CN102586936B - Degradable fibers with good resilience and preparation method thereof - Google Patents
Degradable fibers with good resilience and preparation method thereof Download PDFInfo
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- CN102586936B CN102586936B CN201110453168.4A CN201110453168A CN102586936B CN 102586936 B CN102586936 B CN 102586936B CN 201110453168 A CN201110453168 A CN 201110453168A CN 102586936 B CN102586936 B CN 102586936B
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- 239000000835 fiber Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000009987 spinning Methods 0.000 claims abstract description 8
- 238000002074 melt spinning Methods 0.000 claims abstract description 6
- 239000004970 Chain extender Substances 0.000 claims description 29
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 12
- 238000004804 winding Methods 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 8
- 238000009998 heat setting Methods 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- 206010013786 Dry skin Diseases 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000011067 equilibration Methods 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 229920006306 polyurethane fiber Polymers 0.000 abstract description 2
- 210000004177 elastic tissue Anatomy 0.000 abstract 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 230000004927 fusion Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229940006015 4-hydroxybutyric acid Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000006223 plastic coating Substances 0.000 description 1
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Artificial Filaments (AREA)
Abstract
The invention discloses a method for preparing degradable fibers with good resilience. The method comprises the following steps of: mixing components A, B and C in a mass ratio of 100:(1.5-10):(0.5-2.5), spinning by using melt spinning and coiling equipment to obtain primary fibers, and balancing, drawing and shaping to obtain blend fibers; and balancing the blend fibers again to obtain the target fibers. The fibers prepared by the method are biomass polyester-based elastic fibers, and a main component P(3HB-co-4HB) has high biocompatibility and biodegradability and is sourced from biofermentation but not petroleum, so that the fibers are green sustainable environment-friendly fibers. The elastic fibers are prepared by a melting spinning technology, non polyurethane fibers are prepared by a solution spinning technology, and organic solvents are not used in the production process to avoid environmental pollution.
Description
Technical field
The present invention relates to a kind of good elastic biodegradable fiber and preparation method thereof that has, belong to the fibre in differentiation production technical field.
Background technology
Poly 3-hydroxy butyrate 4 hydroxybutyric acid ester [P (3HB-co-4HB)] is a kind of biomass polyester, generally by biofermentation, prepares.Because it has good biocompatibility and Wholly-degradable, can be used for manufacturing film, plastic containers, the plastic coating of environmental protection, also can, for the preparation of fiber, be used as absorbable operating suture line etc.By adjusting 4HB content in P (3HB-co-4HB), can obtain and there is lower melt temperature and the better P of degree of crystallinity, processing characteristics and heat endurance (3HB-co-4HB) product.Because P (3HB-co-4HB) contains the ester group to water sensitive, and easily produce the post crystallization phenomenon, therefore its spinning technique is always very difficult, main manifestations (1) spinning temperature scope is very narrow, processing temperature is high, and its thermal degradation is serious, and processing temperature is low, fluid mobility is poor, and fiber roll is around difficulty; (2) because the post crystallization effect is arranged, make the as-spun fibre yield stress, difficulty stretches.
Summary of the invention
For addressing the above problem, the invention provides a kind of P of utilization (3HB-co-4HB) preparation and there is good elastic biodegradable fiber and preparation method thereof.Method provided by the invention can effectively solve P (3HB-co-4HB) spinning temperature narrow range, and, because the post crystallization effect is arranged, makes the as-spun fibre yield stress, and the problems such as difficulty stretch.
The following scheme of concrete employing:
Preparation method with good elastic biodegradable fiber, by A, B, tri-kinds of components of C in mass ratio 100: (1.5～10): after mix (0.5～2.5), obtain as-spun fibre by melt spinning winding apparatus spinning moulding, then obtain blended fiber after balance, stretching, typing; This blended fiber is obtained to target fibers after balance again; Wherein,
Described A component and B component need be after dryings under vacuum condition, then mix with component C;
Described component A is P (3HB-co-4HB);
Described B component is EVA;
Described component C is the compound that crosslinking agent mixes with chain extender in 1: 10 in mass ratio～1: 20;
Described crosslinking agent is cumyl peroxide;
Described chain extender contains 5～9 epoxy radicals active groups.
