CN103276473B - A kind of method preparing cellulose and the polymer blended fiber of modified degradable - Google Patents
A kind of method preparing cellulose and the polymer blended fiber of modified degradable Download PDFInfo
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- CN103276473B CN103276473B CN201310245086.XA CN201310245086A CN103276473B CN 103276473 B CN103276473 B CN 103276473B CN 201310245086 A CN201310245086 A CN 201310245086A CN 103276473 B CN103276473 B CN 103276473B
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Abstract
The invention provides a kind of method preparing cellulose and the polymer blended fiber of modified degradable, it is characterized in that, concrete steps comprise: the first step: by degradable macromolecule vacuumize, blended to degradable macromolecule 80-90wt% after vacuumize, active small molecular 9.8-19.9wt% and initator 0.1-0.2wt% rear employing double screw extruder is extruded, obtains graft modification degradable macromolecule; Second step: the graft modification degradable macromolecule vacuumize that cellulose and the first step are obtained, blended for graft modification degradable macromolecule 20-30% after cellulose 20-30wt% after vacuumize, ionic liquid 40-60wt% and vacuumize rear employing double screw extruder is extruded, after being spun by the spinnerets of filament spinning component, the fiber of gained is washed away ionic liquid through tank, then undertaken stretching, reeling by filament spinning component, obtain cellulose and the polymer blended fiber of modified degradable.Present invention gives the good processing characteristics of material and biological property.
Description
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, for the research and development of the abundantest renewable resource of this occurring in nature, particularly to the study on the modification that it carries out, causes the concern widely of people this year.Cellulosic method of modifying conventional at present comprises: derivatization modification, the method such as grafting, copolymerization and modification and blending and modifying, wherein the effectiveness comparison of grafting, copolymerization and modification is 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, extension to be realized further and produce great difficulty in addition, and blending and modifying flow process is simple, easily realize suitability for industrialized production, especially degradable macromolecule such as aliphatic polyester PLA with some, PCL etc. are blended, can obtain completely renewable, degradable macromolecular material, for minimizing environmental pollution, reduce consumption of petroleum etc. and there is very profound significance.
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, molecule chain flexibility is better, and chemical stability is better.By blending and modifying, both imparted the biodegradable performance of blended fiber, also improved cellulosic stability and processing characteristics.According to different purposes and environmental condition, deepen research further, and become the emphasis brainstorm subject of many countries by MOLECULE DESIGN Improvement formula, exploitation controllability environment-degradable plastic.But cellulose contains great amount of hydroxy group and other polar group, easily formed in molecule and intermolecular hydrogen bonding, be difficult to dissolve and melting, limit 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 preparing cellulose and the polymer blended fiber of modified degradable.Adopt double screw extruder, under the plasticization of ionic liquid, cellulose and modified degradable is polymer blended carries out high temperature melt-spun, under the shearing force effect that extruder is powerful, make the mixing of material, melting obtains more abundant, the living beings biodegradable fiber that processability is good, for realize cellulosic high temperature melt-spun through engineering approaches, industrialization produce significant.
In order to achieve the above object, the invention provides a kind of method preparing cellulose and the polymer blended fiber of modified degradable, it is characterized in that, concrete steps comprise:
The first step: by degradable macromolecule vacuumize, blended to degradable macromolecule 80-90wt% after vacuumize, active small molecular 9.8-19.9wt% and initator 0.1-0.2wt% rear employing double screw extruder is extruded, obtains graft modification degradable macromolecule;
Second step: the graft modification degradable macromolecule vacuumize that cellulose and the first step are obtained, blended for graft modification degradable macromolecule 20-30% after cellulose 20-30wt% after vacuumize, ionic liquid 40-60wt% and vacuumize rear employing double screw extruder is extruded, after being spun by the spinnerets of filament spinning component, the fiber of gained is washed away ionic liquid through tank, then undertaken stretching, reeling by filament spinning component, obtain cellulose and the polymer blended fiber of modified degradable.
Preferably, the cellulose in described second step is common cotton fiber, and the degree of polymerization is at 300-600.
Preferably, in the described first step, the baking temperature of degradable macromolecule is 50-80 DEG C, and vacuum is 90 ~ 130Pa, and the time is 12-36h.
Preferably, in described second step, cellulosic baking temperature is 50-80 DEG C, and vacuum is 90 ~ 130Pa, and the time is 12-36h.
Preferably, in described second step, the baking temperature of graft modification degradable macromolecule is 50-80 DEG C, 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-β-hydroxybutyric acid (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, in the described first step and second step, double screw extruder used is all parallel dual-screw extruding machine, and its screw slenderness ratio is all 1: 35-1: 55.
