CN104818543B - A kind of modified polylactic acid fiber haveing excellent performance - Google Patents

A kind of modified polylactic acid fiber haveing excellent performance Download PDF

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CN104818543B
CN104818543B CN201510182220.5A CN201510182220A CN104818543B CN 104818543 B CN104818543 B CN 104818543B CN 201510182220 A CN201510182220 A CN 201510182220A CN 104818543 B CN104818543 B CN 104818543B
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polylactic acid
parts
fiber
powder
acid
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CN104818543A (en
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柳伯强
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Changxing Yong Xin Textile Printing And Dyeing Co Ltd
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Changxing Yong Xin Textile Printing And Dyeing Co Ltd
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Abstract

The invention discloses a kind of modified polylactic acid fibers haveing excellent performance, and are prepared via a method which to obtain:By raw material:PDLLA polylactic acid;PLLA polylactic acid;Hydroxypropul starch;Cellulose diacetate;Nano-tourmaline powder;Nanomete talc powder;Chitosan powder;Nano imvite powder adds in high-speed mixer, polydactyl acid mixture is obtained after high speed dispersion;Mixed uniformly polydactyl acid mixture is made polydactyl acid master batch, and is dried in vacuo by double screw extruder melt blending, extrusion;By polydactyl acid functional agglomerate be sliced and be dried in vacuo common polylactic acid slice put into high-speed mixer be uniformly mixed, mixture obtains modified polylactic acid fiber on melt spinning machine through pentagon spinneret orifice spinning.

