Vertical structure rate polylactic acid stereoscopic composite of height and preparation method thereof
Technical field
The present invention relates to polylactic acid stereoscopic composite and preparation method thereof.
Background technology
The problem of non-renewable and non-degradable of petroleum based material is not present in poly-lactic acid material, is expected to take in many fields
For traditional non-renewable petroleum base high polymer material (such as polypropylene, polyamide, polyester).PLA is with natural reproducible resource
(such as corn, wheat) is raw material, it is fermented, polymerization and obtain, can be with degradable into dioxy when discarded without the use of petroleum resources
Change carbon and water, environmental pollution will not be caused.The advantages of based on more than PLA, PLA has broad application prospects.
But the relatively low softening temperature of PLA and facile hydrolysis limit its large-scale commercial application.It is such as poly-
Lactic acid, which cannot be used for preparing, the packing containers such as lunch box, the cup of heat resistant requirements, can not also be used as engineering plastics in automobile, electricity
Sub- electrical component etc. is applied.High temperature facile hydrolysis limits application of the acid fiber by polylactic in textile industry.Due to poly-
Acid fiber easily hydrolyzes, and is acutely hydrolyzed when higher temperature dyes, and fibrous mechanical property is impaired serious, so acid fiber by polylactic
Relatively low temperature can only be used to dye, cause the dye-uptake of dyestuff low, fabric can only obtain shallower color.
Ikada etc. is in document Macromolecules 1987,20:Reported first in 904-906 and pass through PLLA
(PLLA) and the blending of dextrorotation PLA (PDLA) can form the crystallization of vertical structure, and the stereoscopic composite fusing point is higher than common PLA
30~60 DEG C.Therefore Many researchers are want to improve the performance of PLA by forming polylactic acid stereoscopic crystallization.
Presently disclosed most of polylactic acid stereoscopic spinning process are, it is necessary to use nucleator.Publication number CN 101805941A
Report a kind of method that polylactic acid fiber with high melting point is prepared using PLLA and PDLA blend melt spinnings.This method adds
0.01wt%~5wt% nucleator, prepared acid fiber by polylactic fusing point are 209 DEG C;CN 102409432A disclose it is a kind of with
Alkyl fatty race salt carries out the method that PLLA, PDLA blend melt spinning prepare high heat-proof polylactic acid fiber as nucleator.Should
Fibers melt temperature has ironability more than 190 DEG C, and at 170 DEG C;CN 101528994A disclose one kind with phosphate
Metal salt carries out the method that PLLA, PDLA blend melt spinning prepare acid fiber by polylactic, the heat resistance of the fiber as nucleator
It is excellent with thermal shrinkage.It is configured to however, the addition of nucleator is stood in promotion, is often dropped while improving material thermal resistance
The mechanical property of low material.CN 1400343A report a kind of vertical structure fiber of PLLA and PDLA blending, and the fiber is below 90 DEG C
Intensity be 0.8cN/dtex.But the preparation of the fiber needs very high spinning speed, and complicated hot gas spring condition.It is above-mentioned
Complexity of the method due to technique or the high request to equipment, are all difficult to industrialization promotion.
Vertical structure rate is higher, and the heat resistance and hydrolytic resistance of polylactic acid stereoscopic composite are better.When PLLA and PDLA is mixed
Vertical structure crystallization is readily formed, while can also form homogeneous crystallization.Therefore, simple mixing is extremely difficult to 100% vertical structure
Rate.Therefore, the height for developing a kind of easy large-scale promotion of high-efficient simple founds structure rate (vertical structure rate refers to vertical structure crystallization and accounts for total crystallization
Ratio) the preparation method of polylactic acid stereoscopic composite have great importance.
The content of the invention
Present invention aims at a kind of high vertical structure rate polylactic acid stereoscopic composite and preparation method thereof is provided, to overcome now
The defects of with the presence of technology, meet the needs of people.