In preferred scheme, in described P (3HB-co-4HB), the mol ratio of 3HB and 4HB is 85: 15, and the number-average molecular weight of described P (3HB-co-4HB) is 700,000.
In preferred scheme, the melt flow index of described EVA is 15g/10min, and acetate groups (hereinafter to be referred as VAC) content is 14-19wt.%.
In further preferred scheme, the dried moisture content of described component A is less than 0.005wt.%, and the dried moisture content of B component is less than 0.01wt.%.
In further preferred scheme, the hole diameter of spinneret of melt spinning winding apparatus is 0.3mm, Kong Changwei 0.55mm, and the extruded velocity of strand from spinneret hole is 5-15m/min, and cooling length is 1m, and winding speed is 200-300m/min.
In further preferred scheme, the as-spun fibre equilibrium temperature is 20 ℃ ± 2, and humidity is 65 ± 5%, and equilibration time is 20h at least.
In further preferred scheme, as-spun fibre stretches after balance in water-bath, and draft temperature is 65 ℃～80 ℃, and draw ratio is 8～15 times.
Further in preferred scheme, as-spun fibre be fixed to relaxation heat setting, setting temperature is 70～80 ℃.
In further preferred scheme, blended fiber is balance 48h under 20 ℃ ± 2,65 ± 5% condition, eliminates the fiber internal stress.
What by said method, prepare has a good elastic biodegradable fiber, and its elongation at break is 290%-850%, and when fiber extends respectively 50%, 150%, in the time of 200%, rebound degree is 100%.
The present invention is from the molecular conformation structure, particularly the control of aggregated structure is set out, by by P (3HB-co-4HB) with there is flexible EVA (EVA) blend, and introduce the chain extender that can suppress P (3HB-co-4HB) degraded and can make EVA produce crosslinked cumyl peroxide in Blending Processes, efficiently solve the fibroblast problem of P (3HB-co-4HB), by to fiber slaking stretch processing, the after-drawing performance of as-spun fibre obviously being improved, fiber after maturation process can bear the hot-stretch more than 10 times, and 1 times of underdoneization tensile fiber multiple less than.The two cross-linked networks that form in fiber of the present invention, molecule segment between nexus makes fiber have good ductility, network cross-linked point provides condition for elastic recovery, make fiber still there is good resilience under larger stretching ratio, and because this fibrous body structure is the P (3HB-co-4HB) with biological degradability, so the biodegradable fiber that utilizes it to prepare has good biological degradability equally.
With other elastomer and preparation method, compare, the present invention has following advantage:
(1) elastomer of the present invention is a kind of elastomer based on biomass polyester, its main component P (3HB-co-4HB) has good biocompatibility and biodegradable, and it derives from biofermentation but not oil, be therefore a kind of environmental protection fiber of Green Sustainable.
(2) what elastomer preparation method of the present invention adopted is the melt spinning technology, the solution spining technology that non-polyurethane fiber preparation adopts, and production process not with an organic solvent, can not cause environmental pollution.
(3) elastomer of the present invention, by having widened the process window temperature of P (3HB-co-4HB) adding of EVA and component C, has improved fibre-forming performance, has also improved the elongation at break of fiber.
(4) performance indications such as the elongation at break of elastomer of the present invention, work to break, elastic recovery rate obviously are better than P (3HB-co-4HB) fiber of one-component.
The specific embodiment
The following examples can make the present invention of those of ordinary skill in the art's comprehend, but do not limit the present invention in any way.
The experimental technique used in following embodiment, be conventional method if no special instructions.
The material used in following embodiment, all can obtain if no special instructions from commercial channels.
Fibrous mechanical property and resilience test are all carried out on electronics single fiber tensometer (Laizhou Electron equipment Co., Ltd), test condition is: temperature is 20 ℃, humidity is 65%, and draw speed is 20mm/min, and chuck spaces and averages for every group of sample of 10mm repeats to do 30 times.
Embodiment 1
1. by EVA (VAC content is 14%) and P (3HB-co-4HB) respectively at 70 ℃ and 90 ℃ of lower vacuumize 8h and 30h, and control the moisture content of cutting into slices and be less than respectively 0.01wt.% and 0.005wt.%.
