CN104894676B - A kind of fishing poly butyric hydroxypentanoic acid copolyesters monofilament manufacture method - Google Patents
A kind of fishing poly butyric hydroxypentanoic acid copolyesters monofilament manufacture method Download PDFInfo
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Abstract
A kind of fishing degradable poly hydroxybutyric acid hydroxypentanoic acid copolyesters monofilament manufacture method, the present invention adopts the fishing degradable poly hydroxybutyric acid hydroxypentanoic acid copolyesters monofilament that melt spinning, super drawing technique are obtained；Described poly butyric hydroxypentanoic acid copolyesters number-average molecular weight is 180000～200000；Described poly butyric hydroxypentanoic acid copolyester section baking temperature is 70～120 DEG C, and the time is 24～48 hours, and vacuum is 0.05～0.1MPa；Described melt spinning and super drawing technique are：Spinning temperature is 175～185 DEG C, and spinning speed is 5～50m/min, and draw ratio is 3～5 times, and drawing medium is hot bath, and draft temperature is 60～100 DEG C.
Description
Technical field
The present invention relates to a kind of degradable fishing poly butyric hydroxypentanoic acid copolyesters monofilament and its manufacture method.
Background technology
At present, the fibril materials for using in China is the nondegradable synthetic fibers such as polyethylene, polyamide.Certainly
So in environment, the very difficult degraded of these fishing nets made by nondegradable synthetic fibers, the fishing net given it up, mesh sheet are in sea
Such as a sheet by a sheet " net of ghost ", in ocean, substantial amounts of Fish and mammal are difficult to after being snarled by this " net of ghost " midocean
Escape；Additionally, being easy to snarl propeller for vessels by the large-scale drift net fragment that this kind of nondegradable synthetic fibers are made, danger
Machine navigation safety.These harm phenomenons with global Fisheries Development and the finishing device be made up of persistency material wide
General using and become to be on the rise.For solving this difficult problem, the research and development of degradable fibril materials in sea water have become domestic
The study hotspot in external fishing materials field is had using the fishing net that degradation material is made, along with operation in the seawater
Degraded in journey, makes abandonment capture ability again of fishing net tool in ocean reduce, thus reducing " ghost is fished for " phenomenon.
Poly butyric hydroxypentanoic acid copolyesters (abbreviation PHBV), English name poly (β-hydroxybutyrate-co- β-
Hydroxyvalerate), it is a kind of new Green Polymer Material.It is to be raw material by starch, with fermentation engineering
The biomaterial produced, is a kind of Biopolvester, it is produced by antibacterial, can be by bacterial digestion, can be complete under natural environment
It is decomposed into carbon dioxide, water and biomass.Because PHBV fiber is due to having biodegradability, and no arrange with human body completely
Different reaction, can be widely used for biomedicine field, and can make various environment-friendlyfabric fabric as biodegradable fiber, therefore suffers from
The extensive concern of research worker both at home and abroad.Domestic Donghua University Chen Yanmo professor seminar enters to melt spinning preparation PHBV multifilament
Go long-term and systematic research, find the spinning technique to PHBV fiber for the thermal degradation during melt spinning for the PHBV raw material
And mechanical property has a significant impact, thermal degradation declines except the spinnability that meeting leads to PHBV, also can make the mechanics of obtained fiber
Decline.Use the knot strength of the PHBV fishing monofilament yarn of conventional melt spining technology preparation poor at present.By optimize melt spinning,
First break draft technique prepares the fishing degradable PHBV monofilament of Good All-around Property.
Content of the invention
It is an object of the invention to provide a kind of fishing degradable poly hydroxybutyric acid hydroxypentanoic acid copolyesters monofilament manufacture method.