Preferably, in the extrusion of described second step, temperature is 100-200 DEG C, 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:
Selective ion mode liquid of the present invention is plasticizer, adopt double screw extruder to carry out shearing to cellulose to dissolve, by the high temperature high shear effect of continous mode, improve cellulosic meltbility and spinnability, and chemical structure modification is carried out to degradable macromolecule, to make on its macromolecular chain the group that grafting easily reacts with cellulose hydroxyl group, thus improve the adhesion of cellulose and degradable macromolecule, the mechanical property of raising blended fiber.
Detailed description of the invention
For making the present invention become apparent, hereby with preferred embodiment, and be described in detail below.
Embodiment 1
(1) by degradable macromolecule PEG (LG-DOW, PEG-200) at 60 DEG C, vacuum is vacuumize 24 hours under the condition of 100Pa, by the degradable macromolecule PEG after 300g vacuumize, 30g active small molecular MA (traditional Chinese medicines group, 10013128) and 0.5g initiator DCP (traditional Chinese medicines group, 800486712) blended rear employing parallel dual-screw extruding machine reactive extrursion, screw zones temperature is 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C and 140 DEG C, screw speed is 300rpm, the screw slenderness ratio of double screw extruder is 1: 45, PEG-g-MA is obtained by after unreacted MA acetone extract removing.
(2) by the degree of polymerization be 500 gossypin (Jiangsu Longma, M500) and PEG-g-MA at 60 DEG C, vacuum is vacuumize 24 hours under the condition of 115Pa, by the gossypin after 400g vacuumize, PEG-g-MA after 200g vacuumize, (upper marine origin is prompt for 1000g [BMIM] C1, LM1039) the blended evenly rear parallel dual-screw extruding machine that adopts is extruded, deaeration, after filtration, spun by the spinnerets of filament spinning component, the screw slenderness ratio of double screw extruder is 1: 40, screw zones temperature is 100 DEG C, 110 DEG C, 120 DEG C, 120 DEG C, 130 DEG C and 130 DEG C, screw speed is 250rpm, the head pressure of double screw extruder is 4MPa, vacuum pump pressure is 0.8MPa, spinning temperature is 140 DEG C, by the fiber of gained through tank water eccysis deionization liquid, then stretched by filament spinning component, winding, described winding is completed by the up-coiler in filament spinning component, described up-coiler winding speed is 500m/min, obtain cellulose/PEG-g-MA blended fiber, its fiber number is 4.32dtex, dry fracture strength is 2.87cN/dtex, wet breaking strength is 1.59cN/dtex, dry elongation at break is 22.6%, wet elongation at break is 42.6%.
Embodiment 2
(1) by degradable macromolecule PLA (U.S. NatureWorks, 4032D) at 70 DEG C, vacuum is vacuumize 12 hours under the condition of 110Pa, by the degradable macromolecule PLA after 400g vacuumize, 40g active small molecular AA (traditional Chinese medicines group, 80001428) and 0.4g initiator B PO (traditional Chinese medicines group, 80016028) blended rear employing parallel dual-screw extruding machine reactive extrursion, screw zones temperature is 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C and 120 DEG C, screw speed is 200rpm, the screw slenderness ratio of double screw extruder is 1: 50, PLA-g-AA is obtained by after unreacted AA ethanol extraction removing.
(2) by the degree of polymerization be 500 gossypin (Jiangsu Longma, M500) and PLA-g-AA at 70 DEG C, vacuum is vacuumize 12 hours under the condition of 100Pa, by the gossypin after 400g vacuumize, PLA-g-AA after 300g vacuumize, (upper marine origin is prompt for 1000g [BMIM] Cl, LM1039) the blended evenly rear parallel dual-screw extruding machine that adopts is extruded, deaeration, after filtration, spun by the spinnerets of filament spinning component, the screw slenderness ratio of double screw extruder is 1: 38, screw zones temperature is 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C and 170 DEG C, screw speed is 250rpm, the head pressure of double screw extruder is 5MPa, vacuum pump pressure is 0.8MPa, spinning temperature is 170 DEG C, by the fiber of gained through tank water eccysis deionization liquid, then stretched by filament spinning component, winding, described winding is completed by the up-coiler in filament spinning component, described up-coiler winding speed is 1000m/min, obtain cellulose/PLA-g-AA blended fiber, its fiber number is 3.73dtex, dry fracture strength is 2.51cN/dtex, wet breaking strength is 1.34cN/dtex, dry elongation at break is 26.9%, wet elongation at break is 49.3%.
