CN103276473A - Method for preparing celluloses and modified biodegradable polymer blend fibers - Google Patents

Method for preparing celluloses and modified biodegradable polymer blend fibers Download PDF

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CN103276473A
CN103276473A CN201310245086XA CN201310245086A CN103276473A CN 103276473 A CN103276473 A CN 103276473A CN 201310245086X A CN201310245086X A CN 201310245086XA CN 201310245086 A CN201310245086 A CN 201310245086A CN 103276473 A CN103276473 A CN 103276473A
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degradable
cellulose
modified
blended fiber
vacuum
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CN103276473B (en
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余木火
张玥
李欣达
李海峰
钟璇
黎欢
韩克清
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Donghua University
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Donghua University
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Abstract

The invention provides a method for preparing celluloses and modified biodegradable polymer blend fibers. The method is characterized by comprising the concrete steps: step one, vacuum-drying biodegradable polymers, and blending 80-90 weight percent of the vacuum-dried biodegradable polymers, 9.8-19.9 weight percent of active small molecules and 0.1-0.2 weight percent of initiating agent and then adopting a double-screw extruder to extrude to obtain graft-modified biodegradable polymers; step two, vacuum-drying celluloses and the graft-modified biodegradable polymers obtained in the step one, blending 20-30 weight percent of the vacuum-dried celluloses, 40-60 weight percent of ionic liquid and 20-30 weight percent of the vacuum-dried graft-modified biodegradable polymers and then adopting the double-screw extruder to extrude, and spinning out through a spinneret plate of a spinning pack; and washing off the ionic liquid of the obtained fibers through a water tank, then stretching and winding through the spinning pack, and finally obtaining the celluloses and the modified biodegradable polymer blend fibers. According to the method, the materials have good processing properties and biological properties.

Description

A kind of method for preparing cellulose and the polymer blended fiber of modified degradable
Technical field
The invention belongs to the processing modified field of novel green of macromolecular material, relate to the high-temperature blending melt spinning of cellulose and degradable macromolecule.
Background technology
Cellulose is a kind of common natural macromolecular material, and for the research and development of the abundantest renewable resource of this occurring in nature, particularly the study on the modification that it is carried out has caused people's concern widely this year.Cellulosic method of modifying commonly used at present comprises: the derivatization modification, method such as grafting, copolymerization and modification and blending and modifying, wherein the effect of grafting, copolymerization and modification is relatively good, but grafting, copolymerization and modification is very strict to the requirement of process conditions, the graft modification of existing cellulose and cellulose derivative rests on laboratory stage mostly, to realize further that extension production also has great difficulty, and the blending and modifying flow process is simple, realize suitability for industrialized production easily, especially with some degradable macromolecules aliphatic polyester PLA for example, blend such as PCL, can obtain renewable fully, degradable macromolecular material is for reducing environmental pollution, reduce consumption of petroleum etc. and have very profound significance.
The cellulose moisture-proof is better, but cellulosic non-refractory, intensity is lower, and toughness is also lower.And degradable macromolecule is except having good biological nature, and the molecule chain flexibility is better, and chemical stability is better.By blending and modifying, both given blended fiber biodegradable performance, also improved cellulosic stability and processing characteristics.According to different purposes and environmental condition, further in-depth is studied, and has become the emphasis brainstorm subject of many countries by MOLECULE DESIGN research improvement prescription, exploitation controllability environment-degradable plastic.But cellulose contains great amount of hydroxy group and other polar group, easily forms in the molecule and intermolecular hydrogen bonding, is difficult to dissolving and fusion, has limited cellulose and other high molecular co-blended spinnings.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing cellulose and the polymer blended fiber of modified degradable.Adopt double screw extruder, under the plasticization of ionic liquid, the polymer blended high temperature melt-spun that carries out of cellulose and modified degradable, under the powerful shearing force effect of extruder, make mixing, the fusion of material get more abundant, the living beings biodegradable fiber that processability is good is produced significant for the cellulosic high temperature melt-spun through engineering approaches of realization, industrialization.
