CN102704029A

CN102704029A - Preparation method for functionalized polyamide fiber

Info

Publication number: CN102704029A
Application number: CN2012102203001A
Authority: CN
Inventors: 王彪; 李莉; 王华平
Original assignee: Donghua University
Current assignee: Donghua University
Priority date: 2012-06-28
Filing date: 2012-06-28
Publication date: 2012-10-03
Anticipated expiration: 2032-06-28
Also published as: CN102704029B

Abstract

The invention relates to a preparation method for functionalized polyamide fiber. The functionalized polyamide fiber is formed by blending and spinning polyamide slices and functional powder coated by PBT (polybutylene terephthalate), wherein a preparation method for the functional powder coated by PBT comprises the steps of loading a titanium catalyst on the surface of the functional powder, adding polybutylene terephthalate cyclic oligomers (CBT) to generate polymerization on the surface of the functional powder to generate PBT resin, atomizing and pulverizing to obtain the functional powder powder coated by PBT. The catalyst polymerized by CBT is carried on the surface of the functional powder through loading technology, the mass ratio of the PBT resin and the functional powder is 2-4:1. The mass ratio of the polyamide slices and the functional powder coated by PBT is 10-15:1. In the method, the compatibility of the functional powder coated by PBT and the polyamide is excellent, and the functionalized effect of the obtained functionalized polyamide fiber is excellent.

Description

A kind of preparation method of functional poly nylon

Technical field

The present invention relates to the functional material field, be specifically related to a kind of preparation method of functional poly nylon.

Background technology

Along with the continuous development of fiber industry, people also not only are confined to cover body, attractive in appearance etc. effect to the requirement of fiber in the past, but more pay attention to realize the functionalization and the diversification utilization of fiber.At present; The functional modification work that comprises the multiple synthetic fiber of polyester fiber, polyamide fiber, polypropylene fibre has obtained very big development; Main functionalization means comprise finishing method that fiber is carried out chemical graft, co-blended spinning and fabric or the like; Wherein realize that through the co-blended spinning method functionalization of fiber is the easiest, the most effective means, the functionalization effect of the fiber that obtains is also more lasting.The function powder that adopts in the fiber functionalization process is inorganic material mostly; Relatively poor with the compatibility of polymer; Thereby in the process that is equipped with functional fiber through the co-blended spinning legal system, often having the not good problem of function powder dispersiveness, this defective has influenced the raising of fiber each item performance greatly.Therefore, become based on improving the compatibility of inorganic functional powder that to improve this key of problem technological with resin matrix.

The co-blended spinning method comprises master batch method and modification microtomy; Wherein to be equipped with process simple for the master batch legal system; Universality is high; Be a kind of means commonly used, it is to extrude the functional agglomerate of preparing high function powder content earlier through screw rod, then functional agglomerate is added to being spun into certain functional fiber in the spinning chips.In the preparation process of functional agglomerate; General employing coupling agent carries out surface modification treatment to the inorganic functional powder and improves its dispersiveness in resin matrix; Yet this type clad material can only improve the dispersiveness of inorganic particle in matrix to a certain extent; Powder reuniting phenomenon in the master batch is still relatively more serious, and the existence of agglomeration will influence the functionalization effect of the fiber that obtains, and the while also causes the mechanical property of fiber and seriously influences.Therefore, prepare the powder content height, the master batch of good dispersion is of crucial importance for the spinning of functional fiber.

CBT is the mixture of different molecular weight polybutylene terephthalate (PBT) cyclic oligomer, when being heated to 190 ℃, can become as water, and the viscosity of PBT approximately is its 5000 times under the same conditions.As if the adding catalyst and under the uniform temperature condition, CBT assembles the PBT resin of synthetic high polymer amount.Simultaneously, CBT have that reaction speed is fast, course of reaction do not have that heat discharges and to various organic and inorganic materials by advantages such as good wet abilities.

In CN 101759965A, CN101570622A and CN101570623A patent, related to a kind of CBT in-situ polymerization with the preparation Nano composite material of montmorillonite; Because CBT has the characteristics of low viscosity, high fluidity; Can make nano imvite well be dispersed in the resin matrix; In-situ polymerization takes place in CBT in process, makes the PBT composite; All directly comprised catalyst in the used CBT resin of these three patent applications, but when arriving polymerization temperature polymerization reaction take place just, the viscosity pole of initial reaction stage system is low, imvite through the physical means well dispersed in polymerisation medium.In CN 101768258A, provide a kind of chemical method that the CBT catalyst is connected on the POSS nano material; And join among the CBT; Be used to prepare PBT/POSS novel nano composite, this method makes the POSS nano material become the reactive activity center, has further improved the dispersiveness of function powder in organic matrix; Yet adopt chemical method on nano material, to connect catalytic group and need that material is had certain requirement; Treatment technology is more complicated also, and the applicability of this method is narrow, has certain limitation.Therefore, seeking a kind of method simple, universality solves this problem and has important use and be worth.

Summary of the invention

The preparation method of a kind of functional poly nylon provided by the invention; Be to be raw material with CBT; Simultaneously with the surface of catalyst loading, and after mixing, carry out in-situ polymerization, prepare the function powder that the surface is coated with one deck PBT resin at function powder; Then this powder is added in the polyamide section; Make the functional poly nylon through co-blended spinning,, can improve the dispersion problem of function powder in polymeric matrix greatly because the PBT resin and the spinning chips of powder surface have splendid compatibility.The function powder that the PBT that this method obtained coats is compared with the functional agglomerate that conventional method makes, and has improved the agglomeration of function powder greatly.The key problem in technology that the present invention solves has provided a kind of preparation method of functional poly nylon.

The structural formula of CBT resin is:

The value of n is 2～7.

The preparation method of a kind of functional poly nylon provided by the invention is characterized in that may further comprise the steps:

(1) preparation of the function powder of PBT coating

1) supports the catalyst of last layer CBT on the surface of function powder

A) place ethanol to dissolve titanium class catalyst, the formation mass concentration is 25～35% solution;

B) function powder is added in the above-mentioned solution, and stirs, catalyst can fully be coated on the surface of function powder; The mass ratio of the titanium class catalyst in said function powder and the solution is 15～25:1;

C) standing demix is obtained lower sediment, under 90～100 ℃, further removes alcohol solvent, promptly gets the function powder that supports that supports catalyst;

2) preparation of mixed-powder

A) the CBT powder is mixed with the above-mentioned function powder that supports that supports catalyst, through preliminary mechanical mixture effect, make function powder can be evenly dispersed in the CBT resin, the mass ratio of said CBT and said function powder is 2～4:1;

B) mixed powder is carried out drying, because therefore the CBT resin polymerization process sensitivity suitable to the existence of moisture, must carry out the intensive drying of CBT powder before polymerization;

3) in-situ polymerization

After dried mixed-powder carried out in-situ polymerization and spraying efflorescence, promptly obtain the function powder that PBT coats;

(2) co-blended spinning of the function powder of polyamide section and PBT coating

1) function powder that above-mentioned PBT is coated joins in the polyamide section and carries out co-blended spinning, obtains the spun filament of functional poly nylon, and described polyamide section is 10～20:1 with the mass ratio of the function powder that described PBT coats;

2) spun filament to the above-mentioned functions polyamide fiber stretches, and the back coiling gained fiber that stretches is the functional poly nylon, and according to different polyamide resin lipid species, selects suitable drawing process.

The preparation method of aforesaid a kind of functional poly nylon, described titanium class catalyst is tetraethyl titanate, isopropyl titanate or metatitanic acid 2-ethylhexyl.

The preparation method of aforesaid a kind of functional poly nylon; Described function powder is one or more in CNT, nano titanium oxide, tourmaline powder, Nano Silver series antibacterial agent, nano silicon oxide and the fluorescent material, and the particle diameter of said function powder is 20～80nm.

The preparation method of aforesaid a kind of functional poly nylon, described mixing comprises:

A) CBT is put into high speed disintegrator; Process the CBT powder; Crushing operation is carried out in this process employing intermittently form, promptly adopts to pulverize to stop the repetitive operation of pulverizing again in 5～10 minutes in 2～3 minutes, and be 100～200 purpose CBT powder with the acquisition particle diameter; This operation can avoid long-time crushing process to cause the local polymerization that powder is overheated and produce powder, the phenomenon of caking;

B) obtaining CBT powder is mixed in mixer with the function powder that supports that supports catalyst; Promptly get CBT and the mixed-powder that supports function powder that supports catalyst; Wherein incorporation time is 5～10min; Rotating speed is 400～450rpm/min, can make to support supporting function powder and being evenly dispersed in the CBT powder of catalyst.

