CN109735922A

CN109735922A - Cross section fiber and preparation method thereof containing metal-modified cross carboxylate

Info

Publication number: CN109735922A
Application number: CN201811528496.4A
Authority: CN
Inventors: 孙宾; 纪晓寰; 朱美芳; 冯忠耀; 杨卫忠; 相恒学; 王佳欢; 李忠
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: 2019-05-10
Anticipated expiration: 2038-12-13
Also published as: CN109735922B

Abstract

The present invention relates to a kind of cross section fiber and preparation method thereof containing metal-modified cross carboxylate, the preparation method comprises the following steps: the spinning melt as made from functional agglomerate and polyester slice melt blending, which is carried out melt spinning, is made the cross section fiber containing metal-modified cross carboxylate, contain metal-modified cross carboxylate in functional agglomerate, metal-modified cross carboxylate is cross carboxylate and the network polymer that metal ion crosslinked is formed, metal-modified cross carboxylate has insoluble insoluble characteristic, in 80 DEG C or less insoluble organic solvent Is, it is not melted in room temperature to T range, T >=380 DEG C.Measure wicking height of the fabric in 10min as made from the cross section fiber containing metal-modified cross carboxylate is 150~250mm.The method of the present invention is easy to operate, and final obtained fiber has excellent fire-retardant, antibacterial and moisture absorption sweat discharging functions.

Description

Cross section fiber and preparation method thereof containing metal-modified cross carboxylate

Technical field

The invention belongs to functional fibre technical fields, are related to a kind of cross section containing metal-modified cross carboxylate Fiber and preparation method thereof.

Background technique

Functional fibre, fibre in differentiation and high-performance fiber are the main direction of development of traditional textile industry technology innovation. Functional fibre refers in addition to physical mechanical property possessed by general fiber, also with the novel fibre of certain specific function Dimension.In daily life, due to textile combustion caused by fire incident can bring injures and deaths and property loss, therefore, People's demand urgent at present is had become using fire-retardant tooling and household textiles.

Hygroscopic fibre is usually to make sweat in capillary using capillary phenomenon caused by fiber surface minute groove The surface of fabric and diverging are rapidly migrated under effect, to achieve the purpose that wet-guide quick-drying.Polyester fiber is in terms of dress material Consumption proportion in various synthetic fibers is the largest, but its moisture pick-up properties is worst again, is 20 DEG C and phase in temperature Under conditions of being 65% to humidity, polyester fiber balance Moisture absorption rate is only 0.4%, and ordinary polyester clothing wears and often makes one to feel It is sultry, therefore one of the hot spot of fibre in differentiation now is had become to the research of terylene moisture absorption sweat discharging functions.

In addition, the bacterium on such as underwear of the fabric as made from fiber and sport shirt clothes the health of human body can be generated it is huge Big threat, modified according to functional material, clothes made of anti-bacterial fibre, which are made, can prevent bacterium attached on clothing , to make one the invasion far from germs such as bacteriums.

Therefore, a kind of fiber with fire-retardant, antibacterial and moisture absorption sweat discharging functions is studied to have a very important significance.

Summary of the invention

The purpose of the present invention is overcoming above-mentioned problems of the prior art, provide a kind of with fire-retardant, antibacterial and suction The cross section fiber and preparation method thereof containing metal-modified cross carboxylate of wet perspiration functions.

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

Cross section fiber containing metal-modified cross carboxylate, section be it is cross, mainly by polyester fiber base Body and the metal-modified cross carboxylate composition being dispersed in polyester fiber matrix；

The metal-modified cross carboxylate is the network polymer of cross carboxylate and metal ion crosslinked formation, Metal-modified cross carboxylate has insoluble insoluble characteristic, organic solvent I is not dissolved at 80 DEG C or less, in room temperature to T model It is not melted in enclosing, T >=380 DEG C, the fusing point of metal-modified cross carboxylate of the invention is higher than the molten of most polymer Melt temperature, will not be melted when being blended with polymer melting, because blend machine-shaping is difficult without caused by；

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；

The organic solvent I is aromatic hydrocarbon solvent, fat hydrocarbon solvent, alicyclic hydrocarbon type solvent, halogenated hydrocarbon solvent, alcohol Class solvent, esters solvent, ketones solvent, acetonitrile, pyridine, phenol, N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.This The metal-modified cross carboxylate of invention does not dissolve in most organic solvents, be only herein simply enumerate it is some commonly use it is molten Agent.Metal-modified cross carboxylate of the invention contains metal ion, and metal-modified cross carboxylate is dispersed in fibre In Wiki body, assign that fiber is good fire-retardant and anti-microbial property, at the same the cross section of fiber be it is cross, it is excellent to assign fiber Moisture absorbing and sweat releasing performance, thus the cross section fiber obtained containing metal-modified cross carboxylate have it is excellent it is fire-retardant, Antibacterial and moisture absorbing and sweat releasing performance.

As a preferred technical scheme:

Cross section fiber as described above containing metal-modified cross carboxylate contains metal-modified cross esterification The filament number of the cross section fiber of object is 2.5~3.5dtex, and breaking strength is 4~7cN/dtex, and elongation at break is 20%~50%, Young's modulus is 12~16GPa；

Phosphorus element-containing in metal-modified cross carboxylate, the cross section fiber containing metal-modified cross carboxylate In the content of metal-modified cross carboxylate be 20~60wt%, cross section containing metal-modified cross carboxylate is fine Phosphorus content > 10000ppm of dimension, limit oxygen index are that 33~39%, UL-94 reaches V-0 grades；

Cross section fiber containing metal-modified cross carboxylate is through 50 washings front and rear to Staphylococcus aureus The bacteriostasis rate of bacterium is respectively 92~96% and 84~90%, through being respectively 92 to the bacteriostasis rate of Escherichia coli before and after 50 washings ~98% and 89~92%；

Measure wicking height of the fabric in 10min as made from the cross section fiber containing metal-modified cross carboxylate For 1500~2500mm.Measure wicking height in general fibre fabric 10min is 300~500mm/10min, illustrates fibre of the invention Dimension has excellent moisture absorption sweat discharging functions compared with the prior art.

Cross section 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；

The metal-modified cross aerial initial decomposition temperature of carboxylate is 300~400 DEG C, and the metal changes Partial size when the cross carboxylate of property is dispersed in macromolecule matrix is that (partial size being distributed in PET, PBT is 40 to 40~500nm ~200nm, the partial size being distributed in PP are 200~500nm).