Embodiment 3
(1) by degradable macromolecule PLA (U.S. NatureWorks, 4032D) at 70 DEG C, vacuum is vacuumize 12 hours under the condition of 110Pa, by the degradable macromolecule PLA after 400g vacuumize, 40g active small molecular GMA (traditional Chinese medicines group, 39254470) and 0.4g initiator DCP (traditional Chinese medicines group, 800486712) blended rear employing double screw extruder reactive extrursion, screw zones temperature is 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 130 DEG C and 140 DEG C, screw speed is 200rpm, the screw slenderness ratio of double screw extruder is 1: 50, PLA-g-GMA is obtained by after unreacted GMA acetone extract removing.
(2) by the degree of polymerization be 500 gossypin (Jiangsu Longma, M500) and PLA-g-GMA at 70 DEG C, vacuum is vacuumize 12 hours under the condition of 105Pa, by the gossypin after 400g vacuumize, PEG-g-GMA after 300g vacuumize, (upper marine origin is prompt for 1200g [EMIM] Ac, LM1132) the blended evenly rear double screw extruder that adopts is extruded, deaeration, after filtration, spun by the spinnerets of filament spinning component, the screw slenderness ratio of double screw extruder is 1: 48, screw zones temperature is 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C and 170 DEG C, screw speed is 250rpm, the head pressure of double screw extruder is 5MPa, vacuum pump pressure is 0.8MPa, spinning temperature is 170 DEG C, by the fiber of gained through tank water eccysis deionization liquid, then stretched by filament spinning component, winding, described winding is completed by the up-coiler in filament spinning component, described up-coiler winding speed is 1000m/min, obtain cellulose PLA-g-GMA blended fiber, its fiber number is 3.77dtex, dry fracture strength is 3.31cN/dtex, wet breaking strength is 1.81cN/dtex, dry elongation at break is 25.8%, wet elongation at break is 52.5%.
Embodiment 4
(1) by degradable macromolecule PCL (German BASF, D602) at 70 DEG C, vacuum is vacuumize 24 hours under the condition of 110Pa, by the degradable macromolecule PCL after 300g vacuumize, 20g active small molecular MA (traditional Chinese medicines group, 10013128) and 0.3g initiator B PO (traditional Chinese medicines group, 80016028) blended rear employing double screw extruder reactive extrursion, screw zones temperature is 100 DEG C, 110 DEG C, 120 DEG C, 120 DEG C, 130 DEG C and 130 DEG C, screw speed is 300rpm, the screw slenderness ratio of double screw extruder is 1: 42, PCL-g-MA is obtained by after unreacted MA acetone extract removing.
(2) by the degree of polymerization be 550 gossypin (Jiangsu Longma, M550) and PCL-g-MA at 70 DEG C, vacuum is vacuumize 24 hours under the condition of 95Pa, by the gossypin after 400g vacuumize, PCL-g-MA after 200g vacuumize, (upper marine origin is prompt for 1000g [EMIM] Ac, LM1132) the blended evenly rear double screw extruder that adopts is extruded, deaeration, after filtration, spun by the spinnerets of filament spinning component, the screw slenderness ratio of double screw extruder is 1: 45, screw zones temperature is 100 DEG C, 110 DEG C, 120 DEG C, 120 DEG C, 130 DEG C and 130 DEG C, screw speed is 250rpm, the head pressure of double screw extruder is 3MPa, vacuum pump pressure is 1MPa, spinning temperature is 140 DEG C, by the fiber of gained through tank water eccysis deionization liquid, then stretched by filament spinning component, winding, described winding is completed by the up-coiler in filament spinning component, described up-coiler winding speed is 800m/min, obtain cellulose PCL-g-MA blended fiber, its fiber number is 3.59dtex, dry fracture strength is 2.83cN/dtex, wet breaking strength is 1.56cN/dtex, dry elongation at break is 30.1%, wet elongation at break is 58.4%.
Embodiment 5
(1) by degradable macromolecule PHB (German BASF, F669) 70 DEG C, vacuum be the condition of 100Pa under vacuumize 36 hours, by blended for degradable macromolecule PHB, 40g active small molecular GMA after 300g vacuumize and 0.6g initiator B PO rear employing double screw extruder reactive extrursion, screw zones temperature is 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C and 140 DEG C, screw speed is 350rpm, and the screw slenderness ratio of double screw extruder is by unreacted GMA acetone extract removing after obtain PHB-g-GMA at 1: 45.
