CN104695047A - Novel high-softness polylactic acid fiber composite material and preparation method thereof - Google Patents
Novel high-softness polylactic acid fiber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a novel high-softness polylactic acid fiber composite material and a preparation method thereof. The composite material comprises the following components in parts by weight: 70-90 parts of polylactic acid (PLA), 1-3 parts of poly(1,2-propylene glycol adipate) (PPA), 0.1-1 part of polycarbodiimide (PCDI), and 0.1-1 part of tetrabutyl titanate. The PLA/PPA blend is modified by taking multifunctional PCDI and TT-01 as reactive compatibilizers, the high-temperature stability and compatibility of the material can be well improved by PCDI, and the processing performance is better. After PCDI is added, the breaking strength and elastic modulus of the PLA/PPA blend fiber are reduced, the breaking elongation is obviously improved, and the softness is improved. The transesterification reaction between PLA and PPA can be promoted through the addition of TT-01, so that the stability and compatibility of the product are further improved.
Description
technical field
The present invention relates to biodegradable technical field of polymer materials, be specifically related to composite of a kind of novel acid fiber by polylactic high flexibility and preparation method thereof.
Background technology
PLA/PPA (PLA/PPA) fiber is as a kind of novel environment-friendlyfiber fiber, there is the advantages such as good mechanical performance, degradability, good biocompatibility and energy consumption are low, but in certain field, such as it is medical, packaging and the coated field of cable, because PLA/PPA compatibility is bad, the partial properties causing material particularly flexibility does not reach the requirement of product.Herein for these problems, the multi-functional polycarbodiimide of employing of novelty is as reactive compatibilizer further modification PLA/PPA blend, the interpolation of polycarbodiimide (PCDI) can improve high-temperature stability and the compatibility of blend well, and the processing characteristics of blend improves, after adding PCDI, fracture strength and the elastic modelling quantity of PLA/PPA blend fibers all decrease, therefore the deformability of blended fiber is significantly improved, flexibility improves, and the ester exchange reaction added between catalysis PLA and PPA of butyl titanate, thus further increase compatibility and the flexibility of product.At present, specializing in of polyester modification PLA fiber softening has no report, and the present invention has important Research Significance and using value.
Summary of the invention
The invention provides composite of a kind of novel acid fiber by polylactic high flexibility and preparation method thereof, the preparation method of this composite is simple, and makes the lactic acid composite material obtained have good flexibility.
The object of the invention is prepare a kind of novel composite being improved acid fiber by polylactic flexibility by the mode of blending and modifying, each component comprised and the parts by weight of component as follows:
PLA (PLA) 70 parts-90 parts
PPA (PPA) 10 parts-30 parts
Polycarbodiimide (PCDI) 0.1 part-1 part
Butyl titanate (TT-01) 0.1 part-1 part
Described PLA weight average molecular weight is 80000-150000g/mol.
Described PPA (PPA) its weight average molecular weight is 20000-100000g/mol.
The preparation method of the composite of a kind of novel acid fiber by polylactic high flexibility of the present invention, comprises the preparation process of PLA and blended slice thereof and the preparation process of PLA and blended fiber thereof.
(1) PLA described in and blended slice thereof are prepared by the following method:
By PLA resin under the condition of 60 DEG C through vacuumize 24h, then by 35-45 part PLA, 10-30 part PPA, 0.1-1 part PCDI and 0.1-1 part TT-01 Homogeneous phase mixing by a certain percentage, add double screw extruder melt blending and prepare the section of PLA/PPA/PCDI/TT-01 co-blended spinning, wherein extrusion temperature is between 150-180 DEG C.
(2) PLA described in and blended fiber thereof are prepared by the following method:
PLA/PPA/PCDI/TT-01 blended slice prepared by pure 35-45 part PLA and step (1) in vacuum drying oven at 90 DEG C dry 48h, then prepare fiber by melt spinning-drawing-off two-step method.Then obtain as-spun fibre by spinning machine spinning, after oiling, obtain the preliminary draft silk of different winding speed through winding.
Step (1) described spinning machine spinnerets be 24 holes, aperture is 0.3mm, and spinneret orifice draw ratio (L/D) is 3.
Spinning temperature described in step (2) is between 220-245 DEG C, and drawing temperature is between 80-95 DEG C, and heat setting temperature is between 100-130 DEG C.