The preparation method of aforesaid a kind of functional poly nylon, described in-situ polymerization with the concrete steps of spraying efflorescence is:

A) dried mixed-powder is realized the blend process of fusion, polymerization and the material of CBT through double screw extruder; Operating temperature is controlled at 200～245 ℃, and screw speed is controlled at 100～200r/min, through the twin-screw shear action; Make function powder that good dispersiveness arranged in matrix; Simultaneously, system viscosity helps suppressing the agglomeration again of powder along with the carrying out of polymerization process constantly increases;

B) above-mentioned melt liquid and the hot compressed air that contains function powder sprays through the second fluid nozzle and the high speed that makes progress, and spray tower top leads to cold wind, the rapid cooling curing of hanging drop meeting of ejection; Wherein the temperature of hot compressed air is 220～240 ℃, and gas liquid ratio is 2～3:1 (volume ratio), and the cooling granulation that in spray tower, atomizes obtains the function powder that PBT coats, and the particle diameter of the function powder that said PBT coats is 20～30 μ m.

The preparation method of aforesaid a kind of functional poly nylon, a kind of in PA6 or the PA66 section of described polyamide section.

The preparation method of aforesaid a kind of functional poly nylon; Further; The function powder that described PBT coats adopts gas flow crushing process to pulverize; Used air-flow is the nitrogen after freeze drying, and gas pressure is 0.7～0.8Mpa, and the particle diameter of the function powder that gained PBT coats is 3～5 μ m.

The preparation method of aforesaid a kind of functional poly nylon; Described drying is meant said CBT and function powder mixture vacuumize 40～48h under 80～100 ℃ of conditions; Under this condition; Can remove the moisture in the mixture fully, CBT ring-opening polymerization process can be carried out smoothly.

The preparation method of aforesaid a kind of functional poly nylon; Described co-blended spinning specifically comprises: the filtration of the drying of spinning material, melt Conveying, melt, spinnerets holes in spraying silk, cooling curing and coiling; Wherein, The baking temperature of spinning material is 70～95 ℃, and be 20～25h drying time, to guarantee the intensive drying of spinning material; The interpolation of function powder causes in the spinning material ash content more, and therefore, selecting specification is 100～200 purpose screen packs; Selecting the aperture of spinnerets is 0.3～0.5mm; Guarantee carrying out smoothly of spinning process, spinning temperature is 260～290 ℃, and spinning speed is 600～1500m/min.

The preparation method of aforesaid a kind of functional poly nylon, the technological parameter of described stretching is: 70～150 ℃ of draft temperatures, the draft temperature that carries out under the condition of HEAT SETTING are 110～230 ℃, draw ratio is 3.5～4 times.

Beneficial effect

The present invention is through the method for in-situ polymerization; With the surface coating raw material of CBT as powder; Through selecting suitable processing method and technological parameter, prepared the function powder that PBT coats, because PBT and polyamide (PA6, PA66) all have good compatibility; It is added in the polyamide section, can prepare functionalization effect fiber with excellent material.Its preparation method has following advantage: when preparing the function powder of PBT coating; Adopt physical method to support the catalyst of one deck CBT on the function powder surface; Simple to operate, processing technology environmental protection, and have very high universality, this function powder is not only the center of material performance function; Simultaneously also be the activated centre that ring-opening polymerization takes place CBT, this technical guarantee the PBT resin can coat function powder fully.Simultaneously, compare with the traditional functions master batch, the function powder particle diameter that PBT coats is little, can be well dispersed in the polyamide section, has improved the agglomeration of function powder greatly.When co-blended spinning, the function powder that PBT coats has good dispersiveness in polyamide substrate, and functionalization is remarkably productive.

Description of drawings

Fig. 1 is the sketch map that supports function powder that the surface supports the CBT catalyst

Fig. 2 is with CBT powder and function powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports catalyst

Fig. 3 is the sketch map that PBT coats a function powder

Fig. 4 is the sketch map that PBT coats two function powders

Wherein 1 is function powder, the 2nd, and titanium class catalyst, the 3rd, CBT powder, the 4th, PBT resin.

The specific embodiment

Below in conjunction with the specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.

Embodiment 1

(1) preparation of PBT coated carbon nanotube powder

1) supports the catalyst of last layer CBT on the surface of carbon nanotube dust: place ethanol to dissolve the catalyst Ti acetoacetic ester, form mass concentration and be 25% solution; Carbon nanotube dust is added in the above-mentioned solution, and stirs; The particle diameter of said carbon nanotube dust is 20nm, and the mass ratio of the tetraethyl titanate in said carbon nanotube dust and the solution is 15:1; Standing demix; Obtain lower sediment, under 90 ℃, further remove alcohol solvent, promptly get the carbon nanotube dust that supports that supports tetraethyl titanate; Fig. 1 is the sketch map that supports function powder that the surface supports the CBT catalyst; Promptly the surface supports the sketch map that carbon nanotube dust of tetraethyl titanate, and the function powder of 1 expression is a carbon nanotube dust among the figure, and the titanium class catalyst of 2 expressions is tetraethyl titanates; Carbon nanotube dust 1 has supported one deck tetraethyl titanate 2 on the surface of carbon nanotube dust 1 after the ethanolic solution that contains tetraethyl titanate 2 is handled;

2) preparation of mixed-powder: the CBT powder is mixed with the above-mentioned carbon nanotube dust that supports that supports tetraethyl titanate; The mass ratio of said CBT and said carbon nanotube dust is 2:1; Fig. 2 is with CBT powder and function powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports catalyst; Promptly be with CBT powder and carbon nanotube dust is mixed the back mixed-powder that obtains in mixer the sketch map that supports that supports tetraethyl titanate; The function powder of 1 expression is a carbon nanotube dust among the figure, and the titanium class catalyst of 2 expressions is tetraethyl titanates, and 3 is the CBT powder; Through the mechanical mixture effect, support supporting carbon nanotube dust and can being dispersed in the CBT powder 3 uniformly of tetraethyl titanate; And mixed powder carried out drying;

3) in-situ polymerization: with dried mixed-powder carry out in-situ polymerization with the spraying efflorescence after; Promptly obtain PBT coated carbon nanotube powder; Fig. 3 is the sketch map that PBT coats a function powder; Be the sketch map that PBT coats a carbon nanotube dust, Fig. 4 is the sketch map that PBT coats two function powders, and promptly PBT coats the sketch map of two carbon nanotube dust;

(2) co-blended spinning of PA6 section and PBT coated carbon nanotube powder

1) above-mentioned PBT coated carbon nanotube powder is joined in the PA6 section carry out co-blended spinning, obtain the spun filament of functionalization PA6 fiber, described PA6 section is 10:1 with the mass ratio of described PBT coated carbon nanotube powder;

2) spun filament to above-mentioned functions PA6 fiber stretches, and the back coiling gained fiber that stretches is functionalization PA6 fiber.

The electrical conductivity of measuring the functionalization PA6 fiber of said carbon nanotubes is 2 * 10 ^-5S/cm has higher electric conductivity.

Embodiment 2

(1) preparation of the nano-titanium dioxide powder of PBT coating

1) supports the catalyst of last layer CBT on the surface of nano-titanium dioxide powder: place ethanol to dissolve the catalyst Ti isopropyl propionate, form mass concentration and be 35% solution; Nano-titanium dioxide powder is added in the above-mentioned solution, and stirs; The particle diameter of said nano-titanium dioxide powder is 40nm, and the mass ratio of the isopropyl titanate in said nano-titanium dioxide powder and the solution is 25:1; Standing demix; Obtain lower sediment, under 100 ℃, further remove alcohol solvent, promptly get the nano-titanium dioxide powder that supports that supports isopropyl titanate; Fig. 1 is the sketch map that supports function powder that the surface supports the CBT catalyst; Promptly the surface supports the sketch map that nano-titanium dioxide powder of isopropyl titanate, and the function powder of 1 expression is a nano-titanium dioxide powder among the figure, and the titanium class catalyst of 2 expressions is isopropyl titanates; Nano-titanium dioxide powder 1 has supported one deck isopropyl titanate 2 on the surface of nano-titanium dioxide powder 1 after the ethanolic solution that contains isopropyl titanate 2 is handled;

2) preparation of mixed-powder: the CBT powder is mixed with the above-mentioned nano-titanium dioxide powder that supports that supports isopropyl titanate; The mass ratio of said CBT and said nano-titanium dioxide powder is 4:1; Fig. 2 is with CBT powder and function powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports catalyst; Promptly be with CBT powder and nano-titanium dioxide powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports isopropyl titanate; The function powder of 1 expression is a nano-titanium dioxide powder among the figure, and the titanium class catalyst of 2 expressions is isopropyl titanates, and 3 is the CBT powder; Through the mechanical mixture effect, support supporting nano-titanium dioxide powder and can being dispersed in the CBT powder 3 uniformly of isopropyl titanate; Mixed powder is carried out drying;

3) in-situ polymerization: with dried mixed-powder carry out in-situ polymerization with the spraying efflorescence after; Promptly obtain the nano-titanium dioxide powder that PBT coats; Fig. 3 is the sketch map that PBT coats a function powder; Be the sketch map that PBT coats a nano-titanium dioxide powder, Fig. 4 is the sketch map that PBT coats two function powders, and promptly PBT coats the sketch map of two nano-titanium dioxide powders;

(2) co-blended spinning of the nano-titanium dioxide powder of PA66 section and PBT coating

1) nano-titanium dioxide powder that above-mentioned PBT is coated joins in the PA66 section and carries out co-blended spinning, obtains the spun filament of functionalization PA66 fiber, and described PA66 section is 10:1 with the mass ratio of the nano-titanium dioxide powder that described PBT coats;

2) spun filament to above-mentioned functions PA66 fiber stretches, and the back coiling gained fiber that stretches is functionalization PA66 fiber.