Technical scheme adopts following steps：Poly butyric hydroxypentanoic acid copolyester section is dried, heating is molten
Melt, fondant filter, dosing pump, filament spinning component, spinneret, molding, stretching.Wherein heating melting point multi-region is carried out, and temperature is
150～185 DEG C；Stretching adopts secondary drawing, and draft temperature is 60～100 DEG C.It is characterized in that described poly butyric hydroxyl
The number-average molecular weight of valeric acid copolyesters is 180000～200000；Described poly butyric hydroxypentanoic acid copolyester section is dried
Temperature is 70～120 DEG C, and the time is 24～48 hours, and vacuum is -0.05～-0.1MPa；Described melt spinning and high power
Drawing process is：Spinning temperature is 175～185 DEG C, and spinning speed is 5～50m/min, and draw ratio is 3～5 times, and stretching is situated between
Matter is hot bath, and draft temperature is 60～100 DEG C.
The invention provides a kind of fishing degradable poly hydroxybutyric acid hydroxypentanoic acid copolyesters monofilament manufacture method, described
Manufacture method comprises the following steps：
A, poly butyric hydroxypentanoic acid copolyester section are dried：From number-average molecular weight be 180000～200000 poly-
Hydroxybutyric acid hydroxypentanoic acid copolyester section, is dried under conditions of being -0.05～-0.1MPa in 70～120 DEG C of temperature, vacuum
24～48 hours；
B, heating melting：The poly butyric hydroxypentanoic acid copolyester section that step A obtains, molten through screw extruder heating
Melt, melt extruded by spinneret after metering pump-metered, heating melt temperature is 150～185 DEG C；
C, spinning：Spinning body temperature is 175～185 DEG C；Spinning speed is 5～50m/min；
D, stretching：The spinning that step C obtains carries out hot-stretch after cold water cooling, and draw ratio is 3～5 times, and stretching is situated between
Matter is hot bath, and draft temperature is 60～100 DEG C.
In step B, poly butyric hydroxypentanoic acid copolyester section heats melting through screw extruder, through measuring pump-metered
Melt extruded by spinneret afterwards, heating melting subregion is carried out, and is divided into feed zone, melting zone, compressional zone, metering zone；And feed
Area's temperature is less than melting zone, compressional zone, the temperature of metering zone；Metering zone temperature is not less than the temperature of melting zone, compressional zone.
Preferably, 150 DEG C of feed zone, 170 DEG C～185 DEG C of melting zone, 170 DEG C～185 DEG C of compressional zone, 170 DEG C of metering zone
～185 DEG C.
Beneficial effect
The present invention adopts the poly butyric hydroxypentanoic acid copolyesters monofilament that melt spinning-drawing process is obtained, and performance is steady
Fixed, there is the characteristic of degradable, can be used for manufacturing drift net, silkworm gut, mesh bag, hawser etc..
Specific embodiment
With reference to embodiment, technical scheme and effect are further described.
Embodiment 1
The poly butyric hydroxypentanoic acid copolyester section being 180000 from number-average molecular weight, in temperature 70 C, vacuum
Spend for being dried 48 hours under conditions of -0.05MPa.Poly butyric hydroxypentanoic acid copolyester section is molten through screw extruder heating
Melt, melt extruded by spinneret after metering pump-metered, screw rod spinning temperature：150 DEG C of feed zone, 170 DEG C of melting zone, pressure
170 degree of contracting area, 170 DEG C of metering zone；Spinning body temperature is 175 DEG C；Spinning speed is 5m/min；Extrusion silk is after cold water cooling
Carry out high power hot-stretch, draw ratio is 3 times, drawing medium is hot bath, draft temperature is 60 DEG C.
Embodiment 2
The poly butyric hydroxypentanoic acid copolyester section being 180000 from number-average molecular weight, in 80 DEG C of temperature, vacuum
Spend for being dried 36 hours under conditions of -0.05MPa.Poly butyric hydroxypentanoic acid copolyester section is molten through screw extruder heating
Melt, melt extruded by spinneret after metering pump-metered, screw rod spinning temperature：150 DEG C of feed zone, 170 DEG C of melting zone, pressure
175 DEG C of contracting area, 175 DEG C of metering zone；Spinning body temperature is 175 DEG C；Spinning speed is 10m/min；Extrusion silk cools down through cold water
After carry out high power hot-stretch, draw ratio be 3.5 times, drawing medium be hot bath, draft temperature be 70 DEG C.