Described height founds structure rate polylactic acid stereoscopic composite, is PLLA (PLLA) and dextrorotation PLA (PDLA)
Blend, when being measured with differential scanning calorimeter, there is single melting peak, and the melting peak temperature be 200 DEG C with
On, it is preferred that when being measured with differential scanning calorimeter, there is single melting peak, and the melting peak temperature be 218~
228℃;There was only diffraction maximum that vertical structure crystallizes (2 θ=12 °, 21 °, 24 °) with XRD determining, without homogeneously crystallize diffraction maximum (2 θ=
16°);Crystallinity is 30~60%, and preferably crystallinity is 48~53%;
Softening temperature is 125~165 DEG C, preferably 149~153 DEG C;Fusing point be 200~240 DEG C, preferably 218~224
℃;
After hydrolyzing 1h in 130 DEG C, pH 5 solution, stretching strength retentivity is 65%~95%, preferably 87%
~92%;
Preferably, the weight ratio of described PLLA (PLLA) and dextrorotation PLA (PDLA) is 10:90~90:
10;
Preferably, the weight average molecular weight of described PLLA (PLLA) and dextrorotation PLA (PDLA) is 50,000~35
Ten thousand.
Preferably, the weight average molecular weight ratio of described PLLA (PLLA) and dextrorotation PLA (PDLA) is 1:6 arrive
6:1;
Term " the ratio between weight average molecular weight " refers to the ratio between PLLA and PDLA molecular size range, if PLLA is that 300,000, PDLA is
100000, the ratio between weight average molecular weight is 3:1;
Described height founds the preparation method of structure rate polylactic acid stereoscopic composite, comprises the following steps:
(1) pre- vertical structure:Described PLLA (PLLA) and dextrorotation PLA (PDLA) are melted, then pass through cooling
Obtain the pre- vertical structure thing of PLA of solid-state;
During melt blending, condition is 170~250 DEG C of temperature, is then cooled to 20~120 DEG C, preferably 20~30 DEG C, cooling
1~20 DEG C/min of speed;
The pre- vertical structure thing of solid-state PLA can be plastics, film, fiber or answering using PLA as matrix or reinforcement
Condensation material;
(2) structure is found entirely:By temperature of the pre- vertical structure thing of PLA of the solid-state of step (1) acquisition at 170~230 DEG C, tension force
For heat under 0.3~0.6cN/dtex vertical structure 0~120min, preferably hot vertical 40~60min of structure, room temperature, cooling speed are finally cooled to
Rate is 1~20 DEG C/min, and during being somebody's turn to do, pre- vertical structure thing keeps solid forms, obtains described height and founds structure rate polylactic acid stereoscopic
Compound;
Further, preparation method of the invention, comprises the following steps:
(1) PLLA (PLLA) and dextrorotation PLA (PDLA) are mixed, injects a mixture into extruder and melt
Extrusion, collection obtain as-spun fibre, 2.5~3.5 times of the drawing-off at 100 DEG C~120 DEG C by as-spun fibre, then by after drawing-off
Product, 20~120 DEG C, preferably 20~30 DEG C are cooled to, rate of temperature fall is 1~20 DEG C/min, obtains the poly- of the cooling after drawing-off
Acid fiber, it is the pre- vertical structure thing of PLA of solid-state;
Wherein:Screw rod area temperature is 175~240 DEG C, and spinneret temperature is 230 DEG C~235 DEG C, spinning speed 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 0.3~0.6cN/
0~120min, preferably 40~60min are kept under dtex, carries out secondary vertical structure, described height is obtained and founds structure rate polylactic acid stereoscopic
Compound, for a kind of high vertical structure rate polylactic acid stereoscopic fiber;
Term " tension force " is defined as follows:When object under tension acts on, it is present in inside it and perpendicular to two adjacent parts
Mutual tractive force on contact surface;
By described height stand structure rate polylactic acid stereoscopic fiber using method well known in the art carry out woven, knitting or
It is non-woven, you can the height for obtaining other forms founds structure rate polylactic acid stereoscopic composite, available for clothes, home textile product, women and children
Amenities and industrial nonwoven cloth etc.;
For the present invention without using any nucleator and other additives, products obtained therefrom is 100% polylactic acid article, and technique is simple
It is single, it is adapted to large-scale production.The vertical structure rate that described height founds structure rate polylactic acid stereoscopic composite is 100%, and heat resistance is excellent
It is good.In addition, it is 65%~95% that the product hydrolyzes 1h post-tensioning strength retention in 130 DEG C, pH 5 solution, hydrolytic resistance
It is excellent.