Aforesaid mixing comprises:

A) CBT is put into high speed disintegrator, process the CBT powder, crushing operation is carried out in this process employing intermittently form, promptly adopt to pulverize to stop the repetitive operation of pulverizing again in 5 minutes in 2 minutes, and be 100 purpose CBT powder with the acquisition particle diameter;

B) obtaining CBT powder is mixed in mixer with the nano-titanium dioxide powder that supports that supports isopropyl titanate; Promptly get CBT and the mixed-powder that supports nano-titanium dioxide powder that supports isopropyl titanate; Wherein incorporation time is 5min, and rotating speed is 400rpm/min.

Aforesaid in-situ polymerization with the concrete steps of spraying efflorescence is:

A) dried mixed-powder is realized the blend process of fusion, polymerization and the material of CBT through double screw extruder; Operating temperature is controlled at 200～235 ℃, and screw speed is controlled at 100r/min, through the twin-screw shear action; Make nano-titanium dioxide powder that good dispersiveness arranged in matrix; Simultaneously, system viscosity helps suppressing the agglomeration again of powder along with the carrying out of polymerization process constantly increases;

B) above-mentioned melt liquid and the hot compressed air that contains nano-titanium dioxide powder sprays through the second fluid nozzle and the high speed that makes progress, and spray tower top leads to cold wind, the rapid cooling curing of hanging drop meeting of ejection; Wherein the temperature of hot compressed air is 220 ℃, and gas liquid ratio is 2:1 (volume ratio), and the cooling granulation that in spray tower, atomizes obtains the nano-titanium dioxide powder that PBT coats, and the particle diameter of the nano-titanium dioxide powder that said PBT coats is 30 μ m.

Aforesaid preparation method; The nano-titanium dioxide powder that described PBT coats adopts gas flow crushing process to pulverize; Used air-flow is the nitrogen after freeze drying, and gas pressure is 0.7Mpa, and the particle diameter of the nano-titanium dioxide powder that gained PBT coats is 5 μ m.

Aforesaid drying is meant said CBT and nano-titanium dioxide powder mixture vacuumize 48h under 80 ℃ of conditions, under this condition, can remove the moisture in the mixture fully, and CBT ring-opening polymerization process can be carried out smoothly.

Aforesaid co-blended spinning specifically comprises: the filtration of the drying of spinning material, melt Conveying, melt, spinnerets holes in spraying silk, cooling curing and coiling; Wherein, The baking temperature of spinning material is 85 ℃, and be 20h drying time, to guarantee the intensive drying of spinning material; The interpolation of nano-titanium dioxide powder causes in the spinning material ash content more, and therefore, selecting specification is 200 purpose screen packs, and selecting the aperture of spinnerets is 0.3mm, guarantees carrying out smoothly of spinning process, and spinning temperature is 270 ℃, and spinning speed is 600m/min.

The technological parameter of aforesaid stretching is: 150 ℃ of draft temperatures, the draft temperature that carries out under the condition of HEAT SETTING are 230 ℃, and draw ratio is 4 times.

Measure said UPF＞55 that contain the functionalization PA66 fiber of nano titanium oxide, fiber possesses uvioresistant ability preferably.

Embodiment 3

(1) preparation of the tourmaline powder of PBT coating

1) supports the catalyst of last layer CBT on the surface of tourmaline powder: place ethanol to dissolve catalyst metatitanic acid 2-ethylhexyl, form mass concentration and be 30% solution; Tourmaline powder is added in the above-mentioned solution, and stirs; The particle diameter of said tourmaline powder is 60nm, and the mass ratio of the metatitanic acid 2-ethylhexyl in said tourmaline powder and the solution is 20:1; Standing demix; Obtain lower sediment, under 95 ℃, further remove alcohol solvent, promptly get the tourmaline powder that supports that supports metatitanic acid 2-ethylhexyl; Fig. 1 is the sketch map that supports function powder that the surface supports the CBT catalyst; Promptly the surface supports the sketch map that tourmaline powder of metatitanic acid 2-ethylhexyl, and the function powder of 1 expression is a tourmaline powder among the figure, and the titanium class catalyst of 2 expressions is metatitanic acid 2-ethylhexyls; Tourmaline powder 1 has supported one deck metatitanic acid 2-ethylhexyl 2 on the surface of tourmaline powder 1 after the ethanolic solution that contains metatitanic acid 2-ethylhexyl 2 is handled;

2) preparation of mixed-powder: the CBT powder is mixed with the above-mentioned tourmaline powder that supports that supports metatitanic acid 2-ethylhexyl; The mass ratio of said CBT and said tourmaline powder is 3:1; Fig. 2 is with CBT powder and function powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports catalyst; Promptly be with CBT powder and tourmaline powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports metatitanic acid 2-ethylhexyl; The function powder of 1 expression is a tourmaline powder among the figure, and the titanium class catalyst of 2 expressions is metatitanic acid 2-ethylhexyls, and 3 is the CBT powder; Through the mechanical mixture effect, support supporting tourmaline powder and can being dispersed in the CBT powder 3 uniformly of metatitanic acid 2-ethylhexyl; Mixed powder is carried out drying;

3) in-situ polymerization: with dried mixed-powder carry out in-situ polymerization with the spraying efflorescence after; Promptly obtain the tourmaline powder that PBT coats; Fig. 3 is the sketch map that PBT coats a function powder; Be the sketch map that PBT coats a tourmaline powder, Fig. 4 is the sketch map that PBT coats two function powders, and promptly PBT coats the sketch map of two tourmaline powders;

(2) co-blended spinning of the tourmaline powder of PA6 section and PBT coating

1) tourmaline powder that above-mentioned PBT is coated joins in the PA6 section and carries out co-blended spinning, obtains the spun filament of functionalization PA6 fiber, and described PA6 section is 20:1 with the mass ratio of the tourmaline powder that described PBT coats;

Aforesaid mixing comprises:

A) CBT is put into high speed disintegrator, process the CBT powder, crushing operation is carried out in this process employing intermittently form, promptly adopt to pulverize to stop the repetitive operation of pulverizing again in 10 minutes in 3 minutes, and be 200 purpose CBT powder with the acquisition particle diameter;

B) obtaining CBT powder is mixed in mixer with the tourmaline powder that supports that supports metatitanic acid 2-ethylhexyl; Promptly get CBT and the mixed-powder that supports tourmaline powder that supports metatitanic acid 2-ethylhexyl; Wherein incorporation time is 10min, and rotating speed is 450rpm/min.

A) dried mixed-powder is realized the blend process of fusion, polymerization and the material of CBT through double screw extruder; Operating temperature is controlled at 205～245 ℃, and screw speed is controlled at 200r/min, through the twin-screw shear action; Make tourmaline powder that good dispersiveness arranged in matrix; Simultaneously, system viscosity helps suppressing the agglomeration again of powder along with the carrying out of polymerization process constantly increases;

B) above-mentioned melt liquid and the hot compressed air that contains tourmaline powder sprays through the second fluid nozzle and the high speed that makes progress, and spray tower top leads to cold wind, the rapid cooling curing of hanging drop meeting of ejection; Wherein the temperature of hot compressed air is 240 ℃, and gas liquid ratio is 3:1 (volume ratio), and the cooling granulation that in spray tower, atomizes obtains the tourmaline powder that PBT coats, and the particle diameter of the tourmaline powder that said PBT coats is 20 μ m.