Embodiment 3
The poly butyric hydroxypentanoic acid copolyester section being 190000 from number-average molecular weight, in 90 DEG C of temperature, vacuum
Spend for being dried 36 hours under conditions of -0.05MPa.Poly butyric hydroxypentanoic acid copolyester section is molten through screw extruder heating
Melt, melt extruded by spinneret after metering pump-metered, screw rod spinning temperature：150 DEG C of feed zone, 175 DEG C of melting zone, pressure
175 DEG C of contracting area, 180 DEG C of metering zone；Spinning body temperature is 180 DEG C；Spinning speed is 25m/min；Extrusion silk cools down through cold water
After carry out high power hot-stretch, draw ratio be 4 times, drawing medium be hot bath, draft temperature be 80 DEG C.
Embodiment 4
The poly butyric hydroxypentanoic acid copolyester section being 200000 from number-average molecular weight, in 100 DEG C of temperature, vacuum
Spend for being dried 24 hours under conditions of -0.1MPa.Poly butyric hydroxypentanoic acid copolyester section is molten through screw extruder heating
Melt, melt extruded by spinneret after metering pump-metered, screw rod spinning temperature：150 DEG C of feed zone, 175 DEG C of melting zone, pressure
180 DEG C of contracting area, 185 DEG C of metering zone；Spinning body temperature is 185 DEG C；Spinning speed is 30m/min；Extrusion silk cools down through cold water
After carry out high power hot-stretch, draw ratio be 4.5 times, drawing medium be hot bath, draft temperature be 90 DEG C.
Embodiment 5
The poly butyric hydroxypentanoic acid copolyester section being 200000 from number-average molecular weight, in 120 DEG C of temperature, vacuum
Spend for being dried 24 hours under conditions of -0.1MPa.Poly butyric hydroxypentanoic acid copolyester section is molten through screw extruder heating
Melt, melt extruded by spinneret after metering pump-metered, screw rod spinning temperature：150 DEG C of feed zone, 180 DEG C of melting zone, pressure
180 DEG C of contracting area, 185 DEG C of metering zone；Spinning body temperature is 185 DEG C；Spinning speed is 50m/min；Extrusion silk cools down through cold water
After carry out high power hot-stretch, draw ratio be 5 times, drawing medium be hot bath, draft temperature be 100 DEG C.
Comparative example 1
Other conditions such as embodiment 5, difference is：It is dried under conditions of being -0.2MPa in temperature 60 C, vacuum
24 hours.
Comparative example 2
Other conditions such as embodiment 5, difference is：It is 120 DEG C in 200 DEG C of spinning body temperature, draft temperature.
Test example
Mechanic property test method is with reference to marine industry standard SC/T 5005-2014《Fishing polyethylene monofilament》, embodiment
And the detection data of comparative example is shown in Table 1：
Table 1 embodiment and the detection data of comparative example
| Fracture strength (cN/dtex) | Knot strength (cN/dtex) | |
| Embodiment 1 | 2.8 | 1.9 |
| Embodiment 2 | 3.1 | 2.2 |
| Embodiment 3 | 3.5 | 2.3 |
| Embodiment 4 | 3.8 | 2.5 |
| Embodiment 5 | 3.9 | 2.3 |
| Comparative example 1 | 3.0 | 1.5 |
| Comparative example 2 | 2.5 | 1.3 |
All all best with the fracture strength embodiment 5 of most of condition of comparative example 1,2 is identical, but comparative example 1 vacuum is done
Dry temperature and pressure is different, and the temperature and pressure of dry run determines containing of poly butyric hydroxypentanoic acid copolyester section
Water rate, and the presence of moisture can make poly butyric hydroxypentanoic acid copolyester section drop during heating melt spinning
Solution, therefore can affect fracture strength and the knot strength of final monofilament；Comparative example 2 spinning temperature is 200 DEG C, and temperature drift is made
Become a certain degree of thermal degradation of poly butyric hydroxypentanoic acid copolyesters, draft temperature is 120 DEG C simultaneously, leads to poly butyric
Hydroxypentanoic acid copolyesters cools down slack-off after redrawing so as to crystallization is not perfect, thus directly affects fracture strength and tuberosity
Intensity.