Cross section 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；The present invention only enumerates a kind of preparation method of cross carboxylate, made from other methods Cross carboxylate is also applied for the present invention；

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.The present invention can be selected according to the actual demand of product Different raw materials, the compound and dihydric alcohol of other structures are equally applicable to the present invention, only its cross carboxylate obtained Structure with it is of the invention not fully identical, characteristic is not melted it is also possible to have insoluble, in this regard, the present invention does not visit further Study carefully.

Cross section 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%.Metal ion content is too low to will lead to metal-modified cross carboxylate obtained It is functional poor, and its insoluble insoluble characteristic can be impacted.The present invention can select different according to modified actual demand Metal ion, the present invention only enumerates the feasible metal ion in part, as long as other metal ions its by corresponding metal acetate Salting liquid is equally applicable to the present invention.

Cross section fiber as described above containing metal-modified cross carboxylate, the metal-modified cross ester The preparation step of compound 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；

(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 insoluble insoluble metal-modified cross carboxylate.

After metal acetate salting liquid is added dropwise into cross carboxylate solution, metal ion is simultaneously by mol ratio of metal acetate electricity The electrostatic attraction of the carboxyl end group of electrostatic attraction and cross carboxylate from the acetate ion of formation, due to both Electrostatic attraction is approximate, and metal ion will not be rapidly by the carboxyl total overall reaction on cross carboxylate surface, and metal ion is whole It is slow release during a, the inside of cross carboxylate molecule can be deep into, with pair inside cross carboxylate Oxygen atom on key establishes more stable coordinate bond, and the metal-modified cross carboxylate because prepared by has insoluble insoluble Characteristic.

Cross section fiber as described above containing metal-modified cross carboxylate, it is described organic molten in step (1) Agent II is chloroform, acetone, n,N-Dimethylformamide or tetrahydrofuran, the concentration of the cross carboxylate solution is 0.7~ 1.25mol/L, the concentration of the metal acetate salting liquid are 0.1~0.3mol/L；

In step (2), the stirring is mechanical stirring or magnetic agitation, and the rate of stirring is 50~500rpm, stirring speed Degree determines the size for the metal-modified cross carboxylate to be formed, and the power of the sonic oscillation is 600~1200W, ultrasound The power of oscillation is higher, and obtained metal-modified cross carboxylate structure is more uniform, and too low power will lead to resulting gold Belonging to modified cross carboxylate only surface layer coordination of metal ion, inside is not coordinated, and the speed of the dropwise addition is 0.5~2 drop/sec, The volume of every drop is 0.05~0.1mL, and the molar ratio of cross carboxylate and metal ion is in reaction system after completion of dropwise addition 1:2~9, the additive amount of metal ion is too low cannot to be formed enough coordination structures and will lead to the metal-modified cross ester to be formed The insoluble insoluble property of compound is impacted；

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.

The present invention also provides a kind of cross section fibers prepared as described above containing metal-modified cross carboxylate Method, the spinning melt as made from functional agglomerate and polyester slice melt blending is subjected to melt spinning and is made containing metal-modified The cross section fiber of cross carboxylate contains metal-modified cross carboxylate in the functional agglomerate.

Method as described above, the specific steps are as follows:

(1) functional agglomerate and polyester slice are placed in crystallizer respectively, are persistently added using 120~170 DEG C of hot-airs Hot 1h~3h completes pre-crystallized；

(2) by functional agglomerate and polyester slice under conditions of temperature is 150~170 DEG C 4~8h of aeration-drying to function Moisture content < 20ppm of master batch and polyester slice；

(3) functional agglomerate and polyester slice are added in screw extruder and are melted and be obtained by filtration spinning melt, melted Melting temperature is 270~295 DEG C, and the pore size filter of the filter of filtering is 0.5mm；

(4) spinning melt is delivered to spinning manifold, through metering pump-metered into filament spinning component, through cross spinneret It squeezes out and as-spun fibre is made, the temperature of spinning manifold is 280~300 DEG C, and the temperature of metering pump is 280~290 DEG C；

(5) the cooling obtained cross section containing metal-modified cross carboxylate is carried out to as-spun fibre using cross air blasting Fiber, the temperature of cross air blasting are 20~30 DEG C, and relative humidity is 65~75%, and speed is 0.3~0.6m/s；

(6) the cross section fiber containing metal-modified cross carboxylate is wound using up- coiler, winding speed Degree is 3500~4800m/min.

Method as described above, according to parts by weight, functional agglomerate is by 100 parts of polyester slices or recycled polyester slice, 20 ~60 parts of metal-modified cross carboxylates, 2~6 parts of dispersing agents and 1~3 part of antioxidant composition；

The dispersing agent is one or more of polyethylene wax, calcium stearate and zinc stearate, and the antioxidant is 2, 4- bis--(n-octylthiomethylene) -6- methylphenol or 2,4- bis- (dodecylthiomethyl) -6- methylphenol.

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 , 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 sonic oscillation condition 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, while the defect that general electrification complex ion complex is soluble in organic solvent is avoided, it solves functional cross Carboxylate adding too much when being blended can be processed to blend molding brings difficult problem.

In metal-modified cross carboxylate of the invention containing metal ion and the coordinate bond having and ionic bond with Organic matrix crosslinking belongs to hybrid inorganic-organic materials again, both sent out so that metal ion plays antibacterial and fire-retardant effect The feature of organic functional material multifunctionality has been waved, and has played inorganic material to the mechanics humidification of polymeric matrix, and Contain ester bond in its organic component, so that having good compatibility between functional material and matrix.

The final cross section fiber obtained containing metal-modified cross carboxylate, section are cross (cross Cross-section fibers than conventional circular fiber have higher specific surface area, be conducive to promoted fiber moisture absorbing and sweat releasing performance), mainly by Polyester fiber matrix and the metal-modified cross carboxylate composition being dispersed in polyester fiber matrix, metal-modified cross Type carboxylate may be homogenously dispersed in fibrous matrix, assign that fiber is good fire-retardant and anti-microbial property, while fiber is cross Cross section can be obviously improved the moisture absorbing and sweat releasing performance of fiber, therefore obtained containing the cross of metal-modified cross carboxylate Cross-section fibers have excellent fire-retardant, antibacterial and moisture absorbing and sweat releasing performance.