Aforesaid preparation method, the tourmaline powder that described PBT coats adopts gas flow crushing process to pulverize, and used air-flow is the nitrogen after freeze drying, and gas pressure is 0.8Mpa, and the particle diameter of the tourmaline powder that gained PBT coats is 3 μ m.

Aforesaid drying is meant said CBT and tourmaline powder mixture vacuumize 40h under 100 ℃ of conditions, under this condition, can remove the moisture in the mixture fully, and CBT ring-opening polymerization process can be carried out smoothly.

Aforesaid co-blended spinning specifically comprises: the filtration of the drying of spinning material, melt Conveying, melt, spinnerets holes in spraying silk, cooling curing and coiling; Wherein, The baking temperature of spinning material is 80 ℃, and be 25h drying time, to guarantee the intensive drying of spinning material; The interpolation of tourmaline powder causes in the spinning material ash content more, and therefore, selecting specification is 100 purpose screen packs, and selecting the aperture of spinnerets is 0.3mm, guarantees carrying out smoothly of spinning process, and spinning temperature is 265 ℃, and spinning speed is 800m/min.

The technological parameter of aforesaid stretching is: 75 ℃ of draft temperatures, the draft temperature that carries out under the condition of HEAT SETTING are 120 ℃, and draw ratio is 3.8 times.

Measure the said anion release concentration that contains the functionalization PA6 fiber of tourmaline powder and can reach 4500/cm ³, human body is had good health-care effect.

Embodiment 4

(1) preparation of the Nano Silver series antibacterial agent of PBT coating

1) supports the catalyst of last layer CBT on the surface of Nano Silver series antibacterial agent: place ethanol to dissolve the catalyst Ti acetoacetic ester, form mass concentration and be 25% solution; The Nano Silver series antibacterial agent is added in the above-mentioned solution, and stirs; The particle diameter of said Nano Silver series antibacterial agent is 40nm, and the mass ratio of the tetraethyl titanate in said Nano Silver series antibacterial agent and the solution is 20:1; Standing demix; Obtain lower sediment, under 95 ℃, further remove alcohol solvent, promptly get support tetraethyl titanate support the Nano Silver series antibacterial agent; Fig. 1 is the sketch map that supports function powder that the surface supports the CBT catalyst; Promptly the surface supports the sketch map that the Nano Silver series antibacterial agent of tetraethyl titanate, and the function powder of 1 expression is the Nano Silver series antibacterial agent among the figure, and the titanium class catalyst of 2 expressions is tetraethyl titanates; Nano Silver series antibacterial agent 1 has supported one deck tetraethyl titanate 2 on the surface of Nano Silver series antibacterial agent 1 after the ethanolic solution that contains tetraethyl titanate 2 is handled;

2) preparation of mixed-powder: the CBT powder is mixed with the above-mentioned Nano Silver series antibacterial agent that supports that supports tetraethyl titanate; The mass ratio of said CBT and said Nano Silver series antibacterial agent is 2:1; Fig. 2 is with CBT powder and function powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports catalyst; Promptly be with CBT powder and the Nano Silver series antibacterial agent mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports tetraethyl titanate; The function powder of 1 expression is the Nano Silver series antibacterial agent among the figure, and the titanium class catalyst of 2 expressions is tetraethyl titanates, and 3 is the CBT powder; Through the mechanical mixture effect, support supporting the Nano Silver series antibacterial agent and can being dispersed in the CBT powder 3 uniformly of tetraethyl titanate; Mixed powder is carried out drying;

3) in-situ polymerization: with dried mixed-powder carry out in-situ polymerization with the spraying efflorescence after; Promptly obtain the Nano Silver series antibacterial agent that PBT coats; Fig. 3 is the sketch map that PBT coats a function powder; Be the sketch map that PBT coats a Nano Silver series antibacterial agent, Fig. 4 is the sketch map that PBT coats two function powders, and promptly PBT coats the sketch map of two Nano Silver series antibacterial agents; (2) co-blended spinning of the Nano Silver series antibacterial agent of PA66 section and PBT coating

1) the Nano Silver series antibacterial agent that above-mentioned PBT is coated joins in the PA66 section and carries out co-blended spinning, obtains the spun filament of functionalization PA66 fiber, and described PA66 section is 15:1 with the mass ratio of the Nano Silver series antibacterial agent that described PBT coats;

Aforesaid mixing comprises:

B) obtaining CBT powder is mixed in mixer with the Nano Silver series antibacterial agent that supports that supports tetraethyl titanate, promptly get CBT and the mixed-powder that supports the Nano Silver series antibacterial agent that supports tetraethyl titanate, wherein incorporation time is 8min, and rotating speed is 450rpm/min.

A) dried mixed-powder is realized the blend process of fusion, polymerization and the material of CBT through double screw extruder; Operating temperature is controlled at 200～235 ℃, and screw speed is controlled at 150r/min, through the twin-screw shear action; Make the Nano Silver series antibacterial agent that good dispersiveness arranged in matrix; Simultaneously, system viscosity helps suppressing the agglomeration again of powder along with the carrying out of polymerization process constantly increases;

B) above-mentioned melt liquid and the hot compressed air that contains the Nano Silver series antibacterial agent sprays through the second fluid nozzle and the high speed that makes progress, and spray tower top leads to cold wind, the rapid cooling curing of hanging drop meeting of ejection; Wherein the temperature of hot compressed air is 225 ℃, and gas liquid ratio is 2.5:1 (volume ratio), and the cooling granulation that in spray tower, atomizes obtains the Nano Silver series antibacterial agent that PBT coats, and the particle diameter of the Nano Silver series antibacterial agent that said PBT coats is 25 μ m.

Aforesaid preparation method, the Nano Silver series antibacterial agent that described PBT coats adopts gas flow crushing process to pulverize, and used air-flow is the nitrogen after freeze drying, and gas pressure is 0.7Mpa, and the particle diameter of the Nano Silver series antibacterial agent that gained PBT coats is 5 μ m.

Aforesaid drying is meant said CBT and Nano Silver series antibacterial agent mixture vacuumize 45h under 95 ℃ of conditions, under this condition, can remove the moisture in the mixture fully, and CBT ring-opening polymerization process can be carried out smoothly.

Aforesaid co-blended spinning specifically comprises: the filtration of the drying of spinning material, melt Conveying, melt, spinnerets holes in spraying silk, cooling curing and coiling; Wherein, The baking temperature of spinning material is 95 ℃, and be 22h drying time, to guarantee the intensive drying of spinning material; The interpolation of Nano Silver series antibacterial agent causes in the spinning material ash content more, and therefore, selecting specification is 100 purpose screen packs, and selecting the aperture of spinnerets is 0.3mm, guarantees carrying out smoothly of spinning process, and spinning temperature is 290 ℃, and spinning speed is 800m/min.

Measure the said anti-microbial property that contains the functionalization PA66 fiber of Nano Silver series antibacterial agent: Escherichia coli antibiotic rate >=99%, staphylococcus aureus antibiotic rate >=99%, Candida albicans antibiotic rate >=95%.

Embodiment 5

(1) preparation of the nano silicon oxide of PBT coating

1) supports the catalyst of last layer CBT on the surface of nano silicon oxide: place ethanol to dissolve the catalyst Ti isopropyl propionate, form mass concentration and be 35% solution; Nano silicon oxide is added in the above-mentioned solution, and stirs; The particle diameter of said nano silicon oxide is 40nm, and the mass ratio of the isopropyl titanate in said nano silicon oxide and the solution is 20:1; Standing demix; Obtain lower sediment, under 100 ℃, further remove alcohol solvent, promptly get the nano silicon oxide that supports that supports isopropyl titanate; Fig. 1 is the sketch map that supports function powder that the surface supports the CBT catalyst; Promptly the surface supports the sketch map that nano silicon oxide of isopropyl titanate, and the function powder of 1 expression is a nano silicon oxide among the figure, and the titanium class catalyst of 2 expressions is isopropyl titanates; Nano silicon oxide 1 has supported one deck isopropyl titanate 2 on the surface of nano silicon oxide 1 after the ethanolic solution that contains isopropyl titanate 2 is handled;

2) preparation of mixed-powder: the CBT powder is mixed with the above-mentioned nano silicon oxide that supports that supports isopropyl titanate; The mass ratio of said CBT and said nano silicon oxide is 2:1; Fig. 2 is with CBT powder and function powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports catalyst; Promptly be with CBT powder and nano silicon oxide mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports isopropyl titanate; The function powder of 1 expression is a nano silicon oxide among the figure, and the titanium class catalyst of 2 expressions is isopropyl titanates, and 3 is the CBT powder; Through the mechanical mixture effect, support supporting nano silicon oxide and can being dispersed in the CBT powder 3 uniformly of isopropyl titanate; Mixed powder is carried out drying;