Description

A kind of modified polylactic acid fiber haveing excellent performance
Technical field
The present invention relates to a kind of modified polylactic acid fibers haveing excellent performance, and belong to polymer modification field.
Background technology
The raw materials for production lactic acid of acid fiber by polylactic (PLA) is made from cornstarch, also referred to as zein fiber, is a kind of Ecological friendly materials naturally biodegradable and that " white pollution " will not be caused.Polylactic acid (polylactic acid, PLA) be Under certain temperature, certain pressure, by catalyst action, prepared by lactide ring-opening polymerisation.
With the domestic and international exploitation mechanism of acid fiber by polylactic and being on the increase for enterprise, acid fiber by polylactic is in textile industry Application will be more and more extensive.Using the product that polylactic acid is obtained as raw material, there is good biocompatibility and biological absorbable Property and the performances such as biological degradability, water imbibition, biocidal property, anti-flammability, but easily shrink, stick under wet, thermal environment well Knot, influences the processing and application of acid fiber by polylactic.
Acid fiber by polylactic has fully demonstrated the advantages of natural fiber and synthetic fibers, while overcomes natural fiber and synthesis Some shortcomings of fiber, as it has degradability, sucting wet air permeability and the comfort of natural fiber, and it is strong to overcome natural fiber Spend the shortcomings of low, garment material creases easily;It has born anti-flammability and does not grow many excellent characteristics such as bacterium.Due to These excellent comprehensive performances that acid fiber by polylactic has have huge application prospect in textile industry, gather breast in recent years The exploitation of sour fiber attracts the concern of people in the industry very much, is widely used in home textile, clothes, non-woven fabrics, filtering material, health Articles for use, automotive interior material and furniture covering material etc..
The method that a variety of modified polylactic acid fibers have been disclosed in the prior art, such as Chinese patent application 201210096514.2 A kind of preparation method of hydrolytic-resistant modified polylactic acid fiber is disclosed, including:It is low in parts by weight by 70~98.9 parts of polylactic acid 1~30 part of molecular weight polyester, multi-functional 0.1~5.0 part of mixing of polycarbodiimide, carries out melt blending granulation after mixing Master batch, by obtained master batch it is vacuum dried after by melt spinning, winding obtain undrawn yarn, finally carry out drawing-off, i.e., Obtain modified acid fiber by polylactic.The modified polylactic acid fiber of the invention has excellent feel and flexibility, and can realize Low temperature dyeing, the dye-uptake higher of high-temperature dyeing, since hydrolytic Resistance is good, mechanical property is deteriorated when can avoid high-temperature process Problem.But due to the addition of cross-linking type polycarbodiimide, a small amount of irritative gas can be generated in spinning engineering to human body Cause certain injury.In addition, as Chinese patent application 201310166891.3 disclose a kind of modified polylactic acid fiber and its Preparation method, the modified polylactic acid fiber are made of following components blending:Polylactic acid;Cellulose derivative;Cellulose diacetate Grafted polylactic acid copolymer;Lubricant;Inorganic nanoparticles;Nucleating agent;Antioxidant;Preparation method is by portion by mass component ratio Point polylactic acid slice and all other raw material are added in high-speed mixer, are melted altogether by double screw extruder after high speed dispersion Mixed, extrusion obtains polydactyl acid master batch slice;By above-mentioned polydactyl acid master batch slice and the polylactic acid slice of remaining mass parts After high-speed mixer for dry mixing, through melt spinning machine melt spinning, redraw to get modified polylactic acid fiber;It is obtained to change Property acid fiber by polylactic is at low cost can be environmentally friendly with complete biodegradable;Spinning properties are good, tow stable quality, and Acid fiber by polylactic has excellent flexibility, rub resistance, dyeability and comfort.But above-mentioned technology is all without solving polylactic acid Fiber hygroscopicity difference determines that heat resistance is also to be improved.
Invention content
The present invention for acid fiber by polylactic of the prior art it is poor there are hygroscopicity, facile hydrolysis and cause difficulty in spinning, it is resistance to The defects of mill property is poor, and thermal stability is poor is, and it is an object of the present invention to provide a kind of good hygroscopicity, thermal stability raising, soft comfortable, spinning Silk performance is good, the modified polylactic acid fiber of the fully biodegradable of rub resistance, easy dyeing.
Contain in lactic acid there are one asymmetric carbon atom, there is optical activity, two kinds of optical isomers of polylactic acid are L- respectively Lactic acid and D-ALPHA-Hydroxypropionic acid, therefore lactide has L- lactides, D- lactides, D, four kinds of optics such as L- lactides and Meso- lactides Isomers.The polylactic acid of three kinds of structures can be formed by the various configuration of lactide, be PLLA, PLDA, PDLLA respectively.The present invention Innovatively the PLA of different optical textures is mixed according to a certain percentage, is found under certain component and ratio, is had unexpected Effect.
The regain of PLA fibers is lower than cotton fiber but higher than PET fiber, this is because the moisture pick-up properties of fiber and fiber parent The number of water base group is closely related, and contained big hydrophilic radical is more in macromolecular, and the hygroscopicity of fiber is better.Cotton fiber is natural Cellulose fibre, each glucose in macromolecular are remained in base containing 3 hydroxyls, and hydrophilic radical number is considerably beyond PLA fibers And PET fiber, and there is more ester group and methyl in PLA fibers and PET fiber, without hydrophilic polar group and reaction Property group.PLA fibers and PET fiber just have moisture absorption group only in end group, and the hydrophilic radical in the end group of PLA fibers exists Proportion is more some more than PET fiber in entire macromolecular, so the hygroscopicity of PLA fibers is better and poorer than cotton fiber than PET fiber. Therefore, the hygroscopicity of PLA fibers can be improved by introducing hydrophilic fibers.Therefore, it to the research of recipe ingredient is blended, essentially consists in pair The cellulose of addition, accounts between other components and component between compatibility.
Acid fiber by polylactic can be processed into the monofilament in round section or multifilament and trifoil cross-section fiber, also can working into coil The bent and staple fiber of non-crimping and the bulked continuous filament of two-component.The fiber of odd-shaped cross section can be with the moisture absorption of reinforcing fiber Property.Fiber surface has groove or section heteromorphosis, not only increases surface area, increases fiber surface wettability power, and Also increase the moisture that capillary gap is kept between fiber, therefore its hygroscopicity of the fiber of profiled filament and concave-convex surface is higher than same The smooth fiber in the circular cross-section of component, surface.The present invention also studies the shape of spinneret orifice, finds modified gather Lactic acid master batch can improve the Moisture absorption & moisture conductivity of modified PLA fibers in melt spinning using special-shaped spinneret orifice, and especially pentagon is different Shape spinneret spinning pentagon abnormity PLA fiber effects are especially good.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of modified polylactic acid fiber is prepared via a method which to obtain:
(1) it adds raw materials into high-speed mixer, polydactyl acid mixture is obtained after high speed dispersion:PDLLA polylactic acid; PLLA polylactic acid;Hydroxypropul starch;Cellulose diacetate;Nano-tourmaline powder;Nanomete talc powder;Chitosan powder;Nanometer is covered de- Native powder;