The utility model has the advantages that

(1) preparation method of a kind of cross section fiber containing metal-modified cross carboxylate of the invention, function Functional component (metal-modified cross carboxylate) content is high in master batch, and functional component, which has, is insoluble in common organic solvents And the characteristics of not melting is heated, it approximate can be considered as inorganic particle when processing with polyester slice melt blending, not lose its function Under the premise of energy property, the influence to blend rheological property is reduced, it is ensured that the rheological behavior of blend is conducive to product and processes Molding；

(2) preparation method of a kind of cross section fiber containing metal-modified cross carboxylate of the invention is added The cross functional material of metal coordination, enhances flame-retardant fiber, anti-microbial property, while setting cross for section Type has been obviously improved the moisture absorbing and sweat releasing performance of fiber；

(3) a kind of cross section fiber containing metal-modified cross carboxylate of the invention, with it is excellent it is fire-retardant, Antibacterial and moisture absorption sweat discharging functions realize the high sensibility and high performance of polyester fiber, have good market application prospect.

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,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.

Embodiment 1

A kind of preparation method of the cross section fiber containing metal-modified cross carboxylate, steps are as follows:

(1) metal-modified cross carboxylate is prepared；

(a1) cross carboxylate is prepared；

(a11) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is in nitrogen protection and mixing speed Fusion esterification reaction is carried out under conditions of the mechanical stirring of 300rpm, is collected product, through dissolution, is filtered and be dried to obtain DAPER, Wherein the temperature of fusion esterification reaction is 200 DEG C, reaction time 3h, A₂Structural formula are as follows:

(a12) by dicarboxylic acids B₂It is mixed with ethylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, protected in nitrogen Melt condensation reaction is carried out under conditions of the mechanical stirring that shield and mixing speed are 500rpm, obtains DADA, wherein B₂With 4- first The molar ratio of base 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:

(a13) DAPER is added in the system of step (a12), the molar ratio of DAPER and DADA are 1:4, keep system It is temperature-resistant, be continually fed into neon, carry out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 500rpm, Collect product, through crushing, dissolve, be filtered, washed and dried to obtain cross carboxylate, wherein the time of fusion esterification reaction be 1h, drying refer to the vacuum drying 11h in 30 DEG C of vacuum drying oven, structural formula such as formula (I) institute of cross carboxylate obtained Show；

(b1) 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；

(c1) 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；

(d1) 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 metal-modified cross carboxylate obtained²⁺Content be 11wt%, it is insoluble insoluble metal-modified cross Carboxylate is cross carboxylate and Co²⁺By oxygen atom in cross carboxylate intramolecule C=O and P=O double bond with Co²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Co²⁺The net even formed by ionic bond Network polymer has insoluble insoluble characteristic, and organic solvent I is not dissolved at 80 DEG C or less, and organic solvent I is benzene, toluene, diformazan Benzene, 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, dichloroethanes, methanol, Ethyl alcohol, isopropanol, n-butanol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, methyl acetate, ethyl acetate, propyl acetate, third Ketone, espeleton, methylisobutylketone, cyclohexanone, toluene cyclohexanone, acetonitrile, pyridine, phenol, N,N-dimethylformamide or N, N- dimethyl acetamide, in room temperature to not melting within the scope of 380 DEG C, the metal-modified cross aerial starting point of carboxylate Solving temperature is 340 DEG C；

(2) functional agglomerate is prepared；

Score meter by weight, functional agglomerate is sliced by 100 parts of PET, 40 parts of metal-modified cross carboxylates, 4 parts of poly- second Alkene wax and 2 parts of 2,4- bis--(n-octylthiomethylene) -6- methylphenol composition；

(3) the cross section fiber containing metal-modified cross carboxylate is prepared；

(a3) functional agglomerate and PET slice are placed in crystallizer respectively, it is complete using 150 DEG C of hot-air continuous heating 2h At pre-crystallized；

(b3) by functional agglomerate and PET slice under conditions of temperature is 160 DEG C aeration-drying 6h to functional agglomerate and PET The moisture content of slice is 18ppm；

(c3) functional agglomerate and PET slice are added in screw extruder and are melted and be obtained by filtration spinning melt, melted Melting temperature is 280 DEG C, and the pore size filter of the filter of filtering is 0.5mm；

(d3) spinning melt is delivered to spinning manifold, through metering pump-metered into filament spinning component, through cross spinneret Plate, which squeezes out, is made as-spun fibre, and the temperature of spinning manifold is 290 DEG C, and the temperature of metering pump is 285 DEG C；

(e3) cooling cross section be made containing metal-modified cross carboxylate is carried out to as-spun fibre using cross air blasting Face fiber, the temperature of cross air blasting are 25 DEG C, relative humidity 70%, speed 0.45m/s；

(f3) the cross section fiber containing metal-modified cross carboxylate is wound using up- coiler, winding speed Degree is 4100m/min.

Cross section fiber obtained containing metal-modified cross carboxylate mainly by polyester fiber matrix and uniformly The metal-modified cross carboxylate composition being dispersed in polyester fiber matrix, containing the cross of metal-modified cross carboxylate The filament number of cross-section fibers is 3dtex, and breaking strength 5.5cN/dtex, elongation at break 35%, Young's modulus is 16GPa；

The content of metal-modified cross carboxylate is in cross section fiber containing metal-modified cross carboxylate 40wt%, the phosphorus content 12000ppm of the cross section fiber containing metal-modified cross carboxylate, limit oxygen index are 39%, UL-94 reach V-0 grades, and the cross section fiber containing metal-modified cross carboxylate is through right before and after 50 washings The bacteriostasis rate of staphylococcus aureus is respectively 94% and 86%, through distinguishing before and after 50 washings the bacteriostasis rate of Escherichia coli For 95% and 90%；

Measure wicking height of the fabric in 10min as made from the cross section fiber containing metal-modified cross carboxylate For 200mm.