3) in-situ polymerization: with dried mixed-powder carry out in-situ polymerization with the spraying efflorescence after; Promptly obtain the nano silicon oxide that PBT coats; Fig. 3 is the sketch map that PBT coats a function powder; Be the sketch map that PBT coats a nano silicon oxide, Fig. 4 is the sketch map that PBT coats two function powders, and promptly PBT coats the sketch map of two nano silicon oxides;

(2) co-blended spinning of the nano silicon oxide of PA6 section and PBT coating

1) nano silicon oxide that above-mentioned PBT is coated joins in the PA6 section and carries out co-blended spinning, obtains the spun filament of functionalization PA6 fiber, and described PA6 section is 10:1 with the mass ratio of the nano silicon oxide that described PBT coats;

Aforesaid mixing comprises:

A) CBT is put into high speed disintegrator, process the CBT powder, crushing operation is carried out in this process employing intermittently form, promptly adopt to pulverize to stop the repetitive operation of pulverizing again in 5 minutes in 3 minutes, and be 150 purpose CBT powder with the acquisition particle diameter;

B) obtaining CBT powder is mixed in mixer with the nano silicon oxide that supports that supports isopropyl titanate, promptly get CBT and the mixed-powder that supports nano silicon oxide that supports isopropyl titanate, wherein incorporation time is 8min, and rotating speed is 450rpm/min.

A) dried mixed-powder is realized the blend process of fusion, polymerization and the material of CBT through double screw extruder; Operating temperature is controlled at 200～235 ℃, and screw speed is controlled at 150r/min, through the twin-screw shear action; Make nano silicon oxide that good dispersiveness arranged in matrix; Simultaneously, system viscosity helps suppressing the agglomeration again of powder along with the carrying out of polymerization process constantly increases;

B) above-mentioned melt liquid and the hot compressed air that contains nano silicon oxide sprays through the second fluid nozzle and the high speed that makes progress, and spray tower top leads to cold wind, the rapid cooling curing of hanging drop meeting of ejection; Wherein the temperature of hot compressed air is 225 ℃, and gas liquid ratio is 2.5:1 (volume ratio), and the cooling granulation that in spray tower, atomizes obtains the nano silicon oxide that PBT coats, and the particle diameter of the nano silicon oxide that said PBT coats is 25 μ m.

Aforesaid preparation method, the nano silicon oxide that described PBT coats adopts gas flow crushing process to pulverize, and used air-flow is the nitrogen after freeze drying, and gas pressure is 0.8Mpa, and the particle diameter of the nano silicon oxide that gained PBT coats is 3 μ m.

Aforesaid drying is meant said CBT and nano silicon oxide mixture vacuumize 45h under 90 ℃ of conditions, under this condition, can remove the moisture in the mixture fully, and CBT ring-opening polymerization process can be carried out smoothly.

Aforesaid co-blended spinning specifically comprises: the filtration of the drying of spinning material, melt Conveying, melt, spinnerets holes in spraying silk, cooling curing and coiling; Wherein, The baking temperature of spinning material is 70 ℃, and be 25h drying time, to guarantee the intensive drying of spinning material; The interpolation of nano silicon oxide causes in the spinning material ash content more, and therefore, selecting specification is 100 purpose screen packs, and selecting the aperture of spinnerets is 0.5mm, guarantees carrying out smoothly of spinning process, and spinning temperature is 260 ℃, and spinning speed is 1500m/min.

The technological parameter of aforesaid stretching is: 70 ℃ of draft temperatures, the draft temperature that carries out under the condition of HEAT SETTING are 110 ℃, and draw ratio is 3.5 times.

Measure the said far infrared emitting performance that contains the functionalization PA6 fiber of nano silicon oxide, the infrared emittance of this far IR fibre is 96%.

Embodiment 6

(1) preparation of the fluorescent powder of PBT coating

1) supports the catalyst of last layer CBT on the surface of fluorescent powder: place ethanol to dissolve the catalyst Ti isopropyl propionate, form mass concentration and be 25% solution; Fluorescent powder is added in the above-mentioned solution, and stirs; The particle diameter of said fluorescent powder is 80nm, and the mass ratio of the isopropyl titanate in said fluorescent powder and the solution is 15:1; Standing demix; Obtain lower sediment, under 90 ℃, further remove alcohol solvent, promptly get the fluorescent powder that supports that supports isopropyl titanate; Fig. 1 is the sketch map that supports function powder that the surface supports the CBT catalyst; Promptly the surface supports the sketch map that fluorescent powder of isopropyl titanate, and the function powder of 1 expression is a fluorescent powder among the figure, and the titanium class catalyst of 2 expressions is isopropyl titanates; Fluorescent powder 1 has supported one deck isopropyl titanate 2 on the surface of fluorescent powder 1 after the ethanolic solution that contains isopropyl titanate 2 is handled;

2) preparation of mixed-powder: the CBT powder is mixed with the above-mentioned fluorescent powder that supports that supports isopropyl titanate; The mass ratio of said CBT and said fluorescent powder is 4:1; Fig. 2 is with CBT powder and function powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports catalyst; Promptly be with CBT powder and fluorescent powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports isopropyl titanate; The function powder of 1 expression is a fluorescent powder among the figure, and the titanium class catalyst of 2 expressions is isopropyl titanates, and 3 is the CBT powder; Through the mechanical mixture effect, support supporting fluorescent powder and can being dispersed in the CBT powder 3 uniformly of isopropyl titanate; Mixed powder is carried out drying;

3) in-situ polymerization: with dried mixed-powder carry out in-situ polymerization with the spraying efflorescence after; Promptly obtain the fluorescent powder that PBT coats; Fig. 3 is the sketch map that PBT coats a function powder; Be the sketch map that PBT coats a fluorescent powder, Fig. 4 is the sketch map that PBT coats two function powders, and promptly PBT coats the sketch map of two fluorescent powders;

(2) co-blended spinning of the fluorescent powder of PA6 section and PBT coating

1) fluorescent powder that above-mentioned PBT is coated joins in the PA6 section and carries out co-blended spinning, obtains the spun filament of functionalization PA6 fiber, and described PA6 section is 20:1 with the mass ratio of the fluorescent powder that described PBT coats;

Aforesaid mixing comprises:

B) obtaining CBT powder is mixed in mixer with the fluorescent powder that supports that supports isopropyl titanate, promptly get CBT and the mixed-powder that supports fluorescent powder that supports isopropyl titanate, wherein incorporation time is 10min, and rotating speed is 400rpm/min.

A) dried mixed-powder is realized the blend process of fusion, polymerization and the material of CBT through double screw extruder; Operating temperature is controlled at 215～245 ℃, and screw speed is controlled at 150r/min, through the twin-screw shear action; Make fluorescent powder that good dispersiveness arranged in matrix; Simultaneously, system viscosity helps suppressing the agglomeration again of powder along with the carrying out of polymerization process constantly increases;

B) above-mentioned melt liquid and the hot compressed air that contains fluorescent powder sprays through the second fluid nozzle and the high speed that makes progress, and spray tower top leads to cold wind, the rapid cooling curing of hanging drop meeting of ejection; Wherein the temperature of hot compressed air is 230 ℃, and gas liquid ratio is 2:1 (volume ratio), and the cooling granulation that in spray tower, atomizes obtains the fluorescent powder that PBT coats, and the particle diameter of the fluorescent powder that said PBT coats is 25 μ m.

Aforesaid preparation method, the fluorescent powder that described PBT coats adopts gas flow crushing process to pulverize, and used air-flow is the nitrogen after freeze drying, and gas pressure is 0.7Mpa, and the particle diameter of the fluorescent powder that gained PBT coats is 5 μ m.

Aforesaid drying is meant said CBT and fluorescent powder mixture vacuumize 48h under 80 ℃ of conditions, under this condition, can remove the moisture in the mixture fully, and CBT ring-opening polymerization process can be carried out smoothly.

Aforesaid co-blended spinning specifically comprises: the filtration of the drying of spinning material, melt Conveying, melt, spinnerets holes in spraying silk, cooling curing and coiling; Wherein, The baking temperature of spinning material is 70 ℃, and be 25h drying time, to guarantee the intensive drying of spinning material; The interpolation of fluorescent powder causes in the spinning material ash content more, and therefore, selecting specification is 100 purpose screen packs, and selecting the aperture of spinnerets is 0.4mm, guarantees carrying out smoothly of spinning process, and spinning temperature is 270 ℃, and spinning speed is 800m/min.

