the insoluble insoluble metal-modified cross carboxylate of 12wt%, the modifier A of 1wt% and the auxiliary material of 4wt%；

(6.1) l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are done after mixing Dry obtained mixture, wherein dry temperature is 120 DEG C, time 14h, l-lactic acid slice and dextrorotation polylactic acid slice Mass ratio be 1:1, the mass fraction of function polylactic acid master batch is 18% in mixture；

(6.2) mixture melted, measure pump-metered, spinneret extrusion, winding, molding, boundling, drawing-off, heat calmly The flame-proof polylactic acid fiber containing metal-modified cross carboxylate is obtained after type, curling and cutting, wherein metering pump for amount be 1000g/min, the temperature that spinneret squeezes out are 250 DEG C, and the speed that spinneret squeezes out is 1000m/min, and the multiple of drawing-off is 3.4 Times.

The filament number of flame-proof polylactic acid fiber obtained containing metal-modified cross carboxylate is 3.5dtex, fracture Intensity is 4.20cN/dtex, and elongation at break 50%, line density deviation ratio is 7.5%.

The fusing point of flame-proof polylactic acid fiber containing metal-modified cross carboxylate is 206 DEG C, limit oxygen index 37%, UL-94 reaches V-0 grades.

Embodiment 8

(1) cross carboxylate is prepared；

(a) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is 380rpm in helium protection and mixing speed Mechanical stirring under conditions of carry out fusion esterification reaction, collect product, through dissolution, DAPER is filtered and is dried to obtain, wherein melting The temperature for melting esterification is 180 DEG C, reaction time 1h, A₂Structural formula are as follows:

(b) by dicarboxylic acids B₂It is mixed with propylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, in nitrogen protection With mixing speed to carry out melt condensation reaction under conditions of the mechanical stirring of 370rpm, DADA is obtained, wherein B₂With 4- methyl The molar ratio of benzene sulfonic acid is 1:0.01, and the temperature of melt condensation reaction is 180 DEG C, reaction time 2.5h, B₂Structural formula are as follows:

(c) DAPER is added in the system of step (b), the molar ratio of DAPER and DADA are 1:4, keep the temperature of system It spends constant, is continually fed into neon, carries out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 350rpm, collect Product through crushing, dissolves, is filtered, washed and dried to obtain cross carboxylate, and wherein the time of fusion esterification reaction is 2h, It is dry to refer to the vacuum drying 10h in 50 DEG C of vacuum drying oven, shown in the structural formula such as formula (I) of cross carboxylate obtained；

(2) cross carboxylate is dissolved in obtained in tetrahydrofuran concentration be 1.25mol/L cross carboxylate it is molten Zinc acetate dissolution is obtained the zinc acetate solution that concentration is 0.1mol/L by liquid in deionized water；

(3) under the conditions of stirring and sonic oscillation, zinc acetate solution is added drop-wise in cross carboxylate solution and is carried out instead Should obtain suspension, wherein the rate of stirring is 500rpm, and the power of sonic oscillation is 1200W, the speed of dropwise addition be 0.5 drop/ Second, the volume of every drop is 0.1mL, cross carboxylate and Zn in reaction system after completion of dropwise addition²⁺Molar ratio be 1:8；

Zn in final metal-modified cross carboxylate obtained²⁺Content be 20wt%.It is insoluble insoluble metal-modified Cross carboxylate is cross carboxylate and Zn²⁺By in cross carboxylate intramolecule C=O double bond and P=O double bond Oxygen atom and Zn²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Zn²⁺Connected by ionic bond The network polymer of formation has insoluble insoluble characteristic, at 80 DEG C or less insoluble in organic solvent I, I specific kind of organic solvent Class and embodiment 1 are consistent, in room temperature to not melting within the scope of 380 DEG C, the metal-modified cross aerial starting of carboxylate Decomposition temperature is 300 DEG C, and partial size when being dispersed in PP is 240~330nm；

