CN105401259A - High-stereo-rate polylactic acid stereo compound and preparation method thereof - Google Patents
High-stereo-rate polylactic acid stereo compound and preparation method thereof Download PDFInfo
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- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
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Abstract
The invention discloses a high-stereo-rate polylactic acid stereo compound and a preparation method thereof. The high-stereo-rate polylactic acid stereo compound is a poly-L-lactic acid (PLLA) and a poly-D-lactic acid (PDLA) blend, a result of determination of the compound by a differential scanning calorimeter shows that the compound has a single melting peak, and the temperature of the melting peak is 200DEG C or above, and a result of XRD determination of the compound shows that the compound only has a stereo crystallization diffraction peak (2theta = 12DEG, 21DEG and 24DEG), and the crystallization degree is 30-60%. The polylactic acid stereo compound prepared through the method, having a stereo rate of 100%,, has a single melting peak, and the melting temperature is 200DEG C or above. The softening temperature of the compound is 125-165DEG C, and is far higher than the softening temperature (60-120DEG C) of common PLA fibers. The tensile strength retention rate of the polylactic acid stereo compound after being hydrolyzed at 130DEG C in a solution with the pH value of 5 for 1h is 65-95%, and is far higher than that of common PLA products.
Description
Technical field
The present invention relates to polylactic acid stereoscopic composite and preparation method thereof.
Background technology
There is not the non-renewable and nondegradable problem of petroleum based material in poly-lactic acid material, is expected to replace traditional non-renewable petroleum base macromolecular material (as polypropylene, polyamide, polyester) in a lot of field.PLA, obtain through fermentation, polymerization for raw material with natural reproducible resource (as corn, wheat), does not need use petroleum resources, can degradable one-tenth carbon dioxide and water time discarded, can not cause environmental pollution.Based on advantage more than PLA, PLA has broad application prospects.
But the softening temperature that PLA is lower and facile hydrolysis limit its large-scale commercial application.Such as PLA for the preparation of the packing container such as lunch box, cup having heat resistant requirements, also cannot can not be applied in automobile, electronic apparatus parts etc. as engineering plastics.High temperature facile hydrolysis limits the application of acid fiber by polylactic in textile industry.Because acid fiber by polylactic is easily hydrolyzed, be acutely hydrolyzed when higher temperature dyes, fibrous mechanical property is seriously impaired, so acid fiber by polylactic can only adopt lower temperature dyeing, cause the dye-uptake of dyestuff low, fabric can only obtain more shallow color.
Ikada etc. are at document Macromolecules1987, in 20:904-906, reported first can form vertical structure crystallization by Poly-L-lactic acid (PLLA) and the blended of dextrorotation PLA (PDLA), and this stereoscopic composite fusing point is higher than common PLA 30 ~ 60 DEG C.Therefore Many researchers wants the performance improving PLA by forming polylactic acid stereoscopic crystallization.
Disclosed most of polylactic acid stereoscopic spinning process at present, needs to use nucleator.Publication number CN101805941A reports a kind of method that PLLA of utilization and PDLA blend melt spinning prepare polylactic acid fiber with high melting point.The method adds the nucleator of 0.01wt% ~ 5wt%, and prepared acid fiber by polylactic fusing point is 209 DEG C; CN102409432A discloses a kind of using alkyl fatty race salt as nucleator, carries out the method that PLLA, PDLA blend melt spinning prepares high heat-proof polylactic acid fiber.This fibers melt temperature more than 190 DEG C, and has ironability at 170 DEG C; CN101528994A discloses a kind of using phosphate metal salt as nucleator, and carry out the method that PLLA, PDLA blend melt spinning prepares acid fiber by polylactic, heat resistance and the thermal shrinkage of this fiber are excellent.But being added in of nucleator promotes vertical being configured to, and often reduces the mechanical property of material while improving material thermal resistance.CN1400343A reports the blended vertical structure fiber of a kind of PLLA and PDLA, and the intensity of this fiber below 90 DEG C is 0.8cN/dtex.But the preparation of this fiber needs very high spinning speed, and the hot gas spring condition of complexity.The complexity of said method due to technique or the high request to equipment, be all difficult to carry out industrialization promotion.
Vertical structure rate is higher, the heat resistance of polylactic acid stereoscopic composite and hydrolytic resistance better.Be easy to form vertical structure crystallization during PLLA and PDLA mixing, also can form homogeneous phase crystallization simultaneously.Therefore, simple mixing is difficult to the vertical structure rate reaching 100%.Therefore, the preparation method that the height developing the easy large-scale promotion of a kind of high-efficient simple founds the polylactic acid stereoscopic composite of structure rate (vertical structure rate refers to that vertical structure crystallization accounts for the ratio of total crystallization) has great importance.