The technological parameter of aforesaid stretching is: 70 ℃ of draft temperatures, the draft temperature that carries out under the condition of HEAT SETTING are 110 ℃, and draw ratio is 3.6 times.

Measure said luminous initial strength and the persistence that contains the functionalization PA6 fiber of fluorescent powder, its luminous initial strength is greater than 800mcd/m ², persistence was greater than 8 hours.

Embodiment 7

(1) nano silica powder of PBT coating and the preparation of nano-titanium dioxide powder

1) supports the catalyst of last layer CBT on the surface of nano silica powder and nano-titanium dioxide powder: place ethanol to dissolve the catalyst Ti acetoacetic ester, form mass concentration and be 30% solution; Nano silica powder and nano-titanium dioxide powder are added in the above-mentioned solution, and stir; The particle diameter of said nano silica powder and nano-titanium dioxide powder is 40nm; The gross mass of said nano silica powder and nano-titanium dioxide powder and the mass ratio of the tetraethyl titanate in the solution are 20:1, and the mass ratio of said nano silica powder and nano-titanium dioxide powder is 1.5:1; Standing demix; Obtain lower sediment; Under 95 ℃, further remove alcohol solvent; Promptly get and support supporting nano silica powder and supporting the nano-titanium dioxide powder of tetraethyl titanate of tetraethyl titanate, Fig. 1 is the sketch map that supports function powder that the surface supports the CBT catalyst, and promptly the surface supports supporting nano silica powder or supporting the sketch map that nano-titanium dioxide powder of tetraethyl titanate of tetraethyl titanate; The function powder of 1 expression is nano silica powder or nano-titanium dioxide powder among the figure; The titanium class catalyst of 2 expressions is tetraethyl titanates, and nano silica powder and nano-titanium dioxide powder 1 have supported one deck tetraethyl titanate 2 on the surface of nano silica powder and nano-titanium dioxide powder 1 after the ethanolic solution that contains tetraethyl titanate 2 is handled;

2) preparation of mixed-powder: the CBT powder is mixed with the nano-titanium dioxide powder that supports that supports tetraethyl titanate with the above-mentioned nano silica powder that supports that supports tetraethyl titanate; The quality of said CBT is 4:1 with the ratio of the gross mass of said nano silica powder and nano-titanium dioxide powder; Fig. 2 is with CBT powder and function powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports catalyst; Promptly be that the CBT powder is mixed the sketch map of the mixed-powder that obtains afterwards with the nano silica powder that supports that supports tetraethyl titanate with the nano-titanium dioxide powder that supports that supports tetraethyl titanate in mixer; The function powder of 1 expression is nano silica powder or nano-titanium dioxide powder among the figure; The titanium class catalyst of 2 expressions is tetraethyl titanates; 3 is the CBT powder, through the mechanical mixture effect, supports supporting nano silica powder and supporting supporting nano-titanium dioxide powder and can being dispersed in the CBT powder 3 uniformly of tetraethyl titanate of tetraethyl titanate; Mixed powder is carried out drying;

3) in-situ polymerization: with dried mixed-powder carry out in-situ polymerization with the spraying efflorescence after; Promptly obtain nano silica powder and nano-titanium dioxide powder that PBT coats; Fig. 3 is the sketch map that PBT coats a function powder; It is the sketch map that PBT coats a nano silica powder or a nano-titanium dioxide powder of PBT coating; Fig. 4 is the sketch map that PBT coats two function powders, and promptly PBT coats the sketch map that two nano silica powders, two nano-titanium dioxide powders of PBT coating or PBT coat a nano silica powder and a nano-titanium dioxide powder;

(2) PA6 section and the nano silica powder of PBT coating and the co-blended spinning of nano-titanium dioxide powder

1) nano silica powder that above-mentioned PBT is coated and nano-titanium dioxide powder join PA6 and carry out co-blended spinning in cutting into slices; Obtain the spun filament of functionalization PA6 fiber, the ratio of the nano silica powder that described PA6 chipping qualities and described PBT coat and the gross mass of nano-titanium dioxide powder is 15:1;

Aforesaid mixing comprises:

B) obtaining CBT powder is mixed in mixer with the nano-titanium dioxide powder that supports that supports tetraethyl titanate with the nano silica powder that supports that supports tetraethyl titanate; Promptly get CBT and support supporting nano silica powder and supporting the mixed-powder that nano-titanium dioxide powder of tetraethyl titanate of tetraethyl titanate; Wherein incorporation time is 5min, and rotating speed is 450rpm/min.

A) dried mixed-powder is realized the blend process of fusion, polymerization and the material of CBT through double screw extruder; Operating temperature is controlled at 200～235 ℃, and screw speed is controlled at 200r/min, through the twin-screw shear action; Make nano silica powder and nano-titanium dioxide powder that good dispersiveness arranged in matrix; Simultaneously, system viscosity helps suppressing the agglomeration again of powder along with the carrying out of polymerization process constantly increases;

B) above-mentioned melt liquid and the hot compressed air that contains nano silica powder and nano-titanium dioxide powder sprays through the second fluid nozzle and the high speed that makes progress, and spray tower top leads to cold wind, the rapid cooling curing of hanging drop meeting of ejection; Wherein the temperature of hot compressed air is 230 ℃; Gas liquid ratio is 2:1 (volume ratio); The cooling granulation that in spray tower, atomizes obtains nano silica powder and the nano-titanium dioxide powder that PBT coats, and the nano silica powder that said PBT coats and the particle diameter of nano-titanium dioxide powder are 25 μ m.

Aforesaid preparation method; Nano silica powder that described PBT coats and nano-titanium dioxide powder adopt gas flow crushing process to pulverize; Used air-flow is the nitrogen after freeze drying; Gas pressure is 0.7Mpa, and the nano silica powder that gained PBT coats and the particle diameter of nano-titanium dioxide powder are 5 μ m.

Aforesaid drying is meant said CBT and nano silica powder and nano-titanium dioxide powder mixture vacuumize 40h under 100 ℃ of conditions; Under this condition; Can remove the moisture in the mixture fully, CBT ring-opening polymerization process can be carried out smoothly.

Aforesaid co-blended spinning specifically comprises: the filtration of the drying of spinning material, melt Conveying, melt, spinnerets holes in spraying silk, cooling curing and coiling; Wherein, The baking temperature of spinning material is 85 ℃, and be 22h drying time, to guarantee the intensive drying of spinning material; The interpolation of nano silica powder and nano-titanium dioxide powder causes in the spinning material ash content more, and therefore, selecting specification is 200 purpose screen packs; Selecting the aperture of spinnerets is 0.3mm; Guarantee carrying out smoothly of spinning process, spinning temperature is 265 ℃, and spinning speed is 1000m/min.

The technological parameter of aforesaid stretching is: 85 ℃ of draft temperatures, the draft temperature that carries out under the condition of HEAT SETTING are 120 ℃, and draw ratio is 3.5 times.

Measure the said functionalization effect that contains the functionalization PA6 fiber of nano silica powder and nano-titanium dioxide powder: the infrared emittance of functionalization PA6 fiber is 90%, the UPF of functionalization PA6 fiber＞50.

Embodiment 8

(1) fluorescent powder of PBT coating and the preparation of tourmaline powder

1) supports the catalyst of last layer CBT on the surface of fluorescent powder and tourmaline powder: place ethanol to dissolve the catalyst Ti acetoacetic ester, form mass concentration and be 30% solution; Fluorescent powder and tourmaline powder are added in the above-mentioned solution, and stir; The particle diameter of said fluorescent powder and tourmaline powder is respectively 80nm and 60nm, and the gross mass of said fluorescent powder and tourmaline powder and the mass ratio of the tetraethyl titanate in the solution are 25:1, and the mass ratio of described fluorescent powder and tourmaline powder is 3:1; Standing demix; Obtain lower sediment; Under 95 ℃, further remove alcohol solvent; Promptly get and support supporting fluorescent powder and supporting the tourmaline powder of tetraethyl titanate of tetraethyl titanate, Fig. 1 is the sketch map that supports function powder that the surface supports the CBT catalyst, and promptly the surface supports supporting fluorescent powder or supporting the sketch map that tourmaline powder of tetraethyl titanate of tetraethyl titanate; The functional agglomerate of 1 expression is fluorescent powder or tourmaline powder among the figure; The titanium class catalyst of 2 expressions is tetraethyl titanates, and fluorescent powder and tourmaline powder 1 have supported one deck tetraethyl titanate 2 on the surface of fluorescent powder and tourmaline powder 1 after the ethanolic solution that contains tetraethyl titanate 2 is handled;

