CN103757739A - Biodegradable polymer monofilament and production method thereof - Google Patents
Biodegradable polymer monofilament and production method thereof Download PDFInfo
- Publication number
- CN103757739A CN103757739A CN201310749317.0A CN201310749317A CN103757739A CN 103757739 A CN103757739 A CN 103757739A CN 201310749317 A CN201310749317 A CN 201310749317A CN 103757739 A CN103757739 A CN 103757739A
- Authority
- CN
- China
- Prior art keywords
- temperature
- biodegradable polymer
- monofilament
- melt
- production method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Artificial Filaments (AREA)
Abstract
The invention discloses a biodegradable polymer monofilament, of which the diameter is 0.05-2.0mm, the fracture strength is greater than 3.5 CN/dtex, the elongation at break is 20-35% and the degradation rate is greater than or equal to 3.0% under the soil humidity of 59.3% at 28 DEG C for 28 days. The production method comprises the following steps: mixing a polyesteramide resin with additives, extruding with a screw melt extruder, cooling the extruded melt by water cooling to obtain a freshly formed filament, and carrying out hot water stretching, hot air stretching and thermoforming on the freshly formed filament to obtain the biodegradable polyesteramide monofilament. The biodegradable polyesteramide monofilament has the characteristics of high strength and high toughness; and the method has the advantages of simple preparation process and low cost, and is suitable for the related fields of nets in fishery, agriculture and the like.
Description
Technical field
The present invention relates to a kind of polymer filament, a kind of method that is specifically related to Biodegradable polyester amides monofilament and produces this monofilament.
Background technology
In general, fishing line, fishing net, agricultural net etc. are to adopt the good synthetic fiber such as polyamide monofilament such as processability, intensity, durability, heat resistance, but such synthetic fiber, owing to not possessing decomposability under natural environment, can cause the serious problems such as marine pollution.Natural fabric great majority have biodegradability, but cannot show the contour performances of desired high strength such as fishing line, fishing net, agricultural net.
Polyesteramide combines the advantage of polyester and polyamide, has both had biological degradability, has again the excellent physical mechanical properties such as high-strength, heat-resisting.Need to be by polyesteramide melt spinning but polyesteramide will be manufactured to monofilament, then stretch, at present by the method be also difficult to be fully improved monofilament of mechanical strength.When the polyamide segment of polyester-amide copolymer designs, for biological degradability harmless and this copolymer, chain length will shorten.Therefore, polyester-amide copolymer compare with polyamide homopolymer be crystallinity low, be also difficult to occur oriented crystalline or crystallization speed is slow.Therefore, although can make the amorphism obtaining by chilling, be that drawn yarn stretches, cannot make the orientation of noncrystalline portion fully be fixed up, never can not fully improve mechanical strength.
Also not yet having at present the polyesteramide of employing is raw material, carries out the report that melt spinning is prepared major diameter monofilament.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of biodegradable polymer filament, has higher fracture strength and elongation at break, in soil moisture, is 59.3%, 28 ℃ of temperature, and the time is degradation rate >=3.0% under the condition of 28 days.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A biodegradable polymers monofilament, its innovative point is: the polyesteramide and the 0wt%～5wt% additive that on the molecular backbone that described monofilament contains 95wt%～100wt%, contain amido link and ester bond; The diameter of described monofilament is 0.05～2.0mm, and the fracture strength of described monofilament is greater than 3.5CN/dtex, and elongation at break is 20%～35%, in soil moisture, is 59.3%, 28 ℃ of temperature, and the time is degradation rate >=3.0% under the condition of 28 days.
Further, described polyesteramide is linear polyester acid amides, and its molecular weight is 20000～50000.
Further, described additive is nano titanium oxide or Nano particles of calcium carbonate.In polyesteramide, add nano titanium oxide or nano-calcium carbonate to have and strengthen toughness reinforcing effect, improve intensity and the toughness of monofilament.
Further, described additive also comprises photosensitizing agents, and its quality is 0～3% of monofilament gross mass.