The polylactic acid stereoscopic composite of vertical structure rate 100% prepared by the inventive method has single melting peak, and molten
Melt temperature more than 200 DEG C.Its softening temperature is 125~165 DEG C, far above common PLA fibers (60~120 DEG C).The poly- breast
It is 65%~95% that sour stereoscopic composite hydrolyzes 1h post-tensioning strength retention in 130 DEG C, pH 5 solution, far above common
PLA products.
Brief description of the drawings
Fig. 1 is the result that the differential scanning calorimeter of embodiment 1 measures.
Fig. 2 is the XRD test results of embodiment 1.
Fig. 3 is the result that the differential scanning calorimeter of embodiment 2 measures.
Fig. 4 is the XRD test results of embodiment 2.
Fig. 5 is the result that the differential scanning calorimeter of embodiment 3 measures.
Fig. 6 is the XRD test results of embodiment 3.
Embodiment
Technical scheme and effect are further described with reference to embodiment.These embodiments are only used for
Illustrate the present invention rather than limitation the scope of the present invention.
Embodiment 1
(1) it is that 350,000 PLLA (PLLA) and dextrorotation PLA (PDLA) are dried by weight average molecular weight;
Dried PLLA (PLLA) and dextrorotation PLA (PDLA) each 50g are taken, mixes, injects a mixture into list
Melting extrusion in screw extruder, collection obtain as-spun fibre, are the pre- vertical structure thing of PLA of solid-state;
Wherein:Screw rod area temperature is 240 DEG C, and spinneret temperature is 230 DEG C, spinning speed 800m/min;
As-spun fibre 3.5 times of drawing-off at 120 DEG C, 25 DEG C are then cooled to, rate of temperature fall is 1 DEG C/min;
(2) for the acid fiber by polylactic after drawing-off is cooled down at 205 DEG C, tension force is that 50min is kept under 0.4cN/dtex, carries out two
Secondary vertical structure, obtain described height and found structure rate polylactic acid stereoscopic composite;
The fiber is measured with differential scanning calorimeter and only a melting peak nearby occurs at 228 DEG C, is illustrated in the fiber only
There is vertical structure to crystallize, and without homogeneous crystallization, it is 100% to found structure rate.See Fig. 1
Tested through XRD, the crystallinity of the fiber is 53%, sees Fig. 2
The softening temperature of the acid fiber by polylactic is 153 DEG C, and fusing point is 228 DEG C, and 1h is hydrolyzed in 130 DEG C, pH 5 solution
Post-tensioning strength retention is 92%.
Embodiment 2
PLLA and PDLA that weight average molecular weight is 200,000 are dried;Take dried PLLA 60g and PDLA 40g
It is sufficiently mixed uniformly.Inject a mixture into single screw extrusion machine and melt, extruded through measuring pump and spinneret orifice, collection is come into being
Fiber.Wherein screw rod area temperature is 175 DEG C, and spinneret temperature is 235 DEG C, spinning speed 800m/min.As-spun fibre is 100
2.8 times of drawing-off at DEG C, 30 DEG C are then cooled to, 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 that 60min is kept under 0.3cN/dtex, carries out secondary vertical structure.
The fiber is measured with differential scanning calorimeter and only a melting peak nearby occurs at 218 DEG C, is illustrated in the fiber only
There is vertical structure to crystallize, and without homogeneous crystallization, found structure rate 100%.See Fig. 3
Tested through XRD, the crystallinity of the fiber is 49%.See Fig. 4
The softening temperature of the acid fiber by polylactic is 149 DEG C, and fusing point is 218 DEG C, and 1h is hydrolyzed in 130 DEG C, pH 5 solution
Post-tensioning strength retention is 89%.