(5) function polylactic acid master batch is prepared；

(5.1) function polylactic acid master batch each component is prepared；

(5.2) by polylactic acid powder, C.I pigment yellow 32, insoluble insoluble metal-modified cross carboxylate, modifier A With auxiliary material after mixing first through 150 DEG C of temperature melt blending again through extrusion, cooling, tie rod, pelletizing and dry obtained function Polylactic acid master batch, each component content in function polylactic acid master batch are as follows: the C.I pigment yellow of the polylactic acid powder of 76wt%, 10wt% 32, the insoluble insoluble metal-modified cross carboxylate of 10wt%, the modifier A of 2wt% and the auxiliary material of 2wt%；

(6.1) l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are done after mixing Dry obtained mixture, wherein dry temperature is 120 DEG C, time 16h, l-lactic acid slice and dextrorotation polylactic acid slice Mass ratio be 1:1, the mass fraction of function polylactic acid master batch is 20% in mixture；

(6.2) mixture melted, measure pump-metered, spinneret extrusion, winding, molding, boundling, drawing-off, heat calmly The flame-proof polylactic acid fiber containing metal-modified cross carboxylate is obtained after type, curling and cutting, wherein metering pump for amount be 1000g/min, the temperature that spinneret squeezes out are 230 DEG C, and the speed that spinneret squeezes out is 1000m/min, and the multiple of drawing-off is 3.6 Times.

The filament number of flame-proof polylactic acid fiber obtained containing metal-modified cross carboxylate is 3.4dtex, fracture Intensity is 4.10cN/dtex, and elongation at break 51%, line density deviation ratio is 7.0%.

The fusing point of flame-proof polylactic acid fiber containing metal-modified cross carboxylate is 206 DEG C, phosphorus content 7000ppm, Limit oxygen index is that 36%, UL-94 reaches V-0 grades.

Embodiment 9~22

A kind of preparation method of the flame-proof polylactic acid fiber containing metal-modified cross carboxylate, preparation step is substantially the same as real Example 6 is applied, the difference is that the content of polylactic acid powder and metal-modified cross carboxylate, colorant in function polylactic acid master batch Type and l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are uniformly mixed mixture obtained The mass fraction of middle function polylactic acid master batch, see Table 1 for details.

The filament number of flame-proof polylactic acid fiber obtained containing metal-modified cross carboxylate is Hdtex, and fracture is strong Degree is AcN/dtex, and elongation at break B%, line density deviation ratio is C%.It is fire-retardant poly- containing metal-modified cross carboxylate The fusing point of acid fiber is E DEG C, and limit oxygen index F%, UL-94 reach V-0 grades, and see Table 2 for details for the numerical value of H, A, B, C, E and F.

Table 1

Table 2

Embodiment	H	A	B	C	E	F
							9	3.7	4.2	48	7.0	204	36
10	3.2	3.9	48.2	7.4	205	37
							11	3.3	4.0	47.5	7.2	206	34
12	3.4	4.1	47.8	-7.6	204	35
							13	3.1	3.8	49	-7.5	205	34
14	3.4	4.1	49.5	-7.5	207	35
							15	3.5	4.2	52	-7.6	205	36
16	3.5	4.2	49	7.5	207	35
							17	3.6	4.3	51	-7.8	208	36
18	3.2	3.9	52	-7.4	204	36
							19	3.3	4.05	51	-7.5	205	35
20	3.3	4.0	50	-7.5	206	36
							21	3.4	4.15	46	-7.5	206	34
22	3.3	4.0	49	-7.4	205	35

Claims

1. the flame-proof polylactic acid fiber containing metal-modified cross carboxylate, it is characterized in that: mainly by acid fiber by polylactic matrix with And it is dispersed in modifier A and modifying agent B composition in acid fiber by polylactic matrix；

The acid fiber by polylactic matrix by etc. quality l-lactic acid and dextrorotation polylactic acid form, the modifier A be benzene first The mixture that sour aluminium, hydrated magnesium silicate and silica are mixed to get by the mass ratio of 2:1:1, the modifying agent B be it is insoluble not The network polymer that molten metal-modified cross carboxylate, specially cross carboxylate and metal ion crosslinked are formed, gold Belonging to modified cross carboxylate has insoluble insoluble characteristic, organic solvent I is not dissolved at 80 DEG C or less, in room temperature to T range It does not melt inside, T >=380 DEG C；

The structural formula of the cross carboxylate is as follows:

In formula,The segment between the quaternary carbon C and carboxyl end group of cross carboxylate molecular center is represented,In it is former containing band oxygen The double bond of son；

The crosslinking is to pass through coordination key connection with metal ion by the oxygen atom in cross carboxylate intramolecule double bond The acid ion in cross carboxylate molecule and metal ion are realized by ion key connection simultaneously；

The organic solvent I is that aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon solvent, alcohols are molten Agent, esters solvent, ketones solvent, acetonitrile, pyridine, phenol, N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.