Another object of the present invention is to provide a kind of production method of biodegradable polymers monofilament, comprise that raw material mixes, is dried, melt extrudes, water cooling, hot water stretching, hot blast stretching, HEAT SETTING and coiling technique, specific as follows:
(1) raw material mixes: polyesteramide and additive are proportionally mixed;
(2) dry: mixed raw material is dried to moisture content≤50ppm on drying machine, and baking temperature is 120～180 ℃;
(3) melt extrude: raw material drying melt extrudes and obtains spun filament with the extrusion capacity of 30～100 kgs/hour by screw rod melt extruder, and melt temperature is 260～280 ℃;
(4) water cooling: spun filament is cooled to 30～60 ℃ through water or the aqueous solution of 5～60 ℃;
(5) hot water stretches: cooled spun filament is carried out one stretching in hot bath, and draw ratio is 4.0～6.0, and hot water temperature is 70～90 ℃;
(6) hot blast stretches: draw ratio is 1.2～1.6 times, and temperature is 120～180 ℃;
(7) HEAT SETTING: heat setting temperature is 180～260 ℃;
(8) batch: the monofilament after sizing is wound up on bobbin with the speed of 80～200m/min.
Further, described screw rod melt extruder melt extrudes and obtains spun filament with the extrusion capacity of 40～60 kgs/hour, and melt temperature is 260～280 ℃;
Further, described spun filament is cooled to 40～50 ℃ through water or the aqueous solution of 15～40 ℃.
Further, the draw ratio that described hot water stretches is 4～5, and hot water temperature is 70～90 ℃; The draw ratio that hot blast stretches is 1.3～1.5, and temperature is 130～150 ℃; Heat setting temperature is 200～220 ℃, and coiling speed is 100～120m/min.
Beneficial effect of the present invention: compared with prior art, Biodegradable polyester amides monofilament provided by the invention, in preparation process, add to strengthen, toughness reinforcing nano titanium oxide or nano-calcium carbonate or photosensitizing agents, by adopting suitable technological parameter, prepare the monofilament of diameter between 0.05～2.0mm, the Biodegradable polyester amides monofilament of preparation has the feature of high-strength and high ductility, its fracture strength is greater than 3.5CN/dtex, elongation at break is 20%～35%, in soil moisture, be 59.3%, 28 ℃ of temperature, the time is degradation rate >=3.0% under the condition of 28 days.
The specific embodiment
Below in conjunction with specific embodiment, summary of the invention of the present invention is further explained to explanation, but and non-limiting protection scope of the present invention.
Embodiment 1
Use polyesteramide (Dupont) resin that molecular weight is 25000 on drying machine, to be dried to moisture content≤50ppm, baking temperature is 130 ℃; Then through screw rod melt extruder, with the extrusion capacity of 35 kgs/hour, melt extrude and obtain spun filament, melt temperature is 260 ℃; Spun filament is through be water-cooled to 30 ℃ of 10 ℃; Cooled spun filament is carried out one stretching in hot bath, and draw ratio is 4.0 times, and hot water temperature is 70 ℃; Then carry out two road hot blasts and stretch, draw ratio is 1.2 times, and temperature is 70 ℃; Spun filament is carried out HEAT SETTING 185 ℃ of conditions after stretching; Speed with 90m/min is wound up on bobbin again.
The diameter of the monofilament that the present embodiment obtains is 0.12mm, fracture strength 3.8CN/dtex, and elongation at break is 27.8%, (soil moisture 59.3%, 28 ℃ of temperature, 28 days, degradation rate 3.4%).
Embodiment 2
Polyesteramide (Dupont) raw material that the molecular weight that uses 96wt% is 30000 mixes with the nano titanium oxide of 4wt%, is dried to moisture content≤50ppm on drying machine, and baking temperature is 140 ℃; Then through screw rod melt extruder, with the extrusion capacity of 50 kgs/hour, melt extrude and obtain spun filament, melt temperature is 265 ℃; Spun filament is through emulsion but to 40 ℃ of 20 ℃; Cooled spun filament is carried out one stretching in hot bath, and draw ratio is 4.5 times, and hot water temperature is 75 ℃; Then carry out two road hot blasts and stretch, draw ratio is 1.4 times, 140 ℃ of temperature; Spun filament is carried out HEAT SETTING 200 ℃ of conditions after stretching; Speed with 120m/min is wound up on bobbin again.
The diameter of the monofilament that the present embodiment obtains is 0.15mm, fracture strength 4.1CN/dtex, and elongation at break is 26.7%, soil moisture 59.3%, 28 ℃ of temperature, 28 days, degradation rate 3.6%.