In order to achieve the above object, the invention provides a kind of method for preparing cellulose and the polymer blended fiber of modified degradable, it is characterized in that concrete steps comprise:
The first step: with degradable macromolecule vacuumize, with adopting double screw extruder to extrude after the degradable macromolecule 80-90wt% after the vacuumize, active small molecular 9.8-19.9wt% and the initator 0.1-0.2wt% blend, obtain the graft modification degradable macromolecule;
Second step: the graft modification degradable macromolecule vacuumize that cellulose and the first step are obtained, extrude adopting double screw extruder after the graft modification degradable macromolecule 20-30% blend after the cellulose 20-30wt% after the vacuumize, ionic liquid 40-60wt% and the vacuumize, after being spun by the spinnerets of filament spinning component, fiber process tank flush away ionic liquid with gained, stretch, reel by filament spinning component then, obtain the polymer blended fiber of cellulose and modified degradable.
Preferably, the cellulose in described second step is the common cotton fiber, and the degree of polymerization is at 300-600.
Preferably, the baking temperature of degradable macromolecule is 50-80 ℃ in the described first step, and vacuum is 90~130Pa, and the time is 12-36h.
Preferably, cellulosic baking temperature is 50-80 ℃ in described second step, and vacuum is 90~130Pa, and the time is 12-36h.
Preferably, the baking temperature of graft modification degradable macromolecule is 50-80 ℃ in described second step, and vacuum is 90~130Pa, and the time is 12-36h.
Preferably, the ionic liquid in described second step is 1-butyl-3-methylimidazole villaumite ([BMIM] Cl) or 1-ethyl-3-methylimidazole acetate ([EMIM] Ac).
Preferably, the degradable macromolecule in the described first step is polyethylene glycol (PEG), PLA (PLA), polycaprolactone (PCL) or poly-(PHB).
Preferably, the initator in the described first step is dibenzoyl peroxide (BPO) or cumyl peroxide (DCP).
Preferably, the active small molecular in the described first step is acrylic acid (AA), methacrylic acid (MMA), maleic anhydride (MA) or glycidyl methacrylate (GMA).
Preferably, used double screw extruder was all parallel dual-screw extruding machine during the described first step and second went on foot, and its screw slenderness ratio is all 1: 35-1: 55.
Preferably, in the extrusion in described second step, temperature is 100-200 ℃, and screw speed is 300-400rpm, and the head pressure of double screw extruder is 3-5MPa, and the vacuum pump pressure of double screw extruder is 0.8-1MPa.
Compared with prior art, the invention has the beneficial effects as follows:
It is plasticizer that the present invention selects ionic liquid, adopt double screw extruder that cellulose is sheared dissolving, high temperature high shear forces by continous mode, improve cellulosic meltbility and spinnability, and degradable macromolecule is carried out chemical structure modification, make on its macromolecular chain in the grafting easily the group that reacts with the cellulose hydroxyl, thereby improve the adhesion of cellulose and degradable macromolecule, the mechanical property of raising blended fiber.
The specific embodiment
For the present invention is become apparent, now with preferred embodiment, and be described in detail below.
Embodiment 1
(1) with degradable macromolecule PEG (LG-DOW, PEG-200) at 60 ℃, vacuum is vacuumize 24 hours under the condition of 100Pa, with the degradable macromolecule PEG after the 300g vacuumize, 30g active small molecular MA (traditional Chinese medicines group, 10013128) and 0.5g initiator DCP (traditional Chinese medicines group, 800486712) adopt the parallel dual-screw extruding machine reaction to extrude after the blend, the screw zones temperature is 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and 140 ℃, screw speed is 300rpm, the screw slenderness ratio of double screw extruder is 1: 45, obtains PEG-g-MA after unreacted MA is removed with acetone extract.