Beneficial effect of the present invention:
The multi-functional polycarbodiimide (PCDI) of employing of the present invention's innovation and butyl titanate (TT-01) coupling are used as reactive compatibilizer modification PLA/PPA blend, the interpolation of PCDI can improve high-temperature stability and the compatibility of blend well, and the processing characteristics of blend improves, after adding PCDI, fracture strength and the elastic modelling quantity of PLA/PPA blend fibers all decrease, therefore the deformability of blended fiber is significantly improved, flexibility improves, and the anti-degradation capability of blended fiber is also improved and the ester exchange reaction added between catalysis PLA and PPA of TT-01 simultaneously, thus further increase compatibility and the flexibility of product.
The present invention by PLA section and the blended granulation of PPA, and prepares plasticising PLA fiber by melt spinning.PPA adds the fragility effectively can improving PLA, and along with the increase of PPA content, the glass transition temperature of material reduces, and elongation at break significantly improves, and fracture section is obvious plastic deformation, but the compatibility poor of material.Therefore the present invention adopts multi-functional polycarbodiimide and butyl titanate coupling to be used as reactive compatibilizer to carry out modification PLA/PPA blend, and PCDI can improve high-temperature stability and the compatibility of material well, and processing characteristics also can improve.After adding PCDI, fracture strength and the elastic modelling quantity of PLA/PPA blend fibers all decrease, and elongation at break is significantly improved, and flexibility improves.TT-01 adds the ester exchange reaction facilitated between PLA and PPA, thus further increases stability and the compatibility of product.
Detailed description of the invention
Below in conjunction with specific embodiment, one detailed elaboration is done to the present invention.
The present invention relates to a kind of composite of novel acid fiber by polylactic high flexibility, comprise following component according to parts by weight: PLA (PLA) 70 parts-90 parts, PPA (PPA) 10 parts-30 parts, polycarbodiimide (PCDI) 0.1 part-1 part, butyl titanate (TT-01) 0.1 part-1 part.
In following each example, described PLA weight average molecular weight is 80000-150000g/mol; Described PPA (PPA) its weight average molecular weight is 20000-100000g/mol.
embodiment 1
PLA (PLA) 80 parts, PPA (PPA) 20 parts, polycarbodiimide (PCDI) 0.5 part, butyl titanate 0.5 part.
(1) blend modified polylactic acid fiber is prepared by the following method: by 40 parts of PLA resin under the condition of 60 DEG C through vacuumize 24h, then by PLA (40 parts)/PPA(20 part)/PCDI(0.5 part)/TT-01(0.5 part) Homogeneous phase mixing, add double screw extruder melt blending and prepare spinning chips, extrusion temperature is at 160 DEG C;
(2) preparation of PLA and blended fiber thereof: PLA (40 parts)/PPA(20 part prepared by 40 parts of PLA and step (1))/PCDI(0.5 part)/TT-01(0.5 part) and blended slice in vacuum drying oven at 90 DEG C dry 48h, then prepare fiber by melt spinning-drawing-off two-step method.Wherein, spinnerets is 24 holes, and aperture is 0.3mm, and spinneret orifice draw ratio (L/D) is 3.Then obtain as-spun fibre by spinning machine spinning, after oiling, obtain the preliminary draft silk of different winding speed through winding.Spinning temperature is at 230 DEG C, and drawing temperature is at 85 DEG C, and heat setting temperature is at 115 DEG C.
Embodiment 2-4 is identical with processing conditions with embodiment 1 preparation process, unlike the addition of each raw material.
embodiment 2
PLA (PLA) 70 parts, PPA (PPA) 30 parts, polycarbodiimide (PCDI) 0.1 part, butyl titanate 0.1 part.