Embodiment 3
Polyesteramide (Dupont) raw material that the molecular weight that uses 96wt% is 35000 mixes with the nano-calcium carbonate of 4wt%, is dried to moisture content≤50ppm on drying machine, and baking temperature is 150 ℃; Then through screw rod melt extruder, with the extrusion capacity of 50 kgs/hour, melt extrude and obtain spun filament, melt temperature is 270 ℃; Spun filament is through be water-cooled to 40 ℃ of 20 ℃; Cooled spun filament is carried out one stretching in hot bath, and draw ratio is 5.0 times, and hot water temperature is 80 ℃; Then carry out two road hot blasts and stretch, draw ratio is 1.4 times, 140 ℃ of temperature; Spun filament is carried out HEAT SETTING 210 ℃ of conditions after stretching; Speed with 130m/min is wound up on bobbin again.
The diameter of the monofilament that the present embodiment obtains is 0.18mm, fracture strength 4.3CN/dtex, and elongation at break is 25.6%, soil moisture 59.3%, 28 ℃ of temperature, 28 days, degradation rate 3.5%.
Embodiment 4
Use polyesteramide (Dupont) raw material that 95wt% molecular weight is 45000 to mix with the photosensitizing agents (PAS～33) of 2wt% nano titanium oxide and 3wt%, be dried to moisture content≤50ppm on drying machine, baking temperature is 130 ℃; Then through screw rod melt extruder, with the extrusion capacity of 40 kgs/hour, melt extrude and obtain spun filament, melt temperature is 260 ℃; Spun filament is cooled to 50 ℃ through the emulsion of 40 ℃; Cooled spun filament is carried out one stretching in hot bath, and draw ratio is 5.2 times, and hot water temperature is 82 ℃; Then carry out two road hot blasts and stretch, draw ratio is 1.5 times, and temperature is 165 ℃; Spun filament is carried out HEAT SETTING 230 ℃ of conditions after stretching; Speed with 150m/min is wound up on bobbin again.
The diameter of the monofilament that the present embodiment obtains is 0.14mm, fracture strength 4.8CN/dtex, and elongation at break is 24.3%, soil moisture 59.3%, 28 ℃ of temperature, 28 days, degradation rate 3.8%.
Embodiment 5
Use polyesteramide (Dupont) raw material that 97wt% molecular weight is 50000 to mix with the photosensitizing agents (PAS～33) of 0.5wt% nano-calcium carbonate and 2.5wt%, be dried to moisture content≤50ppm on drying machine, baking temperature is 175 ℃; Then through screw rod melt extruder, with the extrusion capacity of 32 kgs/hour, melt extrude and obtain spun filament, melt temperature is 280 ℃; Spun filament is through be water-cooled to 58 ℃ of 55 ℃; Cooled spun filament is carried out one stretching in hot bath, and draw ratio is 5.8 times, and hot water temperature is 88 ℃; Then carry out two road hot blasts and stretch, draw ratio is 1.6, and temperature is 178 ℃; Spun filament is carried out HEAT SETTING 255 ℃ of conditions after stretching; Speed with 190m/min is wound up on bobbin again.
The diameter of the monofilament that the present embodiment obtains is 0.14mm, fracture strength 4.5CN/dtex, and elongation at break is 26.3%, soil moisture 59.3%, 28 ℃ of temperature, 28 days, degradation rate 3.7%.
Above-described embodiment is only in order to illustrate technical scheme of the present invention; but not design of the present invention and protection domain are limited; those of ordinary skill in the art modifies or is equal to replacement technical scheme of the present invention; and not departing from aim and the scope of technical scheme, it all should be encompassed in claim scope of the present invention.
Claims (9)
1. a biodegradable polymer filament, is characterized in that: the polyesteramide and the 0wt%～5wt% additive that on the molecular backbone that described monofilament contains 95wt%～100wt%, contain amido link and ester bond; The diameter of described monofilament is 0.05～2.0mm, and the fracture strength of described monofilament is greater than 3.5CN/dtex, and elongation at break is 20%～35%, in soil moisture, is 59.3%, 28 ℃ of temperature, and the time is degradation rate >=3.0% under the condition of 28 days.
2. a kind of biodegradable polymer filament according to claim 1, is characterized in that: described polyesteramide is linear polyester acid amides, and its molecular weight is 20000～50000.
3. a kind of biodegradable polymer filament according to claim 1, is characterized in that: described additive is nano titanium oxide or Nano particles of calcium carbonate.
4. a kind of biodegradable polymer filament according to claim 3, is characterized in that: described additive also comprises photosensitizing agents, and its quality is 0～3% of monofilament gross mass.
