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 the preparation method providing a kind of high vertical structure rate polylactic acid stereoscopic composite, to overcome the defect that prior art exists, meets the needs of people.
Described height founds the preparation method of structure rate polylactic acid stereoscopic composite, comprises the steps:
(1) found structure in advance: described Poly-L-lactic acid (PLLA) and dextrorotation PLA (PDLA) are dissolved respectively in a solvent, then by two kinds of solution mixing, desolventizing of then volatilizing obtains solid-state PLA vertical structure thing in advance; Or described Poly-L-lactic acid (PLLA) and dextrorotation PLA (PDLA) are dissolved in a solvent jointly, then to volatilize desolventizing, obtain PLLA/PDLA compound, be solid-state PLA vertical structure thing in advance, described solid-state PLA in advance vertical structure thing can be plastics, film, fiber or take PLA as the composite of matrix or reinforcement;
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;
More than one in the organic solvents such as described solvent selected from chloroform, oxolane, dioxane, hexafluoroisopropanol;
(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;
Further, preparation method of the present invention, comprises the steps:
(1) Poly-L-lactic acid (PLLA) and dextrorotation PLA (PDLA) are dissolved in solvent respectively, and then by two kinds of solution mixing, be paved into film, volatilization desolventizing, obtain PLLA/PDLA compound, then described PLLA/PDLA compound is injected in extruder and melt extrude, 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, obtain the acid fiber by polylactic of the cooling after drawing-off, for 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;
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;
More than one in the organic solvents such as described solvent selected from chloroform, oxolane, dioxane, hexafluoroisopropanol;
(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 founds structure rate polylactic acid stereoscopic composite, 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%;
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.
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 30g of dried PLLA and PDLA to be dissolved in respectively in the chloroform of 300ml, fully dissolve through 20h, then by two kinds of homogeneous solution mix and blend 5h, then mixed solution is paved into film, through solvent evaporates, obtain PLLA/PDLA blend film.Above solution mixed process is equivalent to the pre-vertical structure of the inventive method.
PLLA/PDLA blend film is processed at 205 DEG C 30min to carry out secondary and found structure.Record this film with differential scanning calorimeter and only near 224 DEG C, occur a melting peak, illustrate in this film to only have vertical structure crystallization, and without homogeneous phase crystallization, vertical structure rate 100%.Through XRD test, the degree of crystallinity of this film is 53%.The softening temperature of this polylactic acid membrane is 152 DEG C, and at 130 DEG C, being hydrolyzed 1h after-drawing strength retention in the solution of pH5 is 91%.
Comparative example 4
The PLLA of weight average molecular weight 150,000 is carried out drying; Getting dried PLLA60g is dissolved in the chloroform of 600ml, fully dissolves, then solution is paved into film through 20h, through solvent evaporates, obtains PLLA film.Record this film with differential scanning calorimeter and only near 168 DEG C, occur a melting peak, illustrate in this film to only have homogeneous phase crystallization.Through XRD test, in this film, the degree of crystallinity of homogeneous phase crystal is 31%.The softening temperature of this polylactic acid membrane is 68 DEG C, and at 130 DEG C, being hydrolyzed 1h after-drawing strength retention in the solution of pH5 is 15%.