(1) blend modified polylactic acid fiber is prepared by the following method: by 35 parts of PLA resin under the condition of 60 DEG C through vacuumize 24h, then by PLA(35 part)/PPA(30 part)/PCDI(0.1 part)/TT-01(0.1 part) Homogeneous phase mixing, add double screw extruder melt blending and prepare spinning chips, extrusion temperature is at 150 DEG C;
(2) preparation of PLA and blended fiber thereof: PLA(35 part prepared by 35 parts of PLA and step (1))/PPA(30 part)/PCDI(0.1 part)/TT-01(0.1 part) blended slice in vacuum drying oven at 90 DEG C dry 48h, then prepare fiber by melt spinning-drawing-off two-step method.Wherein, spinnerets is 24 holes, and aperture is 0.3mm, and spinneret orifice draw ratio (L/D) is 3.Then obtain as-spun fibre by spinning machine spinning, after oiling, obtain the preliminary draft silk of different winding speed through winding.Spinning temperature is at 220 DEG C, and drawing temperature is at 80 DEG C, and heat setting temperature is at 100 DEG C.
embodiment 3
PLA (PLA) 90 parts, PPA (PPA) 10 parts, polycarbodiimide (PCDI) 1 part, butyl titanate 1 part.
(1) blend modified polylactic acid fiber is prepared by the following method: by 45 parts of PLA resin under the condition of 60 DEG C through vacuumize 24h, then by PLA(45 part)/PPA(10 part)/PCDI(1 part)/TT-01(1 part) Homogeneous phase mixing, add double screw extruder melt blending and prepare spinning chips, extrusion temperature is at 180 DEG C;
(2) preparation of PLA and blended fiber thereof: PLA(45 part prepared by 45 parts of PLA and step (1))/PPA(10 part)/PCDI(1 part)/TT-01(1 part) blended slice in vacuum drying oven at 90 DEG C dry 48h, then prepare fiber by melt spinning-drawing-off two-step method.Wherein, spinnerets is 24 holes, and aperture is 0.3mm, and spinneret orifice draw ratio (L/D) is 3.Then obtain as-spun fibre by spinning machine spinning, after oiling, obtain the preliminary draft silk of different winding speed through winding.Spinning temperature is at 245 DEG C, and drawing temperature is at 95 DEG C, and heat setting temperature is at 130 DEG C.
embodiment 4
PLA (PLA) 90 parts, PPA (PPA) 10 parts, polycarbodiimide (PCDI) 0.5 part, butyl titanate 0.2 part
(1) blend modified polylactic acid fiber is prepared by the following method: by 45 parts of PLA resin under the condition of 60 DEG C through vacuumize 24h, then by PLA(45 part)/PPA(10 part)/PCDI(0.5 part)/TT-01(0.5 part) Homogeneous phase mixing, add double screw extruder melt blending and prepare spinning chips, extrusion temperature is at 150 DEG C;
(2) preparation of PLA and blended fiber thereof: PLA(45 part prepared by 45 parts of PLA and step (1))/PPA(10 part)/PCDI(0.5 part)/TT-01(0.5 part) blended slice in vacuum drying oven at 90 DEG C dry 48h, then prepare fiber by melt spinning-drawing-off two-step method.Wherein, spinnerets is 24 holes, and aperture is 0.3mm, and spinneret orifice draw ratio (L/D) is 3.Then obtain as-spun fibre by spinning machine spinning, after oiling, obtain the preliminary draft silk of different winding speed through winding.Spinning temperature is at 230 DEG C, and drawing temperature is at 85 DEG C, and heat setting temperature is at 115 DEG C.
comparative example 1pLA (PLA) 90 parts, PPA (PPA) 10 parts
Blend modified polylactic acid fiber is prepared by the following method: by 45 parts of PLA resin under the condition of 60 DEG C through vacuumize 24h, then by PLA (45 parts)/PPA(10 part) Homogeneous phase mixing, add double screw extruder melt blending and prepare spinning chips, extrusion temperature is at 160 DEG C.By 45 parts of PLA and PLA (45 parts)/PPA(10 part) blended slice in vacuum drying oven at 90 DEG C dry 48h, then prepare fiber by melt spinning-drawing-off two-step method.Wherein, spinnerets is 24 holes, and aperture is 0.3mm, and spinneret orifice draw ratio (L/D) is 3.Then obtain as-spun fibre by spinning machine spinning, after oiling, obtain the preliminary draft silk of different winding speed through winding.Spinning temperature is at 230 DEG C, and drawing temperature is at 85 DEG C, and heat setting temperature is at 115 DEG C.