2. the flame-proof polylactic acid fiber according to claim 1 containing metal-modified cross carboxylate, which is characterized in that contain The filament number of the flame-proof polylactic acid fiber of metal-modified cross carboxylate be 3.0~4.4dtex, breaking strength >= 3.70cN/dtex, elongation at break are 45~55%, and line density deviation ratio is -8.0~8.0%；

The fusing point of the flame-proof polylactic acid fiber containing metal-modified cross carboxylate is 200~210 DEG C；

Contain P elements, phosphorus content > 6500ppm, pole in the flame-proof polylactic acid fiber containing metal-modified cross carboxylate Limited oxygen index is that 30~38%, UL-94 reaches V-0 grades.

3. the flame-proof polylactic acid fiber according to claim 1 containing metal-modified cross carboxylate, which is characterized in that institute Stating aromatic hydrocarbon solvent is benzene,toluene,xylene, styrene, butyl toluene or vinyltoluene；The fat hydrocarbon solvent is N-hexane, pentane, hexane or octane；The alicyclic hydrocarbon type solvent is hexamethylene, cyclohexanone or toluene cyclohexanone；The halogenated hydrocarbons Class solvent is chlorobenzene, dichloro-benzenes, methylene chloride, chloroform, carbon tetrachloride, trichloro ethylene, tetrachloro-ethylene, trichloropropane or two chloroethenes Alkane；The alcohols solvent is methanol, ethyl alcohol, isopropanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol or propylene glycol；The ester Class solvent is methyl acetate, ethyl acetate or propyl acetate；The ketones solvent is acetone, espeleton, methylisobutylketone, ring Hexanone or toluene cyclohexanone.

4. the flame-proof polylactic acid fiber according to claim 1 containing metal-modified cross carboxylate, which is characterized in that institute Stating the metal-modified aerial initial decomposition temperature of cross carboxylate is 300~400 DEG C, the metal-modified cross ester It is 40~500nm that compound, which is dispersed in the partial size in macromolecule matrix,.

5. the flame-proof polylactic acid fiber according to claim 1 containing metal-modified cross carboxylate, which is characterized in that institute The preparation step for stating cross carboxylate is as follows:

(a) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, in nitrogen or inert gas shielding and churned mechanically Under the conditions of carry out fusion esterification reaction, collect product, it is post-treated to obtain DAPER；

(b) by dicarboxylic acids B₂Mixed with dihydric alcohol with the molar ratio of 1:1, catalyst be added, in nitrogen or inert gas shielding and Melt condensation reaction is carried out under conditions of mechanical stirring, obtains DADA；

(c) DAPER is added in the system of step (b), the molar ratio of DAPER and DADA are 1:4, keep the temperature of system not Become, be continually fed into nitrogen or inert gas, fusion esterification reaction is carried out under conditions of mechanical stirring, product is collected, after Reason obtains cross carboxylate；

In step (b), the catalyst is 4- toluenesulfonic acid, the B₂Molar ratio with catalyst is 1:0.01, the inertia Gas is argon gas, helium or neon, and the churned mechanically mixing speed is 50~500rpm, the temperature of the melt condensation reaction Degree is 180~200 DEG C, and the reaction time is 1~3h；

The dihydric alcohol is ethylene glycol, propylene glycol or 1,4- butanediol.

6. the flame-proof polylactic acid fiber according to claim 1 containing metal-modified cross carboxylate, which is characterized in that institute Stating metal ion is Co²⁺、Ni²⁺、Cu²⁺Or Zn²⁺, the metal ion provides by its corresponding mol ratio of metal acetate, and the metal changes Property cross carboxylate in the content of metal ion be 10~20wt%.