(2) mixed uniformly polydactyl acid mixture by double screw extruder melt blending, extrusion is made and be modified Polylactic acid master batch, and be dried in vacuo;
(3) common polylactic acid slice is sliced and is dried in vacuo by polydactyl acid functional agglomerate to put into high-speed mixer It is uniformly mixed, mixture obtains modified polylactic acid fiber on melt spinning machine through pentagon spinneret orifice spinning.
The step (1) is preferably:
It is added in high-speed mixer by the raw material of following parts by weight, polydactyl acid mixture is obtained after high speed dispersion:
65~75 parts of PDLLA polylactic acid;
15~20 parts of PLLA polylactic acid;
0.5 part of hydroxypropul starch;
12~13 parts of cellulose diacetate;
1~1.5 part of nano-tourmaline powder;
0.5 part of nanomete talc powder;
0.8 part of chitosan powder;
0.2 part of nano imvite powder;
Further, preferably:
It is added in high-speed mixer by the raw material of following parts by weight, polydactyl acid mixture is obtained after high speed dispersion:
65 parts of PDLLA polylactic acid;
18.5 parts of PLLA polylactic acid;
0.5 part of hydroxypropul starch;
13 parts of cellulose diacetate;
1.5 parts of nano-tourmaline powder;
0.5 part of nanomete talc powder;
0.8 part of chitosan powder;
0.2 part of nano imvite powder;
The step (3) is preferably:
Polydactyl acid functional agglomerate is sliced 30 parts and common 70 parts of the polylactic acid slice of vacuum drying is put into and mixed at a high speed It is uniformly mixed in conjunction machine, mixture obtains modified polylactic acid fiber on melt spinning machine through pentagon spinneret orifice spinning;
The spinning temperature is 190~220 DEG C, and winding speed is 1800~2200m/min;Drawing temperature is 70~90 DEG C, drafting multiple is 3.5 times.
Further, preferably:
Polydactyl acid functional agglomerate is sliced 30 parts and common 70 parts of the polylactic acid slice of vacuum drying is put into and mixed at a high speed It is uniformly mixed in conjunction machine, mixture obtains modified polylactic acid fiber on melt spinning machine through pentagon spinneret orifice spinning;
The spinning temperature is 220 DEG C, winding speed 1900m/min;Drawing temperature is 85 DEG C, drafting multiple 3.5 Times.
The invention has the beneficial effects that:
(1) modified polylactic acid fiber produced by the present invention is heat-resist, easy to process.
(2) modified polylactic acid fiber produced by the present invention has soft feel, outstanding mechanical performance, and hygroscopicity It is greatly improved with dye-uptake, it is comfortable and easy to wear and easy to dye.
(3) modified polylactic acid fiber hydrolysis produced by the present invention, and can be completely by biological hydrolysis.
Specific embodiment
Embodiment 1:
A kind of modified polylactic acid fiber is prepared via a method which to obtain:
(1) it is added in high-speed mixer by the raw material of following parts by weight, polydactyl acid mixing is obtained after high speed dispersion Object:
70 parts of PDLLA polylactic acid;
15 parts of PLLA polylactic acid;
0.5 part of hydroxypropul starch;
12 parts of cellulose diacetate;
1 part of nano-tourmaline powder;
0.5 part of nanomete talc powder;
0.8 part of chitosan powder;
0.2 part of nano imvite powder;
(2) mixed uniformly polydactyl acid mixture by double screw extruder melt blending, extrusion is made and be modified Polylactic acid master batch, and be dried in vacuo;
(3) polydactyl acid functional agglomerate is sliced 30 parts and is dried in vacuo common 70 parts of polylactic acid slice and put at a high speed It is uniformly mixed in mixing machine, mixture obtains modified polylactic acid fiber on melt spinning machine through pentagon spinneret orifice spinning;
The spinning temperature is 190 DEG C, winding speed 1800m/min;Drawing temperature is 70 DEG C, drafting multiple 3.5 Times.
Embodiment 2:
A kind of modified polylactic acid fiber is prepared via a method which to obtain:
(1) it is added in high-speed mixer by the raw material of following parts by weight, polydactyl acid mixing is obtained after high speed dispersion Object:
65 parts of PDLLA polylactic acid;
20 parts of PLLA polylactic acid;
0.5 part of hydroxypropul starch;
12 parts of cellulose diacetate;
1 part of nano-tourmaline powder;
0.5 part of nanomete talc powder;
0.8 part of chitosan powder;
0.2 part of nano imvite powder;
(2) mixed uniformly polydactyl acid mixture by double screw extruder melt blending, extrusion is made and be modified Polylactic acid master batch, and be dried in vacuo;
(3) polydactyl acid functional agglomerate is sliced 30 parts and is dried in vacuo common 70 parts of polylactic acid slice and put at a high speed It is uniformly mixed in mixing machine, mixture obtains modified polylactic acid fiber on melt spinning machine through pentagon spinneret orifice spinning;
The spinning temperature is 220 DEG C, winding speed 2200m/min;Drawing temperature is 90 DEG C, drafting multiple 3.5 Times.
Embodiment 3:
A kind of modified polylactic acid fiber is prepared via a method which to obtain:
(1) it is added in high-speed mixer by the raw material of following parts by weight, polydactyl acid mixing is obtained after high speed dispersion Object:
75 parts of PDLLA polylactic acid;
10 parts of PLLA polylactic acid;
0.5 part of hydroxypropul starch;
12 parts of cellulose diacetate;
1 part of nano-tourmaline powder;
0.5 part of nanomete talc powder;
0.8 part of chitosan powder;
0.2 part of nano imvite powder;
(2) mixed uniformly polydactyl acid mixture by double screw extruder melt blending, extrusion is made and be modified Polylactic acid master batch, and be dried in vacuo;
(3) polydactyl acid functional agglomerate is sliced 30 parts and is dried in vacuo common 70 parts of polylactic acid slice and put at a high speed It is uniformly mixed in mixing machine, mixture obtains modified polylactic acid fiber on melt spinning machine through pentagon spinneret orifice spinning;
The spinning temperature is 200 DEG C, winding speed 2000m/min;Drawing temperature is 80 DEG C, drafting multiple 3.5 Times.
Embodiment 4:
A kind of modified polylactic acid fiber is prepared via a method which to obtain:
(1) it is added in high-speed mixer by the raw material of following parts by weight, polydactyl acid mixing is obtained after high speed dispersion Object:
65 parts of PDLLA polylactic acid;
18.5 parts of PLLA polylactic acid;
0.5 part of hydroxypropul starch;
13 parts of cellulose diacetate;
1.5 parts of nano-tourmaline powder;
0.5 part of nanomete talc powder;
0.8 part of chitosan powder;
0.2 part of nano imvite powder;
(2) mixed uniformly polydactyl acid mixture by double screw extruder melt blending, extrusion is made and be modified Polylactic acid master batch, and be dried in vacuo;
(3) polydactyl acid functional agglomerate is sliced 30 parts and is dried in vacuo common 70 parts of polylactic acid slice and put at a high speed It is uniformly mixed in mixing machine, mixture obtains modified polylactic acid fiber on melt spinning machine through pentagon spinneret orifice spinning;
The spinning temperature is 220 DEG C, winding speed 1900m/min;Drawing temperature is 85 DEG C, drafting multiple 3.5 Times.
Embodiment 5:Effect is tested and assessed
The modified polylactic acid fiber feel that embodiment 1-4 is prepared is significantly more soft than common acid fiber by polylactic, The test of performance is further carried out, the results are shown in Table 1:
Table 1
It can be seen that modified polylactic acid fiber mechanical property produced by the present invention is good, and it is heat-resist, and hygroscopicity is apparent It improves, it is more comfortable to be woven into fabric dress.In addition, dyeability also increases.
It is worth noting that, the indices of embodiment 4 are especially outstanding, especially regain is apparently higher than other implementations Example is the preferred forms of the present invention.
It changes the shape of spinneret of embodiment 4 into round and triangle, it is found that regain has been reduced to 1.1% He 2.0%.This illustrates that pentagon spinneret orifice plays critically important effect to the raising of hydroscopicity.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.