(2) with the degree of polymerization be 500 gossypin (Jiangsu Longma, M500) and PEG-g-MA at 60 ℃, vacuum is vacuumize 24 hours under the condition of 115Pa, with the gossypin after the 400g vacuumize, PEG-g-MA after the 200g vacuumize, 1000g[BMIM] C1 (upward marine origin victory, LM1039) blend evenly adopts parallel dual-screw extruding machine to extrude in the back, deaeration, after the filtration, spinnerets by filament spinning component spins, the screw slenderness ratio of double screw extruder is 1: 40, the screw zones temperature is 100 ℃, 110 ℃, 120 ℃, 120 ℃, 130 ℃ and 130 ℃, screw speed is 250rpm, the head pressure of double screw extruder is 4MPa, vacuum pump pressure is 0.8MPa, spinning temperature is 140 ℃, fiber process tank water eccysis deionization liquid with gained, stretch by filament spinning component then, reel, described coiling is finished by the up-coiler in the filament spinning component, described up-coiler winding speed is 500m/min, obtain cellulose/PEG-g-MA blended fiber, its fiber number is 4.32dtex, dried fracture strength is 2.87cN/dtex, wet breaking strength is 1.59cN/dtex, and dried elongation at break is 22.6%, and wet elongation at break is 42.6%.
Embodiment 2
(1) with degradable macromolecule PLA (U.S. NatureWorks, 4032D) at 70 ℃, vacuum is vacuumize 12 hours under the condition of 110Pa, with the degradable macromolecule PLA after the 400g vacuumize, 40g active small molecular AA (traditional Chinese medicines group, 80001428) and 0.4g initiator B PO (traditional Chinese medicines group, 80016028) adopt the parallel dual-screw extruding machine reaction to extrude after the blend, the screw zones temperature is 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃ and 120 ℃, screw speed is 200rpm, the screw slenderness ratio of double screw extruder is 1: 50, obtains PLA-g-AA after unreacted AA is removed with ethanol extraction.
(2) with the degree of polymerization be 500 gossypin (Jiangsu Longma, M500) and PLA-g-AA at 70 ℃, vacuum is vacuumize 12 hours under the condition of 100Pa, with the gossypin after the 400g vacuumize, PLA-g-AA after the 300g vacuumize, 1000g[BMIM] Cl (upward marine origin victory, LM1039) blend evenly adopts parallel dual-screw extruding machine to extrude in the back, deaeration, after the filtration, spinnerets by filament spinning component spins, the screw slenderness ratio of double screw extruder is 1: 38, the screw zones temperature is 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃ and 170 ℃, screw speed is 250rpm, the head pressure of double screw extruder is 5MPa, vacuum pump pressure is 0.8MPa, spinning temperature is 170 ℃, fiber process tank water eccysis deionization liquid with gained, stretch by filament spinning component then, reel, described coiling is finished by the up-coiler in the filament spinning component, described up-coiler winding speed is 1000m/min, obtain cellulose/PLA-g-AA blended fiber, its fiber number is 3.73dtex, dried fracture strength is 2.51cN/dtex, wet breaking strength is 1.34cN/dtex, and dried elongation at break is 26.9%, and wet elongation at break is 49.3%.
Embodiment 3
(1) with degradable macromolecule PLA (U.S. NatureWorks, 4032D) at 70 ℃, vacuum is vacuumize 12 hours under the condition of 110Pa, with the degradable macromolecule PLA after the 400g vacuumize, 40g active small molecular GMA (traditional Chinese medicines group, 39254470) and 0.4g initiator DCP (traditional Chinese medicines group, 800486712) adopt the double screw extruder reaction to extrude after the blend, the screw zones temperature is 100 ℃, 110 ℃, 120 ℃, 130 ℃, 130 ℃ and 140 ℃, screw speed is 200rpm, the screw slenderness ratio of double screw extruder is 1: 50, obtains PLA-g-GMA after unreacted GMA is removed with acetone extract.
(2) with the degree of polymerization be 500 gossypin (Jiangsu Longma, M500) and PLA-g-GMA at 70 ℃, vacuum is vacuumize 12 hours under the condition of 105Pa, with the gossypin after the 400g vacuumize, PEG-g-GMA after the 300g vacuumize, 1200g[EMIM] Ac (upward marine origin victory, LM1132) blend evenly adopts double screw extruder to extrude in the back, deaeration, after the filtration, spinnerets by filament spinning component spins, the screw slenderness ratio of double screw extruder is 1: 48, the screw zones temperature is 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃ and 170 ℃, screw speed is 250rpm, the head pressure of double screw extruder is 5MPa, vacuum pump pressure is 0.8MPa, spinning temperature is 170 ℃, fiber process tank water eccysis deionization liquid with gained, stretch by filament spinning component then, reel, described coiling is finished by the up-coiler in the filament spinning component, described up-coiler winding speed is 1000m/min, obtain cellulose PLA-g-GMA blended fiber, its fiber number is 3.77dtex, dried fracture strength is 3.31cN/dtex, wet breaking strength is 1.81cN/dtex, and dried elongation at break is 25.8%, and wet elongation at break is 52.5%.