Embodiment 2

(1) metal-modified cross carboxylate is prepared；

(a1) cross carboxylate is prepared；

(a11) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is in argon gas protection and mixing speed Fusion esterification reaction is carried out under conditions of the mechanical stirring of 350rpm, is collected product, through dissolution, is filtered and be dried to obtain DAPER, Wherein the temperature of fusion esterification reaction is 185 DEG C, reaction time 1h, A₂Structural formula are as follows:

(a12) by dicarboxylic acids B₂It is mixed with propylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, protected in nitrogen Melt condensation reaction is carried out under conditions of the mechanical stirring that shield and mixing speed are 300rpm, obtains DADA, wherein B₂With 4- first The molar ratio of base 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:

(a13) DAPER is added in the system of step (a12), the molar ratio of DAPER and DADA are 1:4, keep system It is temperature-resistant, be continually fed into nitrogen, carry out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 450rpm, Collect product, through crushing, dissolve, be 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；

(b1) dissolution of cross carboxylate is obtained into the cross carboxylate solution that concentration is 1.25mol/L in acetone, Nickel acetate dissolution is obtained into the nickel acetate solution that concentration is 0.2mol/L in deionized water；

(c1) 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；

(d1) 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 DEG C, Ni in metal-modified cross carboxylate obtained²⁺Content be 15wt%, insoluble insoluble metal-modified cross ester Compound is cross carboxylate and Ni²⁺Pass through the oxygen atom and Ni in cross carboxylate intramolecule C=O double bond²⁺By matching - the COO of position key connection while cross carboxylate molecular end^-Ion and Ni²⁺The network polymer even formed by ionic bond, With insoluble insoluble characteristic, organic solvent I is not dissolved at 80 DEG C or less, the specific type of organic solvent I and embodiment 1 are consistent, 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；

(2) functional agglomerate is prepared；

Score meter by weight, functional agglomerate is sliced by 100 parts of regenerative PETs, 20 parts of metal-modified cross carboxylates, 2 parts Calcium stearate and 1 part of 2,4- bis- (dodecylthiomethyl) -6- methylphenol composition；

(a3) functional agglomerate and PET slice are placed in crystallizer respectively, it is complete using 120 DEG C of hot-air continuous heating 1h At pre-crystallized；

(b3) by functional agglomerate and PET slice under conditions of temperature is 150 DEG C aeration-drying 4h to functional agglomerate and PET The moisture content of slice is 15ppm；

(c3) functional agglomerate and PET slice are added in screw extruder and are melted and be obtained by filtration spinning melt, melted Melting temperature is 270 DEG C, and the pore size filter of the filter of filtering is 0.5mm；

(d3) spinning melt is delivered to spinning manifold, through metering pump-metered into filament spinning component, through cross spinneret Plate, which squeezes out, is made as-spun fibre, and the temperature of spinning manifold is 280 DEG C, and the temperature of metering pump is 280 DEG C；

(e3) cooling cross section be made containing metal-modified cross carboxylate is carried out to as-spun fibre using cross air blasting Face fiber, the temperature of cross air blasting are 20 DEG C, relative humidity 65%, speed 0.3m/s；

(f4) the cross section fiber containing metal-modified cross carboxylate is wound using up- coiler, winding speed Degree is 3500m/min.

Cross section fiber obtained containing metal-modified cross carboxylate mainly by polyester fiber matrix and uniformly The metal-modified cross carboxylate composition being dispersed in polyester fiber matrix, containing the cross of metal-modified cross carboxylate The filament number of cross-section fibers is 2.5dtex, and breaking strength 4cN/dtex, elongation at break 20%, Young's modulus is 12GPa；

The content of metal-modified cross carboxylate is in cross section fiber containing metal-modified cross carboxylate 20wt%, limit oxygen index 33%, UL-94 reach V-0 grades, the cross section fiber containing metal-modified cross carboxylate Through being respectively 92% and 84% to the bacteriostasis rate of staphylococcus aureus before and after 50 washings, through 50 washings front and rear to big The bacteriostasis rate of enterobacteria is respectively 92% and 89%；

Measure wicking height of the fabric in 10min as made from the cross section fiber containing metal-modified cross carboxylate For 150mm.

Embodiment 3

(1) metal-modified cross carboxylate is prepared；

(a1) cross carboxylate is prepared；

(a11) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is in helium protection and mixing speed Fusion esterification reaction is carried out under conditions of the mechanical stirring of 400rpm, is collected product, through dissolution, is filtered and be dried to obtain DAPER, Wherein the temperature of fusion esterification reaction is 180 DEG C, reaction time 2h, A₂Structural formula are as follows:

(a12) by dicarboxylic acids B₂It is mixed with 1,4-butanediol with the molar ratio of 1:1,4- toluenesulfonic acid is added, in argon Melt condensation reaction is carried out under conditions of the mechanical stirring that gas shielded and mixing speed are 500rpm, obtains DADA, wherein B₂With The molar ratio of 4- toluenesulfonic acid is 1:0.01, and the temperature of melt condensation reaction is 180 DEG C, reaction time 1h, B₂Structure Formula are as follows:

(a13) DAPER is added in the system of step (a12), the molar ratio of DAPER and DADA are 1:4, keep system It is temperature-resistant, be continually fed into neon, carry out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 330rpm, Collect product, through crushing, dissolve, be 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；

(b1) 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；

(c1) 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；

(d1) 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 metal-modified cross carboxylate obtained²⁺Content be 20wt%, it is insoluble insoluble metal-modified cross Carboxylate is cross carboxylate and Cu²⁺Pass through the oxygen atom in cross carboxylate intramolecule C=O double bond and P=O double bond With Cu²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Cu²⁺It is even formed by ionic bond Network polymer has insoluble insoluble characteristic, does not dissolve in organic solvent I, the specific type of organic solvent I and reality at 80 DEG C or less It is consistent to apply example 1, in room temperature to not melting within the scope of 380 DEG C, the metal-modified cross aerial starting of carboxylate is decomposed warm Degree is 360 DEG C；

(2) functional agglomerate is prepared；

Score meter by weight, functional agglomerate is sliced by 100 parts of PET, 60 parts of metal-modified cross carboxylates, 6 parts of tristearin Sour zinc and 3 parts of 2,4- bis- (dodecylthiomethyl) -6- methylphenol compositions；

(a3) functional agglomerate and PET slice are placed in crystallizer respectively, it is complete using 170 DEG C of hot-air continuous heating 3h At pre-crystallized；

(b3) by functional agglomerate and PET slice under conditions of temperature is 170 DEG C aeration-drying 8h to functional agglomerate and PET The moisture content of slice is 18ppm；

(c3) functional agglomerate and PET slice are added in screw extruder and are melted and be obtained by filtration spinning melt, melted Melting temperature is 295 DEG C, and the pore size filter of the filter of filtering is 0.5mm；

(d3) spinning melt is delivered to spinning manifold, through metering pump-metered into filament spinning component, through cross spinneret Plate, which squeezes out, is made as-spun fibre, and the temperature of spinning manifold is 300 DEG C, and the temperature of metering pump is 290 DEG C；

(e3) cooling cross section be made containing metal-modified cross carboxylate is carried out to as-spun fibre using cross air blasting Face fiber, the temperature of cross air blasting are 30 DEG C, relative humidity 75%, speed 0.6m/s；

(f3) the cross section fiber containing metal-modified cross carboxylate is wound using up- coiler, winding speed Degree is 4800m/min.