2. by dried EVA, with P (3HB-co-4HB) section, be to mix at 3: 100 in mass ratio, and add 1 part of (in 100 parts of P (3HB-co-4HB)) cumyl peroxide and chain extender and mixture, wherein the quality proportioning of cumyl peroxide and chain extender is 1: 14.
The present embodiment chain extender used is that BASF AG produces
board ADR 4300 chain extenders, contain 5 epoxy radicals active groups.
3. after above-mentioned three fully being mixed, send into and spin front hopper, in screw extruder in 130 ℃ of-150 ℃ of plastifying fusions, the extruded velocity of 15m/min of take under 140 ℃ is 0.3mm from aperture, extrude in Kong Changwei 0.55mm spinnerets, after air-cooled long through 1m of the strand of extruding, with the winding speed coiling of 200m/min, obtain as-spun fibre.
4. as-spun fibre balance 20h under 20 ℃ ± 2,65 ± 5% relative humidity.Then stretch 12 times in 80 ℃ of water-baths, carry out relaxation heat setting under 70-80 ℃, then fiber balance 48h under 20 ℃ ± 2,65 ± 5% relative humidity, eliminated the fiber internal stress.
The elongation at break that the present embodiment prepares fiber is 770%, and when elongate fiber 50%, 150%, in the time of 200%, rebound degree is 100%.
The elongation at break of P under similarity condition (3HB-co-4HB) one-component fiber is 178%, and when percentage elongation is respectively 50%, 100% and 150%, the rebound degree of fiber is respectively: 83%, 74% and 68%.
Embodiment 2
1. with embodiment 1
2. by dried EVA, with P (3HB-co-4HB) section, be to mix at 3: 100 in mass ratio, and add the mixture of 2 parts of (in 100 parts of P (3HB-co-4HB)) cumyl peroxides and chain extender, wherein the mass ratio of cumyl peroxide and chain extender is 1: 15.
The present embodiment chain extender used is that BASF AG produces
board ADR 4300 chain extenders, contain 5 epoxy radicals active groups.
3. after above-mentioned three fully being mixed, send into and spin front hopper, in screw extruder in 130 ℃ of-150 ℃ of plastifying fusions, the extruded velocity of 15m/min of take under 135 ℃ is 0.3mm from aperture, extrude in Kong Changwei 0.55mm spinnerets, after air-cooled long through 1m of the strand of extruding, with the winding speed coiling of 300m/min, obtain as-spun fibre.
4. as-spun fibre balance 24h under 20 ℃ ± 2,65 ± 5% relative humidity.Then stretch 10 times in 70 ℃ of water-baths, carry out relaxation heat setting under 70-80 ℃, then fiber balance 48h under 20 ℃ ± 2,65 ± 5% relative humidity.
The elongation at break that the present embodiment prepares fiber is 850%, and when elongate fiber 50%, 150%, in the time of 200%, rebound degree is 100%.
Embodiment 3
1. with embodiment 1
2. by dried EVA, with P (3HB-co-4HB) section, be to mix at 10: 100 in mass ratio, and add the mixture of 2 parts of (in 100 parts of P (3HB-co-4HB)) cumyl peroxides and chain extender, wherein the mass ratio of cumyl peroxide and chain extender is 1: 10.
The present embodiment chain extender used is that BASF AG produces
board ADR-4368C/CS chain extender, contain 9 epoxy radicals active groups.
3. after above-mentioned three fully being mixed, send into and spin front hopper, in screw extruder in 130 ℃ of-150 ℃ of plastifying fusions, the extruded velocity of 5m/min of take under 130 ℃ is 0.3mm from aperture, extrude in Kong Changwei 0.55mm spinnerets, after air-cooled long through 1m of the strand of extruding, with the winding speed coiling of 200m/min, obtain as-spun fibre.
4. as-spun fibre balance 24h under 20 ℃ ± 2,65 ± 5% relative humidity.Then stretch 8 times in 65 ℃ of water-baths, carry out relaxation heat setting under 70-80 ℃, then fiber balance 48h under 20 ℃ ± 2,65 ± 5% relative humidity.