Embodiment 4
(1) with degradable macromolecule PCL (German BASF, D602) at 70 ℃, vacuum is vacuumize 24 hours under the condition of 110Pa, with the degradable macromolecule PCL after the 300g vacuumize, 20g active small molecular MA (traditional Chinese medicines group, 10013128) and 0.3g initiator B PO (traditional Chinese medicines group, 80016028) adopt the double screw extruder reaction to extrude after the blend, the screw zones temperature is 100 ℃, 110 ℃, 120 ℃, 120 ℃, 130 ℃ and 130 ℃, screw speed is 300rpm, the screw slenderness ratio of double screw extruder is 1: 42, obtains PCL-g-MA after unreacted MA is removed with acetone extract.
(2) with the degree of polymerization be 550 gossypin (Jiangsu Longma, M550) and PCL-g-MA at 70 ℃, vacuum is vacuumize 24 hours under the condition of 95Pa, with the gossypin after the 400g vacuumize, PCL-g-MA after the 200g vacuumize, 1000g[EMIM] Ac (upward marine origin victory, LM1132) blend evenly adopts double screw extruder to extrude in the back, deaeration, after the filtration, spinnerets by filament spinning component spins, the screw slenderness ratio of double screw extruder is 1: 45, the screw zones temperature is 100 ℃, 110 ℃, 120 ℃, 120 ℃, 130 ℃ and 130 ℃, screw speed is 250rpm, the head pressure of double screw extruder is 3MPa, vacuum pump pressure is 1MPa, spinning temperature is 140 ℃, fiber process tank water eccysis deionization liquid with gained, stretch by filament spinning component then, reel, described coiling is finished by the up-coiler in the filament spinning component, described up-coiler winding speed is 800m/min, obtain cellulose PCL-g-MA blended fiber, its fiber number is 3.59dtex, dried fracture strength is 2.83cN/dtex, wet breaking strength is 1.56cN/dtex, and dried elongation at break is 30.1%, and wet elongation at break is 58.4%.
Embodiment 5
(1) with degradable macromolecule PHB (German BASF, F669) be vacuumize 36 hours under the condition of 100Pa at 70 ℃, vacuum, extrude adopting the double screw extruder reaction after the degradable macromolecule PHB after the 300g vacuumize, 40g active small molecular GMA and the 0.6g initiator B PO blend, the screw zones temperature is 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ and 140 ℃, screw speed is 350rpm, and the screw slenderness ratio of double screw extruder is to obtain PHB-g-GMA after unreacted GMA being removed with acetone extract in 1: 45.
(2) with the degree of polymerization be 600 gossypin (Jiangsu Longma, M600) and PHB-g-GMA at 70 ℃, vacuum is vacuumize 24 hours under the condition of 120Pa, with the gossypin after the 400g vacuumize, PHB-g-GMA after the 200g vacuumize, 1000g[EMIM] Ac (upward marine origin victory, LM1132) blend evenly adopts double screw extruder to extrude in the back, deaeration, after the filtration, spinnerets by filament spinning component spins, the screw slenderness ratio of double screw extruder is 1: 55, the screw zones temperature is 120 ℃, 120 ℃, 140 ℃, 160 ℃, 170 ℃ and 180 ℃, screw speed is 400rpm, the head pressure of double screw extruder is 3MPa, vacuum pump pressure is 0.8MPa, spinning temperature is 180 ℃, fiber process tank water eccysis deionization liquid with gained, stretch by filament spinning component then, reel, described coiling is finished by the up-coiler in the filament spinning component, described up-coiler winding speed is 800m/min, obtain cellulose PHB-g-GMA blended fiber, its fiber number is 3.92dtex, dried fracture strength is 3.15cN/dtex, wet breaking strength is 1.59cN/dtex, and dried elongation at break is 25.5%, and wet elongation at break is 48.7%.