Cross section fiber obtained containing metal-modified cross carboxylate mainly by polyester fiber matrix and uniformly The metal-modified cross carboxylate composition being dispersed in polyester fiber matrix, containing the cross of metal-modified cross carboxylate The filament number of cross-section fibers is 3.5dtex, and breaking strength 7cN/dtex, elongation at break 50%, Young's modulus is 16GPa；

The content of metal-modified cross carboxylate is in cross section fiber containing metal-modified cross carboxylate 60wt%, limit oxygen index 39%, UL-94 reach V-0 grades, the cross section fiber containing metal-modified cross carboxylate Through being respectively 96% and 90% to the bacteriostasis rate of staphylococcus aureus before and after 50 washings, through 50 washings front and rear to big The bacteriostasis rate of enterobacteria is respectively 98% and 92%；

Measure wicking height of the fabric in 10min as made from the cross section fiber containing metal-modified cross carboxylate For 250mm.

Embodiment 4

(1) metal-modified cross carboxylate is prepared；

(a1) cross carboxylate is prepared；

(a11) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is in neon protection and mixing speed Fusion esterification reaction is carried out under conditions of the mechanical stirring of 450rpm, is collected product, through dissolution, is filtered and be dried to obtain DAPER, Wherein the temperature of fusion esterification reaction is 195 DEG C, reaction time 4h, A₂Structural formula are as follows:

(a12) by dicarboxylic acids B₂It is mixed with propylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, protected in helium Melt condensation reaction is carried out under conditions of the mechanical stirring that shield and mixing speed are 300rpm, obtains DADA, wherein B₂With 4- first The molar ratio of base 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:

(a13) DAPER is added in the system of step (a12), the molar ratio of DAPER and DADA are 1:4, keep system It is temperature-resistant, be continually fed into nitrogen, carry out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 500rpm, Collect product, through crushing, dissolve, be filtered, washed and dried to obtain cross carboxylate, wherein the time of fusion esterification reaction be 4h, drying refer to the vacuum drying 6h in 35 DEG C of vacuum drying oven, structural formula such as formula (I) institute of cross carboxylate obtained Show；

(b1) 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；

(c1) 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；

(d1) 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 metal-modified cross carboxylate obtained²⁺Content be 16wt%, it is insoluble insoluble metal-modified cross Carboxylate is cross carboxylate and Zn²⁺Pass through the oxygen atom in cross carboxylate intramolecule C=O double bond and P=O double bond With Zn²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Zn²⁺It is even formed by ionic bond Network polymer has insoluble insoluble characteristic, does not dissolve in organic solvent I, the specific type of organic solvent I and reality at 80 DEG C or less It is consistent to apply example 1, in room temperature to not melting within the scope of 390 DEG C, the metal-modified cross aerial starting of carboxylate is decomposed warm Degree is 371 DEG C；

(2) functional agglomerate is prepared；

Score meter by weight, functional agglomerate is sliced by 100 parts of PET, 25 parts of metal-modified cross carboxylates, 6 parts of dispersions Agent (mixture of polyethylene wax and calcium stearate mass ratio 1:1) and 3 parts of 2,4- bis--(n-octylthiomethylene) -6- methylbenzene Phenol composition；

(a3) functional agglomerate and PET slice are placed in crystallizer respectively, it is complete using 140 DEG C of hot-air continuous heating 2h At pre-crystallized；

(b3) by functional agglomerate and PET slice under conditions of temperature is 160 DEG C aeration-drying 5h to functional agglomerate and PET The moisture content of slice is 15ppm；

(c3) functional agglomerate and PET slice are added in screw extruder and are melted and be obtained by filtration spinning melt, melted Melting temperature is 290 DEG C, and the pore size filter of the filter of filtering is 0.5mm；

(d3) spinning melt is delivered to spinning manifold, through metering pump-metered into filament spinning component, through cross spinneret Plate, which squeezes out, is made as-spun fibre, and the temperature of spinning manifold is 280 DEG C, and the temperature of metering pump is 290 DEG C；

(e3) cooling cross section be made containing metal-modified cross carboxylate is carried out to as-spun fibre using cross air blasting Face fiber, the temperature of cross air blasting are 25 DEG C, relative humidity 70%, speed 0.4m/s；

(f3) the cross section fiber containing metal-modified cross carboxylate is wound using up- coiler, winding speed Degree is 3600m/min.

Cross section fiber obtained containing metal-modified cross carboxylate mainly by polyester fiber matrix and uniformly The metal-modified cross carboxylate composition being dispersed in polyester fiber matrix, containing the cross of metal-modified cross carboxylate The filament number of cross-section fibers is 2.9dtex, and breaking strength 4.5cN/dtex, elongation at break 25%, Young's modulus is 15GPa；

The content of metal-modified cross carboxylate is in cross section fiber containing metal-modified cross carboxylate 28wt%, limit oxygen index 35%, UL-94 reach V-0 grades, the cross section fiber containing metal-modified cross carboxylate Through being respectively 94% and 88% to the bacteriostasis rate of staphylococcus aureus before and after 50 washings, through 50 washings front and rear to big The bacteriostasis rate of enterobacteria is respectively 94% and 90%；

Measure wicking height of the fabric in 10min as made from the cross section fiber containing metal-modified cross carboxylate For 180mm.