Claims (3)
1. a kind of fishing with degradable poly hydroxybutyric acid hydroxypentanoic acid copolyesters monofilament manufacture method it is characterised in that concrete prepare
Step is as follows：
A, poly butyric hydroxypentanoic acid copolyester section are dried：The poly- hydroxyl being 180000～200000 from number-average molecular weight
Butanoic acid hydroxypentanoic acid copolyester section, dry 24 under conditions of being -0.05～-0.1MPa in 70～120 DEG C of temperature, vacuum～
48 hours；
B, heating melting：The poly butyric hydroxypentanoic acid copolyester section that step A obtains, heats melting through screw extruder,
Heating melt temperature is 150～185 DEG C；
C, spinning：Step B heating melting after, through metering pump-metered after melt extruded by spinneret, spinning body temperature be 175～
185℃；Spinning speed is 5～50m/min；
D, stretching：The spinning that step C obtains carries out hot-stretch after cold water cooling, and draw ratio is 3～5 times, and drawing medium is
Hot bath, draft temperature is 60～100 DEG C.
2. a kind of fishing according to claim 1 degradable poly hydroxybutyric acid hydroxypentanoic acid copolyesters monofilament manufacture method,
It is characterized in that, in step B, poly butyric hydroxypentanoic acid copolyester section heats melting, heating melting point through screw extruder
Area is carried out, and is divided into feed zone, melting zone, compressional zone, metering zone；And feed zone temperature is less than melting zone, compressional zone, metering zone
Temperature；Metering zone temperature is not less than the temperature of melting zone, compressional zone.
3. a kind of fishing according to claim 2 degradable poly hydroxybutyric acid hydroxypentanoic acid copolyesters monofilament manufacture method,
It is characterized in that, 150 DEG C of the temperature of feed zone, 170 DEG C～185 DEG C of the temperature of melting zone, the temperature 170 DEG C～185 of compressional zone
DEG C, 170 DEG C～185 DEG C of the temperature of metering zone.
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| CN106521688A (en) * | 2016-09-22 | 2017-03-22 | 江南大学 | High strength coarse denier (3-hydroxybutryate-co-3-hydroxylpentanoate) filament and preparation method thereof |
| CN106400183A (en) * | 2016-09-22 | 2017-02-15 | 江南大学 | Poly-(3-polyhydroxybutyrate-co-3-polyhydroxybutyrate-hydroxyvalerate) multifilament and preparation method thereof |
| CN112877795B (en) * | 2021-01-13 | 2022-07-29 | 中国水产科学研究院东海水产研究所 | Preparation method of fishing polyvinylidene fluoride monofilament |
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| CN101476165B (en) * | 2009-01-12 | 2010-11-17 | 东华大学 | Poly (hydroxybutyrate-hydroxyvalerate) fiber and dry spinning method |
| CN102146598B (en) * | 2011-04-22 | 2012-07-25 | 中国科学院宁波材料技术与工程研究所 | PHBV-containing biobased chemical fiber and preparation method thereof |
| CN102995160A (en) * | 2012-09-20 | 2013-03-27 | 新凤鸣集团股份有限公司 | PLA (Poly Lactic Acid) and PHBV (Poly Hydroxyl Butyrate Valerate) blending modification polyester filament and preparation method thereof |
| CN102936761B (en) * | 2012-12-11 | 2015-09-23 | 江南大学 | A kind of resource is renewable, biodegradable conductive fiber and preparation method thereof |
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