The elongation at break that the present embodiment prepares fiber is 550%, and when elongate fiber 50%, 150%, in the time of 200%, rebound degree is 100%.
Embodiment 4
1. with embodiment 1
2. by dried EVA, with P (3HB-co-4HB) section, be to mix at 1.5: 100 in mass ratio, and add the compound of 1 part of (in 100 parts of P (3HB-co-4HB)) cumyl peroxide and chain extender, wherein the mass ratio of cumyl peroxide and chain extender is 1: 20.
The present embodiment chain extender used is that BASF AG produces
board ADR 4370 chain extenders, contain 7 epoxy radicals active groups.
3. after above-mentioned three fully being mixed, send into and spin front hopper, in screw extruder in 130 ℃ of-150 ℃ of plastifying fusions, the extruded velocity of 15m/min of take under 140 ℃ is 0.3mm from aperture, extrude in Kong Changwei 0.55mm spinnerets, after air-cooled long through 1m of the strand of extruding, with the winding speed coiling of 300m/min, obtain as-spun fibre.
4. as-spun fibre balance 24h under 20 ℃ ± 2,65 ± 5% relative humidity.Then stretch 15 times in 80 ℃ of water-baths, carry out relaxation heat setting under 70-80 ℃, then fiber balance 48h under 20 ℃ ± 2,65 ± 5% relative humidity.
The elongation at break that the present embodiment prepares fiber is 750%, and when elongate fiber 50%, 150%, in the time of 200%, rebound degree is 100%.
Embodiment 5
1. with embodiment 1
2. by dried EVA, with P (3HB-co-4HB) section, be to mix at 5: 100 in mass ratio, and add the mixture of 2.5 parts of (in 100 parts of P (3HB-co-4HB)) cumyl peroxides and chain extender, wherein the mass ratio of cumyl peroxide and chain extender is 1: 14.
The present embodiment chain extender used is that BASF AG produces
board ADR 4300 chain extenders, contain 5 epoxy radicals active groups.
3. after above-mentioned three fully being mixed, send into and spin front hopper, in screw extruder in 130 ℃ of-150 ℃ of plastifying fusions, the extruded velocity of 15m/min of take under 140 ℃ is 0.3mm from aperture, extrude in Kong Changwei 0.55mm spinnerets, after air-cooled long through 1m of the strand of extruding, with the winding speed coiling of 200m/min, obtain as-spun fibre.
4. as-spun fibre balance 24h under 20 ℃ ± 2,65 ± 5% relative humidity.Then stretch 12 times in 75 ℃ of water-baths, carry out relaxation heat setting under 70-80 ℃, then fiber balance 48h under 20 ℃ ± 2,65 ± 5% relative humidity.
The elongation at break that the present embodiment prepares fiber is 450%, and when elongate fiber 50%, 150%, in the time of 200%, rebound degree is 100%.
Embodiment 6
1. by EVA (VAC content is 19wt.%) and P (3HB-co-4HB) dry 8h and 30h under 70 ℃ and 90 ℃ of lower vacuum respectively, and control the moisture content (mass fraction) of cutting into slices and be less than respectively 0.01% and 0.005%.
2. by dried EVA, with P (3HB-co-4HB) section, be to mix at 3: 100 in mass ratio, and add the mixture of 1 part of (in 100 parts of P (3HB-co-4HB)) cumyl peroxide and chain extender, wherein the mass ratio of cumyl peroxide and chain extender is 1: 14.
The present embodiment chain extender used is that BASF AG produces
board ADR 4300 chain extenders, contain 5 epoxy radicals active groups.
3. after the three fully being mixed, send into and spin front hopper, in screw extruder in 130 ℃ of-150 ℃ of plastifying fusions, the extruded velocity of 15m/min of take under 140 ℃ is 0.3mm from aperture, extrude in Kong Changwei 0.55mm spinnerets, after air-cooled long through 1m of the strand of extruding, with the winding speed coiling of 250m/min, obtain as-spun fibre.
4. as-spun fibre balance 20h under 20 ℃ ± 2,65 ± 5% relative humidity.Then stretch 15 times in 80 ℃ of water-baths, carry out relaxation heat setting under 70-80 ℃, then fiber balance 48h under 20 ℃ ± 2,65 ± 5% relative humidity, eliminated the fiber internal stress.