Embodiment 5

(1) metal-modified cross carboxylate is prepared；

(a1) cross carboxylate is prepared；

(a11) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is in nitrogen protection and mixing speed Fusion esterification reaction is carried out under conditions of the mechanical stirring of 500rpm, is collected product, through dissolution, is filtered and be dried to obtain DAPER, Wherein the temperature of fusion esterification reaction is 180 DEG C, reaction time 1.5h, A₂Structural formula are as follows:

(a12) 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 gas shielded and mixing speed are 500rpm, obtains DADA, wherein B₂With The molar ratio of 4- toluenesulfonic acid is 1:0.01, and the temperature of melt condensation reaction is 195 DEG C, reaction time 3h, B₂Structure Formula are as follows:

(a13) DAPER is added in the system of step (a12), the molar ratio of DAPER and DADA are 1:4, keep system It is temperature-resistant, be continually fed into argon gas, carry out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 340rpm, Collect product, through crushing, dissolve, be filtered, washed and dried to obtain cross carboxylate, wherein the time of fusion esterification reaction be 3h, drying refer to the vacuum drying 15h in 30 DEG C of vacuum drying oven, structural formula such as formula (I) institute of cross carboxylate obtained Show；

(b1) 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；

(c1) 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；

(d1) 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 DEG C, Co in metal-modified cross carboxylate obtained²⁺Content be 11wt%, insoluble insoluble metal-modified cross ester Compound is cross carboxylate and Co²⁺By oxygen atom in cross carboxylate intramolecule C=O double bond and P=O double bond with Co²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Co²⁺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 380 DEG C, the metal-modified cross aerial initial decomposition temperature of carboxylate It is 300 DEG C；

(2) functional agglomerate is prepared；

Score meter by weight, functional agglomerate is sliced by 100 parts of regenerative PETs, 30 parts of metal-modified cross carboxylates, 3 parts (n-octyl sulphur is sub- by dispersing agent (mixture of polyethylene wax, calcium stearate and zinc stearate mass ratio 1:1:1) and 4 parts of 2,4- bis-- Methyl) -6- methylphenol composition；

(c3) functional agglomerate and PET slice are added in screw extruder and are melted and be obtained by filtration spinning melt, melted Melting temperature is 275 DEG C, and the pore size filter of the filter of filtering is 0.5mm；

(d3) spinning melt is delivered to spinning manifold, through metering pump-metered into filament spinning component, through cross spinneret Plate, which squeezes out, is made as-spun fibre, and the temperature of spinning manifold is 285 DEG C, and the temperature of metering pump is 285 DEG C；

(e3) cooling cross section be made containing metal-modified cross carboxylate is carried out to as-spun fibre using cross air blasting Face fiber, the temperature of cross air blasting are 30 DEG C, relative humidity 70%, speed 0.4m/s；

(f3) the cross section fiber containing metal-modified cross carboxylate is wound using up- coiler, winding speed Degree is 3900m/min.

Cross section fiber obtained containing metal-modified cross carboxylate mainly by polyester fiber matrix and uniformly The metal-modified cross carboxylate composition being dispersed in polyester fiber matrix, containing the cross of metal-modified cross carboxylate The filament number of cross-section fibers is 2.7dtex, and breaking strength 4.9cN/dtex, elongation at break 30%, Young's modulus is 14.5GPa；

The content of metal-modified cross carboxylate is in cross section fiber containing metal-modified cross carboxylate 30wt%, limit oxygen index 35%, UL-94 reach V-0 grades, the cross section fiber containing metal-modified cross carboxylate Through being respectively 93% and 89% to the bacteriostasis rate of staphylococcus aureus before and after 50 washings, through 50 washings front and rear to big The bacteriostasis rate of enterobacteria is respectively 94% and 91%；

Measure wicking height of the fabric in 10min as made from the cross section fiber containing metal-modified cross carboxylate For 190mm.

Embodiment 6

(1) metal-modified cross carboxylate is prepared；

(a1) cross carboxylate is prepared；

(a11) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is in helium protection and mixing speed Fusion esterification reaction is carried out under conditions of the mechanical stirring of 50rpm, is collected product, through dissolution, is filtered and be dried to obtain DAPER, Wherein the temperature of fusion esterification reaction is 190 DEG C, reaction time 2.5h, A₂Structural formula are as follows:

(a12) by dicarboxylic acids B₂It is mixed with ethylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, protected in nitrogen Melt condensation reaction is carried out under conditions of the mechanical stirring that shield and mixing speed are 50rpm, obtains DADA, wherein B₂With 4- methyl The molar ratio of benzene 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:

(a13) DAPER is added in the system of step (a12), the molar ratio of DAPER and DADA are 1:4, keep system It is temperature-resistant, be continually fed into nitrogen, carry out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 50rpm, Collect product, through crushing, dissolve, be 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；

(b1) dissolution of cross carboxylate is obtained into the cross carboxylate solution that concentration is 0.75mol/L in acetone, Nickel acetate dissolution is obtained into the nickel acetate solution that concentration is 0.2mol/L in deionized water；

(c1) 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；

(d1) 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 DEG C, Ni in metal-modified cross carboxylate obtained²⁺Content be 10wt%, insoluble insoluble metal-modified cross ester Compound is cross carboxylate and Ni²⁺Pass through the oxygen atom and Ni in cross carboxylate intramolecule C=O double bond²⁺By matching - the COO of position key connection while cross carboxylate molecular end^-Ion and Ni²⁺The network polymer even formed by ionic bond, With insoluble insoluble characteristic, organic solvent I is not dissolved at 80 DEG C or less, the specific type of organic solvent I and embodiment 1 are consistent, In room temperature to not melting within the scope of 390 DEG C, the metal-modified cross aerial initial decomposition temperature of carboxylate is 330 DEG C；

(2) functional agglomerate is prepared；

Score meter by weight, functional agglomerate is sliced by 100 parts of PET, 45 parts of metal-modified cross carboxylates, 5 parts of tristearin Sour calcium and 3 parts of 2,4- bis- (dodecylthiomethyl) -6- methylphenol compositions；

(b3) by functional agglomerate and PET slice under conditions of temperature is 165 DEG C aeration-drying 6h to functional agglomerate and PET The moisture content of slice is 15ppm；

(d3) spinning melt is delivered to spinning manifold, through metering pump-metered into filament spinning component, through cross spinneret Plate, which squeezes out, is made as-spun fibre, and the temperature of spinning manifold is 290 DEG C, and the temperature of metering pump is 290 DEG C；

(e3) cooling cross section be made containing metal-modified cross carboxylate is carried out to as-spun fibre using cross air blasting Face fiber, the temperature of cross air blasting are 26 DEG C, relative humidity 72%, speed 0.45m/s；

(f3) the cross section fiber containing metal-modified cross carboxylate is wound using up- coiler, winding speed Degree is 4000m/min.