2) preparation of mixed-powder: the CBT powder is mixed with the tourmaline powder that supports that supports tetraethyl titanate with the above-mentioned fluorescent powder that supports that supports tetraethyl titanate; The quality of said CBT is 3:1 with the ratio of the gross mass of said fluorescent powder and tourmaline powder; Fig. 2 is with CBT powder and function powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports catalyst; Promptly be that the CBT powder is mixed the sketch map of the mixed-powder that obtains afterwards with the fluorescent powder that supports that supports tetraethyl titanate with the tourmaline powder that supports that supports tetraethyl titanate in mixer; The functional agglomerate of 1 expression is fluorescent powder or tourmaline powder among the figure; The titanium class catalyst of 2 expressions is tetraethyl titanates; 3 is the CBT powder, through the mechanical mixture effect, supports supporting fluorescent powder and supporting supporting tourmaline powder and can being dispersed in the CBT powder 3 uniformly of tetraethyl titanate of tetraethyl titanate; Mixed powder is carried out drying;

3) in-situ polymerization: with dried mixed-powder carry out in-situ polymerization with the spraying efflorescence after; Promptly obtain fluorescent powder and tourmaline powder that PBT coats; Fig. 3 is the sketch map that PBT coats a function powder; It is the sketch map that PBT coats a fluorescent powder or a tourmaline powder of PBT coating; Fig. 4 is the sketch map that PBT coats two function powders, and promptly PBT coats the sketch map that two fluorescent powders, two tourmaline powders of PBT coating or PBT coat a fluorescent powder and a tourmaline powder;

(2) PA6 section and the fluorescent powder of PBT coating and the co-blended spinning of tourmaline powder

1) fluorescent powder that above-mentioned PBT is coated and tourmaline powder join PA6 and carry out co-blended spinning in cutting into slices; Obtain the spun filament of functionalization PA6 fiber, the ratio of the fluorescent powder that described PA6 chipping qualities and described PBT coat and the gross mass of tourmaline powder is 10:1;

Aforesaid mixing comprises:

B) obtaining CBT powder is mixed in mixer with the tourmaline powder that supports that supports tetraethyl titanate with the fluorescent powder that supports that supports tetraethyl titanate; Promptly get CBT and support supporting fluorescent powder and supporting the mixed-powder that tourmaline powder of tetraethyl titanate of tetraethyl titanate; Wherein incorporation time is 10min, and rotating speed is 400rpm/min.

A) dried mixed-powder is realized the blend process of fusion, polymerization and the material of CBT through double screw extruder; Operating temperature is controlled at 200～235 ℃, and screw speed is controlled at 150r/min, through the twin-screw shear action; Make fluorescent powder and tourmaline powder that good dispersiveness arranged in matrix; Simultaneously, system viscosity helps suppressing the agglomeration again of powder along with the carrying out of polymerization process constantly increases;

B) above-mentioned melt liquid and the hot compressed air that contains fluorescent powder and tourmaline powder sprays through the second fluid nozzle and the high speed that makes progress, and spray tower top leads to cold wind, the rapid cooling curing of hanging drop meeting of ejection; Wherein the temperature of hot compressed air is 220 ℃, and gas liquid ratio is 3:1 (volume ratio), and the cooling granulation that in spray tower, atomizes obtains fluorescent powder and the tourmaline powder that PBT coats, and the fluorescent powder that said PBT coats and the particle diameter of tourmaline powder are 25 μ m.

Aforesaid preparation method; Fluorescent powder that described PBT coats and tourmaline powder adopt gas flow crushing process to pulverize; Used air-flow is the nitrogen after freeze drying, and gas pressure is 0.8Mpa, and the fluorescent powder that gained PBT coats and the particle diameter of tourmaline powder are 3 μ m.

Aforesaid drying is meant said CBT and fluorescent powder and tourmaline powder mixture vacuumize 40h under 100 ℃ of conditions, under this condition, can remove the moisture in the mixture fully, and CBT ring-opening polymerization process can be carried out smoothly.

Aforesaid co-blended spinning specifically comprises: the filtration of the drying of spinning material, melt Conveying, melt, spinnerets holes in spraying silk, cooling curing and coiling; Wherein, The baking temperature of spinning material is 75 ℃, and be 22h drying time, to guarantee the intensive drying of spinning material; The interpolation of fluorescent powder and tourmaline powder causes in the spinning material ash content more, and therefore, selecting specification is 200 purpose screen packs; Selecting the aperture of spinnerets is 0.3mm; Guarantee carrying out smoothly of spinning process, spinning temperature is 260 ℃, and spinning speed is 800m/min.

The technological parameter of aforesaid stretching is: 75 ℃ of draft temperatures, the draft temperature that carries out under the condition of HEAT SETTING are 115 ℃, and draw ratio is 3.5 times.

Measure the said functionalization effect that contains the functionalization PA6 fiber of fluorescent powder and tourmaline powder: the luminous initial strength of functionalization PA6 fiber is greater than 700mcd/m ², persistence, the anion release concentration of functionalization PA6 fiber can reach 3800/cm greater than 7 hours ³

Embodiment 9

(1) preparation of fluorescent powder, tourmaline powder and the nano-titanium dioxide powder of PBT coating

1) supports the catalyst of last layer CBT on the surface of fluorescent powder, tourmaline powder and nano-titanium dioxide powder: place ethanol to dissolve the catalyst Ti isopropyl propionate, form mass concentration and be 35% solution; Fluorescent powder, tourmaline powder and nano-titanium dioxide powder are added in the above-mentioned solution, and stir; The particle diameter of said fluorescent powder, tourmaline powder and nano-titanium dioxide powder is respectively 80nm, 60nm and 40nm; The gross mass of said fluorescent powder, tourmaline powder and nano-titanium dioxide powder and the mass ratio of the isopropyl titanate in the solution are 20:1, and the mass ratio of described fluorescent powder, tourmaline powder and nano-titanium dioxide powder is 3:2:1; Standing demix; Obtain lower sediment; Under 90 ℃, further remove alcohol solvent; Promptly get and support supporting fluorescent powder, supporting supporting tourmaline powder and supporting the nano-titanium dioxide powder of isopropyl titanate of isopropyl titanate of isopropyl titanate; Fig. 1 is the sketch map that supports function powder that the surface supports the CBT catalyst; Promptly the surface supports supporting fluorescent powder, supporting supporting tourmaline powder or supporting the sketch map that nano-titanium dioxide powder of isopropyl titanate of isopropyl titanate of isopropyl titanate, and the function powder of 1 expression is fluorescent powder, tourmaline powder or nano-titanium dioxide powder among the figure, and the titanium class catalyst of 2 expressions is isopropyl titanates; Fluorescent powder, tourmaline powder and nano-titanium dioxide powder 1 have supported one deck isopropyl titanate 2 on the surface of fluorescent powder, tourmaline powder and nano-titanium dioxide powder 1 after the ethanolic solution that contains isopropyl titanate 2 is handled;

2) preparation of mixed-powder: the CBT powder is mixed with the above-mentioned nano-titanium dioxide powder that supports that supports tourmaline powder and support isopropyl titanate that supports fluorescent powder, supports isopropyl titanate that supports isopropyl titanate; The quality of said CBT is 2:1 with the ratio of the gross mass of said fluorescent powder, tourmaline powder and nano-titanium dioxide powder; Fig. 2 is with CBT powder and function powder mixes the back mixed-powder that obtains in mixer the sketch map that supports that supports catalyst; Promptly be with the CBT powder with support isopropyl titanate support fluorescent powder, support isopropyl titanate support tourmaline powder and support isopropyl titanate support nano-titanium dioxide powder in mixer, mix the back mixed-powder that obtains sketch map; The function powder of 1 expression is fluorescent powder, tourmaline powder or nano-titanium dioxide powder among the figure; The titanium class catalyst of 2 expressions is an isopropyl titanate; 3 is the CBT powder; Through the mechanical mixture effect, support supporting fluorescent powder, supporting supporting tourmaline powder and supporting supporting nano-titanium dioxide powder and can being dispersed in the CBT powder 3 uniformly of isopropyl titanate of isopropyl titanate of isopropyl titanate; Mixed powder is carried out drying;

3) in-situ polymerization: with dried mixed-powder carry out in-situ polymerization with the spraying efflorescence after; Promptly obtain fluorescent powder, tourmaline powder and nano-titanium dioxide powder that PBT coats; Fig. 3 is the sketch map that PBT coats a function powder; Be that PBT coats the sketch map that a fluorescent powder, tourmaline powder of PBT coating or PBT coat a nano-titanium dioxide powder; Fig. 4 is the sketch map that PBT coats two function powders, and promptly PBT coats two fluorescent powders, PBT and coats two tourmaline powders, PBT and coat two tourmaline powders, PBT and coat a fluorescent powder and tourmaline powder, a PBT and coat the sketch map that a nano-titanium dioxide powder and tourmaline powder or PBT coat a fluorescent powder and a nano-titanium dioxide powder; (2) co-blended spinning of fluorescent powder, tourmaline powder and the nano-titanium dioxide powder of PA6 section and PBT coating

1) fluorescent powder, tourmaline powder and the nano-titanium dioxide powder that above-mentioned PBT is coated joins in the PA6 section and carries out co-blended spinning; Obtain the spun filament of functionalization PA6 fiber, described PA6 chipping qualities is 15:1 with the ratio of the gross mass of fluorescent powder, tourmaline powder and the nano-titanium dioxide powder of described PBT coating;

2) spun filament to above-mentioned functions PA6 fiber stretches, and the back coiling gained fiber that stretches is functionalization PBT fiber.