(2) by the degree of polymerization be 600 gossypin (Jiangsu Longma, M600) and PHB-g-GMA at 70 DEG C, vacuum is vacuumize 24 hours under the condition of 120Pa, by the gossypin after 400g vacuumize, PHB-g-GMA after 200g vacuumize, (upper marine origin is prompt for 1000g [EMIM] Ac, LM1132) the blended evenly rear double screw extruder that adopts is extruded, deaeration, after filtration, spun by the spinnerets of filament spinning component, the screw slenderness ratio of double screw extruder is 1: 55, screw zones temperature is 120 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 170 DEG C and 180 DEG C, screw speed is 400rpm, the head pressure of double screw extruder is 3MPa, vacuum pump pressure is 0.8MPa, spinning temperature is 180 DEG C, by the fiber of gained through tank water eccysis deionization liquid, then stretched by filament spinning component, winding, described winding is completed by the up-coiler in filament spinning component, described up-coiler winding speed is 800m/min, obtain cellulose PHB-g-GMA blended fiber, its fiber number is 3.92dtex, dry fracture strength is 3.15cN/dtex, wet breaking strength is 1.59cN/dtex, dry elongation at break is 25.5%, wet elongation at break is 48.7%.
Claims (1)
1. prepare a method for cellulose and the polymer blended fiber of modified degradable, it is characterized in that, concrete steps comprise:
The first step: by degradable macromolecule vacuumize, described degradable macromolecule is polyethylene glycol, PLA, polycaprolactone or poly-β-hydroxybutyric acid, the baking temperature of degradable macromolecule is 50-80 DEG C, vacuum is 90 ~ 130Pa, time is 12-36h, blended to degradable macromolecule 80-90wt% after vacuumize, active small molecular 9.8-19.9wt% and initator 0.1-0.2wt% rear employing double screw extruder is extruded, obtains graft modification degradable macromolecule; Described active small molecular is acrylic acid, methacrylic acid, maleic anhydride or glycidyl methacrylate, and described initator is dibenzoyl peroxide or cumyl peroxide;
Second step: the graft modification degradable macromolecule vacuumize that cellulose and the first step are obtained, cellulose is common cotton fiber, the degree of polymerization is at 300-600, cellulosic baking temperature is 50-80 DEG C, vacuum is 90 ~ 130Pa, time is 12-36h, the baking temperature of graft modification degradable macromolecule is 50-80 DEG C, vacuum is 90 ~ 130Pa, time is 12-36h, by the cellulose 20-30wt% after vacuumize, the blended rear employing double screw extruder of graft modification degradable macromolecule 20-30% after ionic liquid 40-60wt% and vacuumize is extruded, in extrusion, temperature is 100-200 DEG C, screw speed is 300-400rpm, the head pressure of double screw extruder is 3-5MPa, the vacuum pump pressure of double screw extruder is 0.8-1MPa, after being spun by the spinnerets of filament spinning component, the fiber of gained is washed away ionic liquid through tank, then stretched by filament spinning component, winding, obtain cellulose and the polymer blended fiber of modified degradable, described ionic liquid is 1-butyl-3-methylimidazole villaumite or 1-ethyl-3-methylimidazole acetate.
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| CN104151622B (en) * | 2014-08-08 | 2016-09-07 | 华中科技大学 | A kind of biodegradable cellulose intermingling material and preparation method thereof |
| EP3181124A1 (en) * | 2015-12-16 | 2017-06-21 | Universität Basel | Abuse deterrent pharmaceutical dosage forms |
| 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 |
| 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 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706883A (en) * | 2004-06-09 | 2005-12-14 | 华东理工大学 | Completely biodegradable hydrophobic material and its prepn |
| CN102191587A (en) * | 2010-03-03 | 2011-09-21 | 盐城纺织职业技术学院 | Biodegradable two-component low-melting point composite fiber |
| CN102965752A (en) * | 2012-11-28 | 2013-03-13 | 东华大学 | Cellulose in-situ urea modified plastification melt spinning method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706883A (en) * | 2004-06-09 | 2005-12-14 | 华东理工大学 | Completely biodegradable hydrophobic material and its prepn |
| CN102191587A (en) * | 2010-03-03 | 2011-09-21 | 盐城纺织职业技术学院 | Biodegradable two-component low-melting point composite fiber |
| CN102965752A (en) * | 2012-11-28 | 2013-03-13 | 东华大学 | Cellulose in-situ urea modified plastification melt spinning method |
Non-Patent Citations (1)
| Title |
|---|
| 纤维素基可生物降解共混高分子材料的制备和性能;段丽艳等;《高分子材料科学与工程》;20080930;第24卷(第9期);第32-35页，第40页 * |
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