Cross section fiber obtained containing metal-modified cross carboxylate mainly by polyester fiber matrix and uniformly The metal-modified cross carboxylate composition being dispersed in polyester fiber matrix, containing the cross of metal-modified cross carboxylate The filament number of cross-section fibers is 2.9dtex, and breaking strength 5.6cN/dtex, elongation at break 35%, Young's modulus is 14.5GPa；

The content of metal-modified cross carboxylate is in cross section fiber containing metal-modified cross carboxylate 35wt%, the phosphorus content 11300ppm of the cross section fiber containing metal-modified cross carboxylate, limit oxygen index are 36%, UL-94 reach V-0 grades, and the cross section fiber containing metal-modified cross carboxylate is through right before and after 50 washings The bacteriostasis rate of staphylococcus aureus is respectively 93% and 89%, through distinguishing before and after 50 washings the bacteriostasis rate of Escherichia coli For 94% and 90%；

Embodiment 7

(1) metal-modified cross carboxylate is prepared；

(a1) cross carboxylate is prepared；

(a11) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is in nitrogen protection and mixing speed Fusion esterification reaction is carried out under conditions of the mechanical stirring of 350rpm, is collected product, through dissolution, is filtered and be dried to obtain DAPER, Wherein the temperature of fusion esterification reaction is 200 DEG C, reaction time 3.5h, A₂Structural formula are as follows:

(a12) 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 Melt condensation reaction is carried out under conditions of the mechanical stirring that shield and mixing speed are 400rpm, obtains DADA, wherein B₂With 4- first The molar ratio of base 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:

(a13) DAPER is added in the system of step (a12), the molar ratio of DAPER and DADA are 1:4, keep system It is temperature-resistant, be continually fed into helium, carry out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 370rpm, Collect product, through crushing, dissolve, be filtered, washed and dried to obtain cross carboxylate, wherein the time of fusion esterification reaction be 1h, drying refer to the vacuum drying 14h in 40 DEG C of vacuum drying oven, structural formula such as formula (I) institute of cross carboxylate obtained Show；

(b1) being dissolved in cross carboxylate and obtaining concentration in N,N-dimethylformamide is the cross of 0.9mol/L Copper acetate dissolution is obtained the acetic acid copper solution that concentration is 0.2mol/L by carboxylate solution in deionized water；

(c1) 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；

(d1) 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, Cu in metal-modified cross carboxylate obtained²⁺Content be 16wt%, it is insoluble insoluble metal-modified cross Carboxylate is cross carboxylate and Cu²⁺Pass through the oxygen atom and Cu in cross carboxylate intramolecule C=O double bond²⁺Pass through - the COO of coordination key connection while cross carboxylate molecular end^-Ion and Cu²⁺The network polymerization even formed by ionic bond Object has insoluble insoluble characteristic, does not dissolve in organic solvent I, the specific type of organic solvent I and embodiment 1 one at 80 DEG C or less It causes, in room temperature to not melting within the scope of 385 DEG C, the metal-modified cross aerial initial decomposition temperature of carboxylate is 400 ℃；

(2) functional agglomerate is prepared；

Score meter by weight, functional agglomerate is sliced by 100 parts of PET or 45 parts of metal-modified cross carboxylates, 6 parts it is hard Resin acid calcium and 3 parts of 2,4- bis- (dodecylthiomethyl) -6- methylphenol compositions；

(a3) functional agglomerate and PET slice are placed in crystallizer respectively, it is complete using 170 DEG C of hot-air continuous heating 1h At pre-crystallized；

(b3) by functional agglomerate and PET slice under conditions of temperature is 150 DEG C aeration-drying 4h to functional agglomerate and PET The moisture content of slice is 16ppm；

(f3) the cross section fiber containing metal-modified cross carboxylate is wound using up- coiler, winding speed Degree is 4200m/min.

Cross section fiber obtained containing metal-modified cross carboxylate mainly by polyester fiber matrix and uniformly The metal-modified cross carboxylate composition being dispersed in polyester fiber matrix, containing the cross of metal-modified cross carboxylate The filament number of cross-section fibers is 3dtex, and breaking strength 5.8cN/dtex, elongation at break 40%, Young's modulus is 15.4GPa；

The content of metal-modified cross carboxylate is in cross section fiber containing metal-modified cross carboxylate 45wt%, the phosphorus content 12500ppm of the cross section fiber containing metal-modified cross carboxylate, limit oxygen index are 36%, UL-94 reach V-0 grades, and the cross section fiber containing metal-modified cross carboxylate is through right before and after 50 washings The bacteriostasis rate of staphylococcus aureus is respectively 95% and 87%, through distinguishing before and after 50 washings the bacteriostasis rate of Escherichia coli For 94% and 89%；

Measure wicking height of the fabric in 10min as made from the cross section fiber containing metal-modified cross carboxylate For 220mm.

Embodiment 8

(1) metal-modified cross carboxylate is prepared；

(a1) cross carboxylate is prepared；

(a11) by binary acid A₂It is mixed with pentaerythrite with the molar ratio of 4:1, is in helium protection and mixing speed Fusion esterification reaction is carried out under conditions of the mechanical stirring of 380rpm, is collected product, through dissolution, is filtered and be dried to obtain DAPER, Wherein the temperature of fusion esterification reaction is 180 DEG C, reaction time 1h, A₂Structural formula are as follows:

(a12) by dicarboxylic acids B₂It is mixed with propylene glycol with the molar ratio of 1:1,4- toluenesulfonic acid is added, protected in nitrogen Melt condensation reaction is carried out under conditions of the mechanical stirring that shield and mixing speed are 370rpm, obtains DADA, wherein B₂With 4- first The molar ratio of base 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:

(a13) DAPER is added in the system of step (a12), the molar ratio of DAPER and DADA are 1:4, keep system It is temperature-resistant, be continually fed into neon, carry out fusion esterification reaction under conditions of the mechanical stirring that low whipping speed is 350rpm, Collect product, through crushing, dissolve, be filtered, washed and dried to obtain cross carboxylate, wherein the time of fusion esterification reaction be 2h, drying refer to the vacuum drying 10h in 50 DEG C of vacuum drying oven, structural formula such as formula (I) institute of cross carboxylate obtained Show；

(b1) 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；

(c1) 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；

(d1) 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 DEG C, Zn in metal-modified cross carboxylate obtained²⁺Content be 20wt%, insoluble insoluble metal-modified cross ester Compound is cross carboxylate and Zn²⁺By oxygen atom in cross carboxylate intramolecule C=O double bond and P=O double bond with Zn²⁺Pass through-the COO of coordination key connection while cross carboxylate molecular end^-Ion and Zn²⁺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 380 DEG C, the metal-modified cross aerial initial decomposition temperature of carboxylate It is 300 DEG C；