Summary of the invention
The object of the invention is to provide a kind of high vertical structure rate polylactic acid stereoscopic composite and preparation method thereof, to overcome the defect that prior art exists, meets the needs of people.
Described height founds structure rate polylactic acid stereoscopic composite, for the blend of Poly-L-lactic acid (PLLA) and dextrorotation PLA (PDLA), when measuring with differential scanning calorimeter, there is single melting peak, and this melting peak temperature is more than 200 DEG C, preferably, when measuring with differential scanning calorimeter, there is single melting peak, and this melting peak temperature is 218 ~ 228 DEG C; The diffraction maximum (2 θ=12 °, 21 °, 24 °) of vertical structure crystallization is only had, without the diffraction maximum (2 θ=16 °) of homogeneous phase crystallization with XRD determining; Degree of crystallinity is 30 ~ 60%, and preferred degree of crystallinity is 48 ~ 53%;
Softening temperature is 125 ~ 165 DEG C, preferably 149 ~ 153 DEG C; Fusing point is 200 ~ 240 DEG C, is preferably 218 ~ 224 DEG C;
At 130 DEG C, after being hydrolyzed 1h in the solution of pH5, stretching strength retentivity is 65% ~ 95%, preferably 87% ~ 92%;
Preferably, described Poly-L-lactic acid (PLLA) and the weight ratio of dextrorotation PLA (PDLA) are 10:90 ~ 90:10;
Preferably, described Poly-L-lactic acid (PLLA) and the weight average molecular weight of dextrorotation PLA (PDLA) are 50,000 ~ 350,000.
Preferably, described Poly-L-lactic acid (PLLA) and the weight average molecular weight of dextrorotation PLA (PDLA) are than being 1:6 to 6:1;
Term " ratio of weight average molecular weight " refers to the ratio of the molecular size range of PLLA and PDLA, is 100,000 if PLLA is 300,000, PDLA, and the ratio of weight average molecular weight is 3:1;
Described height founds the preparation method of structure rate polylactic acid stereoscopic composite, comprises the steps:
(1) found structure in advance: by described Poly-L-lactic acid (PLLA) and dextrorotation PLA (PDLA) melting, then obtain solid-state PLA vertical structure thing in advance by cooling;
During melt blending, condition is temperature 170 ~ 250 DEG C, is then cooled to 20 ~ 120 DEG C, preferably 20 ~ 30 DEG C, rate of temperature fall 1 ~ 20 DEG C/min;
Described solid-state PLA in advance vertical structure thing can be plastics, film, fiber or take PLA as the composite of matrix or reinforcement;
(2) vertical structure entirely: the solid-state PLA that step (1) is obtained in advance vertical structure thing be 0.3 ~ 0.6cN/dtex at temperature, the tension force of 170 ~ 230 DEG C under the vertical structure 0 ~ 120min of heat, preferred heat founds structure 40 ~ 60min, finally be cooled to room temperature, rate of temperature fall is 1 ~ 20 DEG C/min, in this process, pre-vertical structure thing keeps solid forms, and the height described in acquisition founds structure rate polylactic acid stereoscopic composite;
Further, preparation method of the present invention, comprises the steps:
(1) by Poly-L-lactic acid (PLLA) and dextrorotation PLA (PDLA) mixing, compound is injected in extruder and melt extrudes, collection obtains as-spun fibre, by as-spun fibre drawing-off 2.5 ~ 3.5 times at 100 DEG C ~ 120 DEG C, then by the product after drawing-off, be cooled to 20 ~ 120 DEG C, preferably 20 ~ 30 DEG C, rate of temperature fall is 1 ~ 20 DEG C/min, obtains the acid fiber by polylactic of the cooling after drawing-off, is solid-state PLA vertical structure thing in advance;
Wherein: screw rod district temperature is 175 ~ 240 DEG C, spinneret temperature is 230 DEG C ~ 235 DEG C, and spinning speed is 800m/min;
(2) by the acid fiber by polylactic after drawing-off at 170 ~ 230 DEG C, preferably 190 ~ 205 DEG C, tension force is keep 0 ~ 120min under 0.3 ~ 0.6cN/dtex, preferably 40 ~ 60min, carry out secondary and found structure, height described in acquisition founds structure rate polylactic acid stereoscopic composite, is a kind of high vertical structure rate polylactic acid stereoscopic fiber;
Term " tension force " is defined as follows: during the effect of object under tension, is present in that it is inner and perpendicular to the mutual tractive force on two adjacent part contact surface;
Described height being found structure rate polylactic acid stereoscopic fiber, to adopt method well known in the art to carry out woven, knitting or non-woven, the height that can obtain other forms founds structure rate polylactic acid stereoscopic composite, can be used for clothes, home textile product, maternity and child hygiene articles for use and industrial nonwoven cloth etc.;
The present invention is without the need to using any nucleator and other additive, and products obtained therefrom is 100% polylactic acid article, and technique is simple, is applicable to large-scale production.The vertical structure rate that described height founds structure rate polylactic acid stereoscopic composite is 100%, excellent heat resistance.In addition, this product is at 130 DEG C, and being hydrolyzed 1h after-drawing strength retention in the solution of pH5 is 65% ~ 95%, and hydrolytic resistance is excellent.