7. preparing the flame-proof polylactic acid fiber as described in any one of claims 1 to 6 containing metal-modified cross carboxylate Method, it is characterized in that: by l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch after mixing using molten Melt spin processes and the flame-proof polylactic acid fiber containing metal-modified cross carboxylate is made, the l-lactic acid slice and dextrorotation are poly- The mass ratio of lactic acid slice is 1:1, contains modifier A and modifying agent B in the function polylactic acid master batch.

8. the method according to the description of claim 7 is characterized in that steps are as follows:

(1) l-lactic acid slice, dextrorotation polylactic acid slice and function polylactic acid master batch are dried after mixing obtained Mixture, wherein the mass fraction of function polylactic acid master batch is 10~30%, and dry temperature is 110~125 DEG C, and the time is 13~16h；

(2) mixture melted, measure pump-metered, spinneret extrusion, winding, molding, boundling, drawing-off, thermal finalization, curling With the flame-proof polylactic acid fiber containing metal-modified cross carboxylate is obtained after cutting, wherein metering pump for amount for 780~ 1000g/min, the temperature that spinneret squeezes out are 225~260 DEG C, and the speed that spinneret squeezes out is 980~1100m/min, drawing-off Multiple be 3.1~3.6 times.

9. the method according to the description of claim 7 is characterized in that poly- cream of the function polylactic acid master batch by 63~83wt% Sour powder, the colorant of 5~15wt%, the modifying agent B of 10~30wt%, the modifier A of 1~3wt% and the auxiliary material of 1~5wt% Composition；

The function polylactic acid master batch the preparation method comprises the following steps: polylactic acid powder, colorant, modifying agent B, modifier A and auxiliary material are mixed It is made after closing uniformly through melt blending, extrusion, cooling, tie rod, pelletizing and drying, the temperature of melt blending is 150~180 DEG C；

The polylactic acid powder is made by l-lactic acid slice and dextrorotation polylactic acid slice by grinding after the mass ratio mixing of 1:1 ?；

The colorant is C.I. Pigment white 6, white 18:1, C.I paratonere 101 of C.I. face, C.I pigment red 4 9:1, C.I paratonere 68, C.I pigment yellow 32, C.I. pigment yellow 16, C.I. pigment black 11, C.I. pigment black 15, C.I. solvent yellow 19, C.I. pigment orange 24, C.I pigment violet 3, C.I. pigment blue 10, phthalocyanine blue b, C.I. pigment blue 29, C.I pigment blue 1 7:1, C.I naphthol green 8, sun-proof One or more of emerald green color lake, environmentally-friecarbon carbon black FR8150 and environmentally-friecarbon carbon black FR5200；

The auxiliary material is the mixture of polyethylene wax and nanometer calcium carbonate, wherein the content of polyethylene wax is 40~60wt%.

10. the method according to the description of claim 7 is characterized in that the preparation step of the modifying agent B is as follows:

(1) cross carboxylate and mol ratio of metal acetate are dissolved in organic solvent II and deionized water respectively and obtain cross ester Compound solution and metal acetate salting liquid；

(2) under the conditions of stirring and sonic oscillation, metal acetate salting liquid is added drop-wise in cross carboxylate solution and is carried out instead It should obtain suspension；

(3) suspension after reaction is post-processed to obtain modifying agent B；

In step (1), the organic solvent II be chloroform, acetone, n,N-Dimethylformamide or tetrahydrofuran, it is described cross The concentration of carboxylate solution is 0.7~1.25mol/L, and the concentration of the metal acetate salting liquid is 0.1~0.3mol/L；

In step (2), the stirring is mechanical stirring or magnetic agitation, and the rate of stirring is 50~500rpm, the ultrasound vibration The power swung is 600~1200W, and the speed of the dropwise addition is 0.5~2 drop/sec, and the volume of every drop is 0.05~0.1mL, is added dropwise After in reaction system the molar ratio of cross carboxylate and metal ion be 1:2~9；

In step (3), the post-processing, which refers to, to be filtered, washed and dried, wherein drying carries out under vacuum conditions, very Reciprocal of duty cycle is -0.1MPa, and drying time is 8~12h, and drying temperature is 25 DEG C.