Claims (10)

1. method for preparing cellulose and the polymer blended fiber of modified degradable is characterized in that concrete steps comprise:
The first step: with degradable macromolecule vacuumize, with adopting double screw extruder to extrude after the degradable macromolecule 80-90wt% after the vacuumize, active small molecular 9.8-19.9wt% and the initator 0.1-0.2wt% blend, obtain the graft modification degradable macromolecule;
Second step: the graft modification degradable macromolecule vacuumize that cellulose and the first step are obtained, extrude adopting double screw extruder after the graft modification degradable macromolecule 20-30% blend after the cellulose 20-30wt% after the vacuumize, ionic liquid 40-60wt% and the vacuumize, after being spun by the spinnerets of filament spinning component, fiber process tank flush away ionic liquid with gained, stretch, reel by filament spinning component then, obtain the polymer blended fiber of cellulose and modified degradable.
2. the method for preparing cellulose and the polymer blended fiber of modified degradable as claimed in claim 1 is characterized in that, the cellulose in described second step is the common cotton fiber, and the degree of polymerization is at 300-600.
3. the method for preparing cellulose and the polymer blended fiber of modified degradable as claimed in claim 1 is characterized in that, the baking temperature of degradable macromolecule is 50-80 ℃ in the described first step, and vacuum is 90~130Pa, and the time is 12-36h.
4. the method for preparing cellulose and the polymer blended fiber of modified degradable as claimed in claim 1 is characterized in that, cellulosic baking temperature is 50-80 ℃ in described second step, and vacuum is 90~130Pa, and the time is 12-36h.
5. the method for preparing cellulose and the polymer blended fiber of modified degradable as claimed in claim 1 is characterized in that, the baking temperature of graft modification degradable macromolecule is 50-80 ℃ in described second step, and vacuum is 90~130Pa, and the time is 12-36h.
6. the method for preparing cellulose and the polymer blended fiber of modified degradable as claimed in claim 1 is characterized in that, the ionic liquid in described second step is 1-butyl-3-methylimidazole villaumite or 1-ethyl-3-methylimidazole acetate.
7. the method for preparing cellulose and the polymer blended fiber of modified degradable as claimed in claim 1 is characterized in that, the degradable macromolecule in the described first step is polyethylene glycol, PLA, polycaprolactone or poly-.
8. the method for preparing cellulose and the polymer blended fiber of modified degradable as claimed in claim 1 is characterized in that, the initator in the described first step is dibenzoyl peroxide or cumyl peroxide.
9. the method for preparing cellulose and the polymer blended fiber of modified degradable as claimed in claim 1 is characterized in that, the active small molecular in the described first step is acrylic acid, methacrylic acid, maleic anhydride or glycidyl methacrylate.
10. the method for preparing cellulose and the polymer blended fiber of modified degradable as claimed in claim 1, it is characterized in that, in the extrusion in described second step, temperature is 100-200 ℃, screw speed is 300-400rpm, the head pressure of double screw extruder is 3-5MPa, and the vacuum pump pressure of double screw extruder is 0.8-1MPa.
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CN109705601A (en) * 2019-03-01 2019-05-03 安徽森泰木塑集团股份有限公司 The outdoor template formula of modeling packet wood and technique
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Publication number Priority date Publication date Assignee Title
CN104151622A (en) * 2014-08-08 2014-11-19 华中科技大学 Biodegradable cellulose blending material and preparation method thereof
EP3181124A1 (en) * 2015-12-16 2017-06-21 Universität Basel Abuse deterrent pharmaceutical dosage forms
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CN108728923A (en) * 2018-06-07 2018-11-02 新沂市中诺新材料科技有限公司 A kind of preparation method of Neu tuberosum
CN109705601A (en) * 2019-03-01 2019-05-03 安徽森泰木塑集团股份有限公司 The outdoor template formula of modeling packet wood and technique
CN109705601B (en) * 2019-03-01 2021-04-09 安徽森泰木塑集团股份有限公司 Formula and process for plastic-clad wood outdoor template
CN113026127A (en) * 2021-02-08 2021-06-25 东华大学 Degradable silk and preparation method thereof

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