The elongation at break that the present embodiment prepares fiber is 650%, and when elongate fiber 50%, 150%, in the time of 200%, rebound degree is 100%.
Claims (10)
1. the preparation method with good elastic biodegradable fiber, after by A, B, tri-kinds of components of C, mix 100:1.5～10:0.5～2.5 in mass ratio, obtain as-spun fibre by melt spinning winding apparatus spinning moulding, then obtain blended fiber after balance, stretching, typing; This blended fiber is obtained to target fibers after balance again; Wherein,
Described A component and B component need be after dryings under vacuum condition, then mix with component C;
Described component A is P (3HB-co-4HB);
Described B component is EVA;
Described component C is crosslinking agent and the chain extender compound of 1:10～1:20 in mass ratio;
Described crosslinking agent is cumyl peroxide;
Described chain extender contains 5～9 epoxy radicals active groups.
2. method according to claim 1, is characterized in that, in described P (3HB-co-4HB), the mol ratio of 3HB and 4HB is 85:15, and the number-average molecular weight of described P (3HB-co-4HB) is 700,000.
3. method according to claim 1, is characterized in that, the melt flow index of described EVA is 15g/10min, and acetate groups content is 14-19wt.%.
4. according to the described method of any one claim in claim 1～3, it is characterized in that, the dried moisture content of described component A is less than 0.005wt.%, and the dried moisture content of B component is less than 0.01wt.%.
5. according to the described method of any one claim in claim 1～3, it is characterized in that, the hole diameter of spinneret of melt spinning winding apparatus is 0.3mm, Kong Changwei 0.55mm, the extruded velocity of strand from spinneret hole is 5-15m/min, and cooling length is 1m, and winding speed is 200-300m/min.
6. according to the described method of any one claim in claim 1～3, it is characterized in that, the as-spun fibre equilibrium temperature is 20 ± 2 ℃, and humidity is 65 ± 5%, and equilibration time is 20h at least.
7. according to the described method of any one claim in claim 1～3, it is characterized in that, as-spun fibre stretches after balance in water-bath, and draft temperature is 65 ℃～80 ℃, and draw ratio is 8～15 times.
8. according to the described method of any one claim in claim 1～3, it is characterized in that, as-spun fibre be fixed to relaxation heat setting, setting temperature is 70～80 ℃.
9. according to the described method of any one claim in claim 1～3, it is characterized in that, blended fiber is at 20 ± 2 ℃, and balance 48h under 65 ± 5% conditions, eliminate the fiber internal stress.
10. prepared by the described method of claim 1 has good elastic biodegradable fiber, and its elongation at break is 290%-850%, and when fiber extends respectively 50%, 150%, in the time of 200%, rebound degree is 100%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538750A (en) * | 2008-03-18 | 2009-09-23 | 天津国韵生物材料有限公司 | Polyhydroxyalkanoates fiber and preparation method thereof |
| CN102108562A (en) * | 2010-11-16 | 2011-06-29 | 清华大学 | Method for preparing polyhydroxyalkanoate (PHA) fibers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538750A (en) * | 2008-03-18 | 2009-09-23 | 天津国韵生物材料有限公司 | Polyhydroxyalkanoates fiber and preparation method thereof |
| CN102108562A (en) * | 2010-11-16 | 2011-06-29 | 清华大学 | Method for preparing polyhydroxyalkanoate (PHA) fibers |
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| Title |
|---|
| Biodegradability of poly(3-hydroxybutyrate) blended with poly(ethylene-co-vinyl acetate) or poly(ethylene oxide);Mal-Nam Kim et al.;《European Polymer Journal》;19990131;第35卷(第6期);第1153-1158页 * |
| Mal-Nam Kim et al..Biodegradability of poly(3-hydroxybutyrate) blended with poly(ethylene-co-vinyl acetate) or poly(ethylene oxide).《European Polymer Journal》.1999,第35卷(第6期),第1153-1158页. |
| 安玉贤等.聚β－羟基丁酸酯／聚醋酸乙烯酯共混体系的相容性与结晶行为.《应用化学》.1996,第13卷(第6期),第42-45页. * |
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