Embodiment 3
The PLLA of weight average molecular weight 250,000 and weight average molecular weight 80,000 PDLA are dried;Take dried PLLA and
Each 50g of PDLA are sufficiently mixed uniformly.Inject a mixture into single screw extrusion machine and melt, extruded through measuring pump and spinneret orifice, received
Collection obtains as-spun fibre.Wherein screw rod area temperature is 220 DEG C, and spinneret temperature is 235 DEG C, spinning speed 800m/min.Just
Raw fiber 2.5 times of drawing-off at 100 DEG C.Then 25 DEG C are cooled to, 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 to keep 45min to carry out secondary vertical structure under 0.6cN/dtex.
The fiber is measured with differential scanning calorimeter and only a melting peak nearby occurs at 224 DEG C, illustrates only vertical structure knot in the fiber
Crystalline substance, and without homogeneous crystallization, found structure rate 100%.See Fig. 5
Tested through XRD, the fibre crystallinity is 48%.See Fig. 6
The softening temperature of the acid fiber by polylactic is 151 DEG C, and fusing point is 224 DEG C, and 1h is hydrolyzed in 130 DEG C, pH 5 solution
Post-tensioning strength retention is 87%.
Comparative example 1
The PLLA that weight average molecular weight is 350,000 is dried;Take dried PLLA 100g injections single screw extrusion machine
Interior melting, extruded through measuring pump and spinneret orifice, collection obtains as-spun fibre.Wherein screw rod area temperature is 220 DEG C, spinneret temperature
For 210 DEG C, spinning speed 800m/min.As-spun fibre 3.5 times of drawing-off at 90 DEG C.Acid fiber by polylactic after drawing-off is existed
110 DEG C, tension force is thermal finalization 20min under 0.4cN/dtex.The fiber is measured with differential scanning calorimeter only at 170 DEG C nearby to go out
An existing melting peak, illustrate only homogeneous crystallization in the fiber, and crystallized without vertical structure.Tested through XRD, the homogeneous crystal of the fiber
Crystallinity is 38%.
The softening temperature of the acid fiber by polylactic is 74 DEG C, and 1h post-tensioning intensity is hydrolyzed in 130 DEG C, pH 5 solution and is kept
Rate is 17%.
Comparative example 2
PLLA and PDLA that weight average molecular weight is 350,000 are dried;Dried each 50g of PLLA and PDLA is taken to fill
Divide well mixed.Inject a mixture into single screw extrusion machine and melt, extruded through measuring pump and spinneret orifice, collection obtains nascent fibre
Dimension.Wherein screw rod area temperature is 240 DEG C, and spinneret temperature is 230 DEG C, spinning speed 800m/min.As-spun fibre is at 120 DEG C
Lower 3.5 times of drawing-off.The fiber is measured with differential scanning calorimeter and two melting peaks nearby occurs at 170 DEG C and 225 DEG C respectively, is said
Only not vertical structure crystallization in the bright fiber, and have homogeneous crystallization.Tested through XRD, the crystallinity of the fiber neutrality structure crystal is
31%, the crystallinity of homogeneous crystal is 12%, founds structure rate 72%.The softening temperature of the acid fiber by polylactic is 127 DEG C, 130
DEG C, it is 71% that 1h post-tensioning strength retention is hydrolyzed in pH 5 solution.
Comparative example 3
PLLA and weight average molecular weight that weight average molecular weight is 250,000 PDLA for being 80,000 are dried;Take dried
Each 50g of PLLA and PDLA are sufficiently mixed uniformly;Inject a mixture into single screw extrusion machine and melt, squeezed through measuring pump and spinneret orifice
Go out, collection obtains as-spun fibre.Wherein screw rod area temperature is 240 DEG C, and spinneret temperature is 230 DEG C, spinning speed 800m/
min.As-spun fibre 2.5 times of drawing-off at 120 DEG C.It is attached at 168 DEG C and 221 DEG C respectively that the fiber is measured with differential scanning calorimeter
Closely there are two melting peaks, illustrate only not vertical structure crystallization in the fiber, and have homogeneous crystallization.Tested through XRD, in the fiber
The crystallinity of vertical structure crystal is 28%, and the crystallinity of homogeneous crystal is 19%, founds structure rate 60%.The vertical structure rate 100%
The softening temperature of acid fiber by polylactic is 113 DEG C, and 1h post-tensioning strength retentions are hydrolyzed in 130 DEG C, pH=5 solution and are
66%.