Aforesaid mixing comprises:

B) obtaining CBT powder is mixed in mixer with the nano-titanium dioxide powder that supports that supports tourmaline powder and support isopropyl titanate that supports fluorescent powder, supports isopropyl titanate that supports isopropyl titanate; Promptly get CBT and support supporting fluorescent powder, supporting supporting tourmaline powder and supporting the mixed-powder that nano-titanium dioxide powder of isopropyl titanate of isopropyl titanate of isopropyl titanate; Wherein incorporation time is 10min, and rotating speed is 400rpm/min.

A) dried mixed-powder is realized the blend process of fusion, polymerization and the material of CBT through double screw extruder; Operating temperature is controlled at 210～245 ℃, and screw speed is controlled at 100r/min, through the twin-screw shear action; Make fluorescent powder, tourmaline powder and nano-titanium dioxide powder that good dispersiveness arranged in matrix; Simultaneously, system viscosity helps suppressing the agglomeration again of powder along with the carrying out of polymerization process constantly increases;

B) above-mentioned melt liquid and the hot compressed air that contains fluorescent powder, tourmaline powder and nano-titanium dioxide powder sprays through the second fluid nozzle and the high speed that makes progress, and spray tower top leads to cold wind, the rapid cooling curing of hanging drop meeting of ejection; Wherein the temperature of hot compressed air is 220 ℃; Gas liquid ratio is 2:1 (volume ratio); The cooling granulation that in spray tower, atomizes obtains fluorescent powder, tourmaline powder and the nano-titanium dioxide powder that PBT coats, and the particle diameter of fluorescent powder, tourmaline powder and nano-titanium dioxide powder that said PBT coats is 30 μ m.

Aforesaid preparation method; The fluorescent powder that described PBT coats, tourmaline powder and nano-titanium dioxide powder adopt gas flow crushing process to pulverize; Used air-flow is the nitrogen after freeze drying; Gas pressure is 0.7Mpa, and the particle diameter of fluorescent powder, tourmaline powder and nano-titanium dioxide powder that gained PBT coats is 5 μ m.

Aforesaid drying is meant said CBT and fluorescent powder, tourmaline powder and nano-titanium dioxide powder mixture vacuumize 48h under 80 ℃ of conditions; Under this condition; Can remove the moisture in the mixture fully, CBT ring-opening polymerization process can be carried out smoothly.

Aforesaid co-blended spinning specifically comprises: the filtration of the drying of spinning material, melt Conveying, melt, spinnerets holes in spraying silk, cooling curing and coiling; Wherein, The baking temperature of spinning material is 85 ℃, and be 20h drying time, to guarantee the intensive drying of spinning material; The interpolation of fluorescent powder, tourmaline powder and nano-titanium dioxide powder causes in the spinning material ash content more; Therefore; Selecting specification is 200 purpose screen packs, and selecting the aperture of spinnerets is 0.5mm, guarantees carrying out smoothly of spinning process; Spinning temperature is 270 ℃, and spinning speed is 1000m/min.

The technological parameter of aforesaid stretching is: 80 ℃ of draft temperatures, the draft temperature that carries out under the condition of HEAT SETTING are 120 ℃, and draw ratio is 3.8 times.

Measure the said functionalization effect that contains the functionalization PA6 fiber of fluorescent powder, tourmaline powder and nano-titanium dioxide powder: the luminous initial strength of functionalization PA6 fiber is greater than 680mcd/m2; Persistence was greater than 7 hours; The anion release concentration of functionalization PA6 fiber can reach 3500/cm3, the UPF of functionalization PA6 fiber＞50.

Claims

1. the preparation method of a functional poly nylon is characterized in that may further comprise the steps:

(1) preparation of the function powder of PBT coating

1) supports the catalyst of last layer CBT on the surface of function powder

B) function powder is added in the above-mentioned solution, and stirs; The mass ratio of the titanium class catalyst in said function powder and the solution is 15～25:1;

2) preparation of mixed-powder

A) the CBT powder is mixed with the above-mentioned function powder that supports that supports catalyst, the mass ratio of said CBT and said function powder is 2～4:1;

B) mixed powder is carried out drying;

3) in-situ polymerization

2) spun filament to the above-mentioned functions polyamide fiber stretches, and the back coiling gained fiber that stretches is the functional poly nylon.

2. the preparation method of a kind of functional poly nylon according to claim 1 is characterized in that, described titanium class catalyst is tetraethyl titanate, isopropyl titanate or metatitanic acid 2-ethylhexyl.

3. the preparation method of a kind of functional poly nylon according to claim 1; It is characterized in that; Described function powder is one or more in CNT, nano titanium oxide, tourmaline powder, Nano Silver series antibacterial agent, nano silicon oxide and the fluorescent material, and the particle diameter of said function powder is 20～80nm.

4. the preparation method of a kind of functional poly nylon according to claim 1 is characterized in that, described mixing comprises:

A) CBT is put into high speed disintegrator, process the CBT powder, crushing operation is carried out in this process employing intermittently form, promptly adopt to pulverize to stop the repetitive operation of pulverizing again in 5～10 minutes in 2～3 minutes, and be 100～200 purpose CBT powder with the acquisition particle diameter;

B) obtaining CBT powder is mixed in mixer with the function powder that supports that supports catalyst, promptly get CBT and the mixed-powder that supports function powder that supports catalyst, wherein incorporation time is 5～10min, and rotating speed is 400～450rpm/min.

5. the preparation method of a kind of functional poly nylon according to claim 1 is characterized in that, described in-situ polymerization with the concrete steps of spraying efflorescence is:

A) dried mixed-powder is through the blend process of fusion, polymerization and the material of double screw extruder realization CBT, and operating temperature is controlled at 200～245 ℃, and screw speed is controlled at 100～200r/min;

B) melt liquid and the hot compressed air that contain function powder after the blend are through second fluid nozzle and upwards ejection at a high speed, and spray tower top lead to cold wind, rapidly the hanging drop that sprays of cooling curing; Wherein the temperature of hot compressed air is 220～240 ℃, and gas liquid ratio is 2～3:1 (volume ratio), and the cooling granulation that in spray tower, atomizes obtains the function powder that PBT coats, and the particle diameter of the function powder that said PBT coats is 20～30 μ m.

6. the preparation method of a kind of functional poly nylon according to claim 1 is characterized in that, a kind of in PA6 or the PA66 section of described polyamide section.

7. the preparation method of a kind of functional poly nylon according to claim 1; It is characterized in that; The function powder that described PBT coats adopts gas flow crushing process to pulverize; Used air-flow is the nitrogen after freeze drying, and gas pressure is 0.7～0.8Mpa, and the particle diameter of the function powder that gained PBT coats is 3～5 μ m.

8. the preparation method of a kind of functional poly nylon according to claim 1 is characterized in that, described drying is meant said CBT and function powder mixture vacuumize 40～48h under 80～100 ℃ of conditions.

9. the preparation method of a kind of functional poly nylon according to claim 1; It is characterized in that; Described co-blended spinning specifically comprises: the filtration of the drying of spinning material, melt Conveying, melt, spinnerets holes in spraying silk, cooling curing and coiling; Wherein, the baking temperature of spinning material is 70～95 ℃, and be 20～25h drying time; The specification of screen pack is 100～200 orders, and the aperture of spinnerets is 0.3～0.5mm, and spinning temperature is 260～290 ℃, and spinning speed is 600～1500m/min.

10. the preparation method of a kind of functional poly nylon according to claim 1; It is characterized in that; The technological parameter of described stretching is: 70～150 ℃ of draft temperatures, the draft temperature that carries out under the condition of HEAT SETTING are 110～230 ℃, and draw ratio is 3.5～4 times.