Performance test:
Composite fiber prepared by above-mentioned enforcement 1-4 and comparative example 1 is made batten, with XQ-1 fiber strength and elongation instrument according to standard ISO 527-1:2012, ISO527-2:2012 and ISO178:2010 tests, test clamp distance is 10mm, crack velocity is 20mm/min, and test data is as following table 1:
Table 1
| Test event | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| TENSILE STRENGTH | MPa | 2.9 | 3.2 | 3.3 | 3.5 | 7.8 |
| Elastic modelling quantity | MPa | 33.2 | 44.3 | 45.6 | 38.1 | 82 |
| Elongation at break | % | 280 | 300 | 350 | 272 | 18.7 |
Data show the mechanical property of PLA/PPA and PLA/PPA/PCDI/TT-01 blended fiber.Compared with PLA/PPA blended fiber, add the mechanical property that PCDI and TT-01 does not improve blended fiber, declining all appears in the TENSILE STRENGTH of material and elastic modelling quantity.This may be that macromolecular flexibility increases because add after PCDI, fiber can also become large by drafting multiple, maximum drafting multiple can reach about 20 times.Therefore the interpolation of PCDI and TT-01 can improve high-temperature stability and the compatibility of blend well, and deformability and surface flatness are significantly improved, and flexibility improves.
Claims (7)
1. a novel high flexibility acid fiber by polylactic composite, is characterized in that: each component comprised and the parts by weight of component as follows:
PLA 70 parts-90 parts
PPA 10 parts-30 parts
Polycarbodiimide 0.1 part-1 part
Butyl titanate 0.1 part-1 part.
2. a kind of novel high flexibility acid fiber by polylactic composite according to claim 1, is characterized in that: described PLA weight average molecular weight is 80000-150000g/mol.
3. a kind of novel high flexibility acid fiber by polylactic composite according to claim 1, is characterized in that: described PPA weight average molecular weight is 20000-100000g/mol.
4. the preparation method of a kind of novel high flexibility acid fiber by polylactic composite according to any one of claim 1-3, is characterized in that: comprise the preparation process of PLA and blended slice thereof and the preparation process of PLA and blended fiber thereof.
5. the preparation method of a kind of novel high flexibility acid fiber by polylactic composite according to claim 4, is characterized in that:
(1) described PLA and blended slice thereof are prepared by the following method:
By PLA under the condition of 60 DEG C through vacuumize 24h, then by dried 35-45 part PLA, 10-30 part PPA, 0.1-1 part polycarbodiimide and 0.1-1 part butyl titanate Homogeneous phase mixing in proportion, add double screw extruder melt blending and prepare PLA/PPA/polycarbodiimide/butyl titanate co-blended spinning section, extrusion temperature is between 150-180 DEG C;
(2) PLA and blended fiber thereof are prepared by the following method:
PLA/PPA/polycarbodiimide/butyl titanate co-blended spinning 35-45 part PLA and step (1) prepared to be cut into slices in vacuum drying oven dry 48h at 90 DEG C, then prepares fiber by melt spinning-drawing-off two-step method; Then obtain as-spun fibre by spinning machine spinning, after oiling, obtain the preliminary draft silk of different winding speed through winding.
6. the preparation method of a kind of novel high flexibility acid fiber by polylactic composite according to claim 5, is characterized in that: the spinnerets of step (1) described spinning machine is 24 holes, and aperture is 0.3mm, and spinneret orifice draw ratio (L/D) is 3.
7. the preparation method of a kind of novel high flexibility acid fiber by polylactic composite according to claim 5, is characterized in that: described spinning temperature is between 220-245 DEG C, and drawing temperature is between 80-95 DEG C, and heat setting temperature is between 100-130 DEG C.
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| CN110144639A (en) * | 2019-06-06 | 2019-08-20 | 东华大学 | A kind of soft, hydrolytic-resistant polylactic acid fiber and preparation method thereof |
| CN111572983A (en) * | 2020-04-26 | 2020-08-25 | 浙江天益塑业有限公司 | High-strength degradable paper-plastic composite bag and preparation method thereof |
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| CN112410929A (en) * | 2020-11-03 | 2021-02-26 | 南通大学 | PLA/PTMC biomass composite fiber and preparation method and application thereof |
| CN115948815A (en) * | 2022-11-18 | 2023-04-11 | 湖北博韬合纤有限公司 | Preparation method of PLA degradable short fibers |
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