(2) functional agglomerate is prepared；

Score meter by weight, functional agglomerate is sliced by 100 parts of PET, 55 parts of metal-modified cross carboxylates, 2 parts of tristearin Sour zinc and 3 parts of 2,4- bis--(n-octylthiomethylene) -6- methylphenol composition；

(a3) functional agglomerate and PET slice are placed in crystallizer respectively, it is complete using 165 DEG C of hot-air continuous heating 3h At pre-crystallized；

(b3) by functional agglomerate and PET slice under conditions of temperature is 170 DEG C aeration-drying 6h to functional agglomerate and PET The moisture content of slice is 18ppm；

(e3) cooling cross section be made containing metal-modified cross carboxylate is carried out to as-spun fibre using cross air blasting Face fiber, the temperature of cross air blasting are 25 DEG C, relative humidity 70%, speed 0.6m/s；

(f3) the cross section fiber containing metal-modified cross carboxylate is wound using up- coiler, winding speed Degree is 4500m/min.

Cross section fiber obtained containing metal-modified cross carboxylate mainly by polyester fiber matrix and uniformly The metal-modified cross carboxylate composition being dispersed in polyester fiber matrix, containing the cross of metal-modified cross carboxylate The filament number of cross-section fibers is 3.2dtex, and breaking strength 6.5cN/dtex, elongation at break 40%, Young's modulus is 15.8GPa；

The content of metal-modified cross carboxylate is in cross section fiber containing metal-modified cross carboxylate 55wt%, the phosphorus content 13500ppm of the cross section fiber containing metal-modified cross carboxylate, limit oxygen index are 38%, UL-94 reach V-0 grades, and the cross section fiber containing metal-modified cross carboxylate is through right before and after 50 washings The bacteriostasis rate of staphylococcus aureus is respectively 95% and 89%, through distinguishing before and after 50 washings the bacteriostasis rate of Escherichia coli For 96% and 91%；

Measure wicking height of the fabric in 10min as made from the cross section fiber containing metal-modified cross carboxylate For 230mm.

Claims

1. the cross section fiber containing metal-modified cross carboxylate, it is characterized in that: section be it is cross, mainly by polyester Fibrous matrix and the metal-modified cross carboxylate composition being dispersed in polyester fiber matrix；

The metal-modified cross carboxylate is cross carboxylate and the network polymer that metal ion crosslinked is formed, metal 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, 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 containing band oxygen The double bond of atom；

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 cross section fiber according to claim 1 containing metal-modified cross carboxylate, which is characterized in that contain The filament number of the cross section fiber of metal-modified cross carboxylate be 2.5~3.5dtex, breaking strength be 4~ 7cN/dtex, elongation at break are 20%~50%, and Young's modulus is 12~16GPa；

Phosphorus element-containing in metal-modified cross carboxylate, gold in the cross section fiber containing metal-modified cross carboxylate The content for belonging to modified cross carboxylate is 20~60wt%, the cross section fiber containing metal-modified cross carboxylate Phosphorus content > 10000ppm, limit oxygen index are that 33~39%, UL-94 reaches V-0 grades；

Cross section fiber containing metal-modified cross carboxylate is through 50 washings front and rear to staphylococcus aureus Bacteriostasis rate is respectively 92~96% and 84~90%, through before and after 50 washings to the bacteriostasis rate of Escherichia coli be respectively 92~ 98% and 89~92%；

Measure wicking height of the fabric in 10min as made from the cross section fiber containing metal-modified cross carboxylate be 150~250mm.

3. the cross section 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；

The metal-modified cross aerial initial decomposition temperature of carboxylate be 300~400 DEG C, described metal-modified ten Partial size when font carboxylate is dispersed in macromolecule matrix is 40~500nm.

4. the cross section 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.

5. the cross section 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%.

6. the cross section fiber according to claim 5 containing metal-modified cross carboxylate, which is characterized in that institute The preparation step for stating metal-modified cross carboxylate 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；

7. the cross section fiber according to claim 6 containing metal-modified cross carboxylate, which is characterized in that step Suddenly in (1), the organic solvent II is chloroform, acetone, n,N-Dimethylformamide or tetrahydrofuran, the cross carboxylate The concentration of 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.

8. preparing the cross section fiber as described in any one of claims 1 to 7 containing metal-modified cross carboxylate Method contains it is characterized in that: the spinning melt as made from functional agglomerate and polyester slice melt blending is carried out melt spinning and is made The cross section fiber of metal-modified cross carboxylate contains metal-modified cross carboxylate in the functional agglomerate.

9. according to the method described in claim 8, it is characterized in that, specific step is as follows:

(1) functional agglomerate and polyester slice are placed in crystallizer respectively, using 120~170 DEG C of hot-air continuous heating 1h ~3h completes pre-crystallized；

(2) by functional agglomerate and polyester slice under conditions of temperature is 150~170 DEG C 4~8h of aeration-drying to functional agglomerate With moisture content < 20ppm of polyester slice；

(3) functional agglomerate and polyester slice are added in screw extruder and are melted and be obtained by filtration spinning melt, melting temperature Degree is 270~295 DEG C, and the pore size filter of the filter of filtering is 0.5mm；

(4) spinning melt is delivered to spinning manifold, through metering pump-metered into filament spinning component, is squeezed out through cross spinneret As-spun fibre is made, the temperature of spinning manifold is 280~300 DEG C, and the temperature of metering pump is 280~290 DEG C；

(5) the cooling cross section fibre being made containing metal-modified cross carboxylate is carried out to as-spun fibre using cross air blasting Dimension, the temperature of cross air blasting are 20~30 DEG C, and relative humidity is 65~75%, and speed is 0.3~0.6m/s；

(6) the cross section fiber containing metal-modified cross carboxylate is wound using up- coiler, winding speed is 3500~4800m/min.

10. according to the method described in claim 8, it is characterized in that, according to parts by weight, functional agglomerate is cut by 100 parts of polyester Piece or recycled polyester slice, 20~60 parts of metal-modified cross carboxylates, 2~6 parts of dispersing agents and 1~3 part of antioxidant group At；

The dispersing agent is one or more of polyethylene wax, calcium stearate and zinc stearate, and the antioxidant is 2,4- bis-- (n-octylthiomethylene) -6- methylphenol or 2,4- bis- (dodecylthiomethyl) -6- methylphenol.