The polylactic acid stereoscopic composite of vertical structure rate 100% prepared by the inventive method has single melting peak, and melt temperature is more than 200 DEG C.Its softening temperature is 125 ~ 165 DEG C, far above common PLA fiber (60 ~ 120 DEG C).This polylactic acid stereoscopic composite is at 130 DEG C, and being hydrolyzed 1h after-drawing strength retention in the solution of pH5 is 65% ~ 95%, far above common PLA goods.
Accompanying drawing explanation
Fig. 1 is the result that the differential scanning calorimeter of embodiment 1 records.
Fig. 2 is the XRD test result of embodiment 1.
Fig. 3 is the result that the differential scanning calorimeter of embodiment 2 records.
Fig. 4 is the XRD test result of embodiment 2.
Fig. 5 is the result that the differential scanning calorimeter of embodiment 3 records.
Fig. 6 is the XRD test result of embodiment 3.
Detailed description of the invention
Below in conjunction with embodiment, technical scheme of the present invention and effect are further described.These embodiments are only not used in for illustration of the present invention and limit the scope of the invention.
Embodiment 1
(1) Poly-L-lactic acid (PLLA) and the dextrorotation PLA (PDLA) that weight average molecular weight are 350,000 carry out drying;
Get dried Poly-L-lactic acid (PLLA) and dextrorotation PLA (PDLA) each 50g, mixing, injects compound in single screw extrusion machine and melt extrudes, and collects and obtains as-spun fibre, is solid-state PLA vertical structure thing in advance;
Wherein: screw rod district temperature is 240 DEG C, spinneret temperature is 230 DEG C, and spinning speed is 800m/min;
As-spun fibre is drawing-off 3.5 times at 120 DEG C, is then cooled to 25 DEG C, and rate of temperature fall is 1 DEG C/min;
(2) by cooled for drawing-off acid fiber by polylactic at 205 DEG C, tension force is keep 50min under 0.4cN/dtex, and carry out secondary and found structure, the height described in acquisition founds structure rate polylactic acid stereoscopic composite;
Record this fiber with differential scanning calorimeter and only near 228 DEG C, occur a melting peak, illustrate in this fiber to only have vertical structure crystallization, and without homogeneous phase crystallization, vertical structure rate is 100%.See Fig. 1.
Through XRD test, the degree of crystallinity of this fiber is 53%, sees Fig. 2.
The softening temperature of this acid fiber by polylactic is 153 DEG C, and fusing point is 228 DEG C, and at 130 DEG C, being hydrolyzed 1h after-drawing strength retention in the solution of pH5 is 92%.
Embodiment 2
PLLA and PDLA weight average molecular weight being 200,000 carries out drying; Get dried PLLA60g and PDLA40g fully to mix.Compound is injected melting in single screw extrusion machine, extrude through measuring pump and spinneret orifice, collect and obtain as-spun fibre.Wherein screw rod district temperature is 175 DEG C, and spinneret temperature is 235 DEG C, and spinning speed is 800m/min.As-spun fibre is drawing-off 2.8 times at 100 DEG C, is then cooled to 30 DEG C, and rate of temperature fall is 20 DEG C/min;
By the acid fiber by polylactic after drawing-off at 195 DEG C, tension force is keep 60min under 0.3cN/dtex, carries out secondary and founds structure.
Record this fiber with differential scanning calorimeter and only near 218 DEG C, occur a melting peak, illustrate in this fiber to only have vertical structure crystallization, and without homogeneous phase crystallization, vertical structure rate 100%.See Fig. 3.
Through XRD test, the degree of crystallinity of this fiber is 49%.See Fig. 4.
The softening temperature of this acid fiber by polylactic is 149 DEG C, and fusing point is 218 DEG C, and at 130 DEG C, being hydrolyzed 1h after-drawing strength retention in the solution of pH5 is 89%.