Claims (1)

1. a kind of preparation method of modified polylactic acid fiber, its step are as follows:
(1)It is added in high-speed mixer by the raw material of following parts by weight, polydactyl acid mixture is obtained after high speed dispersion:
65 parts of PDLLA polylactic acid;
18.5 parts of PLLA polylactic acid;
0.5 part of hydroxypropul starch;
13 parts of cellulose diacetate;
1.5 parts of nano-tourmaline powder;
0.5 part of nanomete talc powder;
0.8 part of chitosan powder;
0.2 part of nano imvite powder;
(2)Modified poly- breast is made by double screw extruder melt blending, extrusion in mixed uniformly polydactyl acid mixture Sour master batch, and be dried in vacuo;
(3)Polydactyl acid functional agglomerate is sliced 30 parts and is dried in vacuo common 70 parts of polylactic acid slice and puts into mixed at high speed It is uniformly mixed in machine, mixture obtains modified polylactic acid fiber on melt spinning machine through pentagon spinneret orifice spinning;
The spinning temperature is 220 DEG C, and winding speed is 1900 m/min;Drawing temperature is 85 DEG C, and drafting multiple is 3.5 times;
The modified polylactic acid fiber that the method is prepared has following performance:Fracture strength is 4.8 cN/dTex, and dimension is blocked Softening point is 140 degrees Celsius, regain 3.1%, dye-uptake 68%.
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