Embodiment 3
The PDLA of the PLLA of weight average molecular weight 250,000 and weight average molecular weight 80,000 is carried out drying; Get each 50g of dried PLLA and PDLA fully to mix.Compound is injected melting in single screw extrusion machine, extrude through measuring pump and spinneret orifice, collect and obtain as-spun fibre.Wherein screw rod district temperature is 220 DEG C, and spinneret temperature is 235 DEG C, and spinning speed is 800m/min.As-spun fibre is drawing-off 2.5 times at 100 DEG C.Then be cooled to 25 DEG C, rate of temperature fall is 15 DEG C/min;
By the acid fiber by polylactic after drawing-off at 190 DEG C, tension force is keep 45min to carry out secondary under 0.6cN/dtex to found structure.Record this fiber with differential scanning calorimeter and only near 224 DEG C, occur a melting peak, illustrate in this fiber to only have vertical structure crystallization, and without homogeneous phase crystallization, vertical structure rate 100%.See Fig. 5.
Through XRD test, this fibre crystallinity is 48%.See Fig. 6.
The softening temperature of this acid fiber by polylactic is 151 DEG C, and fusing point is 224 DEG C, and at 130 DEG C, being hydrolyzed 1h after-drawing strength retention in the solution of pH5 is 87%.
Comparative example 1
By weight average molecular weight be 350,000 PLLA carry out drying; Get dried PLLA100g and inject melting in single screw extrusion machine, extrude through measuring pump and spinneret orifice, collect and obtain as-spun fibre.Wherein screw rod district temperature is 220 DEG C, and spinneret temperature is 210 DEG C, and spinning speed is 800m/min.As-spun fibre is drawing-off 3.5 times at 90 DEG C.By the acid fiber by polylactic after drawing-off at 110 DEG C, tension force is HEAT SETTING 20min under 0.4cN/dtex.Record this fiber with differential scanning calorimeter and only near 170 DEG C, occur a melting peak, illustrate in this fiber to only have homogeneous phase crystallization, and without vertical structure crystallization.Through XRD test, the degree of crystallinity of this fiber homogeneous phase crystal is 38%.
The softening temperature of this acid fiber by polylactic is 74 DEG C, and at 130 DEG C, being hydrolyzed 1h after-drawing strength retention in the solution of pH5 is 17%.
Comparative example 2
PLLA and PDLA weight average molecular weight being 350,000 carries out drying; Get each 50g of dried PLLA and PDLA fully to mix.Compound is injected melting in single screw extrusion machine, extrude through measuring pump and spinneret orifice, collect and obtain as-spun fibre.Wherein screw rod district temperature is 240 DEG C, and spinneret temperature is 230 DEG C, and spinning speed is 800m/min.As-spun fibre is drawing-off 3.5 times at 120 DEG C.Record this fiber with differential scanning calorimeter and near 170 DEG C and 225 DEG C, occur two melting peaks respectively, illustrate in this fiber not only have vertical structure crystallization, and have homogeneous phase crystallization.Through XRD test, the degree of crystallinity of the neutral structure crystal of this fiber is 31%, and the degree of crystallinity of homogeneous phase crystal is 12%, vertical structure rate 72%.The softening temperature of this acid fiber by polylactic is 127 DEG C, and at 130 DEG C, being hydrolyzed 1h after-drawing strength retention in the solution of pH5 is 71%.
Comparative example 3
By weight average molecular weight be 250,000 PLLA and weight average molecular weight be 80,000 PDLA carry out drying; Get each 50g of dried PLLA and PDLA fully to mix; Compound is injected melting in single screw extrusion machine, extrude through measuring pump and spinneret orifice, collect and obtain as-spun fibre.Wherein screw rod district temperature is 240 DEG C, and spinneret temperature is 230 DEG C, and spinning speed is 800m/min.As-spun fibre is drawing-off 2.5 times at 120 DEG C.Record this fiber with differential scanning calorimeter and near 168 DEG C and 221 DEG C, occur two melting peaks respectively, illustrate in this fiber not only have vertical structure crystallization, and have homogeneous phase crystallization.Through XRD test, the degree of crystallinity of the neutral structure crystal of this fiber is 28%, and the degree of crystallinity of homogeneous phase crystal is 19%, vertical structure rate 60%.The softening temperature of the acid fiber by polylactic of this vertical structure rate 100% is 113 DEG C, and at 130 DEG C, being hydrolyzed 1h after-drawing strength retention in the solution of pH=5 is 66%.
Claims (10)
1. high vertical structure rate polylactic acid stereoscopic composite, it is characterized in that, for the blend of Poly-L-lactic acid (PLLA) and dextrorotation PLA (PDLA), when measuring with differential scanning calorimeter, there is single melting peak, and this melting peak temperature is more than 200 DEG C, only have the diffraction maximum (2 θ=12 °, 21 °, 24 °) of vertical structure crystallization with XRD determining, degree of crystallinity is 30 ~ 60%.
2. height according to claim 1 founds structure rate polylactic acid stereoscopic composite, it is characterized in that, when measuring with differential scanning calorimeter, has single melting peak, and this melting peak temperature is 218 ~ 228 DEG C.
3. height according to claim 1 founds structure rate polylactic acid stereoscopic composite, it is characterized in that, degree of crystallinity is 48 ~ 53%.
4. height according to claim 1 founds structure rate polylactic acid stereoscopic composite, it is characterized in that, softening temperature is 125 ~ 165 DEG C, and fusing point is 200 ~ 240 DEG C.
5. height according to claim 4 founds structure rate polylactic acid stereoscopic composite, it is characterized in that, softening temperature is 149 ~ 153 DEG C, fusing point 218 ~ 224 DEG C.
6. height according to claim 1 founds structure rate polylactic acid stereoscopic composite, it is characterized in that, described Poly-L-lactic acid (PLLA) and the weight average molecular weight of dextrorotation PLA (PDLA) are 50,000 ~ 350,000, and described Poly-L-lactic acid (PLLA) and the weight average molecular weight of dextrorotation PLA (PDLA) are than being 1:6 to 6:1.
7. the height according to any one of claim 1 ~ 6 founds structure rate polylactic acid stereoscopic composite, it is characterized in that, at 130 DEG C, after being hydrolyzed 1h in the solution of pH5, stretching strength retentivity is 65% ~ 95%.
8. the height according to any one of claim 1 ~ 7 founds the preparation method of structure rate polylactic acid stereoscopic composite, it is characterized in that, comprises the steps:
(1) found structure in advance: by described Poly-L-lactic acid (PLLA) and dextrorotation PLA (PDLA) melting, then obtain solid-state PLA vertical structure thing in advance by cooling;
During melt blending, condition is temperature 170 ~ 250 DEG C, is then cooled to 20 ~ 120 DEG C, preferably 20 ~ 30 DEG C, rate of temperature fall 1 ~ 20 DEG C/min;
(2) vertical structure entirely: the solid-state PLA that step (1) is obtained in advance vertical structure thing be 0.3 ~ 0.6cN/dtex at temperature, the tension force of 170 ~ 230 DEG C under the vertical structure 0 ~ 120min of heat, finally be cooled to room temperature, rate of temperature fall is 1 ~ 20 DEG C/min, in this process, pre-vertical structure thing keeps solid forms, and the height described in acquisition founds structure rate polylactic acid stereoscopic composite.
9. the height according to any one of claim 1 ~ 7 founds the preparation method of structure rate polylactic acid stereoscopic composite, it is characterized in that, comprises the steps:
(1) by Poly-L-lactic acid (PLLA) and dextrorotation PLA (PDLA) mixing, compound is injected in extruder and melt extrudes, collection obtains as-spun fibre, by as-spun fibre drawing-off 2.5 ~ 3.5 times at 100 DEG C ~ 120 DEG C, then by the product after drawing-off, be cooled to 20 ~ 120 DEG C, preferably 20 ~ 30 DEG C, rate of temperature fall is 1 ~ 20 DEG C/min, obtains the acid fiber by polylactic of the cooling after drawing-off, is solid-state PLA vertical structure thing in advance;
(2) by the acid fiber by polylactic after drawing-off at 170 ~ 230 DEG C, preferably 190 ~ 205 DEG C, tension force be under 0.3 ~ 0.6cN/dtex keep 0 ~ 120min, carry out secondary and found structure, the height described in acquisition founds structure rate polylactic acid stereoscopic composite.
10. method according to claim 9, is characterized in that, described height is found structure rate polylactic acid stereoscopic fiber and carry out woven, knitting or non-woven, the height that can obtain other forms founds structure rate polylactic acid stereoscopic composite.
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| CN110624484A (en) * | 2019-07-26 | 2019-12-31 | 东华大学 | All-stereo polylactic acid porous microsphere and preparation method thereof |
| WO2020043065A1 (en) * | 2018-08-30 | 2020-03-05 | 北京服装学院 | High stereocomplex polylactic acid material and preparation method therefor |
| CN111218730A (en) * | 2018-11-26 | 2020-06-02 | 安徽丰原生物材料股份有限公司 | High-temperature-resistant polylactic acid fiber and preparation method thereof |
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