5. a production method that realizes a kind of biodegradable polymer filament claimed in claim 1, is characterized in that: comprise that raw material mixes, is dried, melt extrudes, water cooling, hot water stretching, hot blast stretching, HEAT SETTING and coiling technique, specific as follows:
(1) raw material mixes: polyesteramide and additive are proportionally mixed;
(2) dry: mixed raw material is dried to moisture content≤50ppm on drying machine, and baking temperature is 120～180 ℃;
(3) melt extrude: raw material drying melt extrudes and obtains spun filament with the extrusion capacity of 30～100 kgs/hour by screw rod melt extruder, and melt temperature is 260～280 ℃;
(4) water cooling: spun filament is cooled to 30～60 ℃ through water or the aqueous solution of 5～60 ℃;
(5) hot water stretches: cooled spun filament is carried out one stretching in hot bath, and draw ratio is 4.0～6.0, and hot water temperature is 70～90 ℃;
(6) hot blast stretches: draw ratio is 1.2～1.6 times, and temperature is 120～180 ℃;
(7) HEAT SETTING: heat setting temperature is 180～260 ℃;
(8) batch: the monofilament after sizing is wound up on bobbin with the speed of 80～200m/min.
6. the production method of a kind of biodegradable polymer filament according to claim 5, is characterized in that: the aqueous solution in described step (4) is polyacrylamide amine emulsifier.
7. the production method of a kind of biodegradable polymer filament according to claim 5, is characterized in that: described screw rod melt extruder melt extrudes and obtains spun filament with the extrusion capacity of 45～55 kgs/hour, and melt temperature is 260～280 ℃.
8. the production method of a kind of biodegradable polymer filament according to claim 5, is characterized in that: described spun filament is cooled to 30～40 ℃ through water or the aqueous solution of 25～35 ℃.
9. the production method of a kind of biodegradable polymer filament according to claim 5, is characterized in that: the draw ratio that described hot water stretches is 4～5 times, and hot water temperature is 70～90 ℃; The draw ratio that hot blast stretches is 1.3～1.5, and temperature is 130～150 ℃; Heat setting temperature is 200～220 ℃, and coiling speed is 100～120m/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310749317.0A CN103757739A (en) | 2013-12-31 | 2013-12-31 | Biodegradable polymer monofilament and production method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310749317.0A CN103757739A (en) | 2013-12-31 | 2013-12-31 | Biodegradable polymer monofilament and production method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103757739A true CN103757739A (en) | 2014-04-30 |
Family
ID=50525049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310749317.0A Pending CN103757739A (en) | 2013-12-31 | 2013-12-31 | Biodegradable polymer monofilament and production method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103757739A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104264271A (en) * | 2014-10-15 | 2015-01-07 | 吴竟成 | Preparation method of polyester monofilaments for automobile safety belts |
| CN106048771A (en) * | 2016-07-13 | 2016-10-26 | 南通中兴多元复合钢管有限公司 | Biodegradable polymer monofilaments and producing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196738A (en) * | 1996-04-30 | 1998-10-21 | 东丽株式会社 | Polyester amide complymer and process for production thereof, polyester amide monomer and process for production thereof and polyester amide resin composition |
| CN1285853A (en) * | 1998-01-10 | 2001-02-28 | 拜尔公司 | Biodegradable polyester amides with block-shaped polyester and polyamide segments |
| CN1401021A (en) * | 2000-02-10 | 2003-03-05 | 吴羽化学工业株式会社 | High strength polyester amide fiber and process for producing the same |
-
2013
- 2013-12-31 CN CN201310749317.0A patent/CN103757739A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196738A (en) * | 1996-04-30 | 1998-10-21 | 东丽株式会社 | Polyester amide complymer and process for production thereof, polyester amide monomer and process for production thereof and polyester amide resin composition |
| CN1285853A (en) * | 1998-01-10 | 2001-02-28 | 拜尔公司 | Biodegradable polyester amides with block-shaped polyester and polyamide segments |
| CN1401021A (en) * | 2000-02-10 | 2003-03-05 | 吴羽化学工业株式会社 | High strength polyester amide fiber and process for producing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104264271A (en) * | 2014-10-15 | 2015-01-07 | 吴竟成 | Preparation method of polyester monofilaments for automobile safety belts |
| CN106048771A (en) * | 2016-07-13 | 2016-10-26 | 南通中兴多元复合钢管有限公司 | Biodegradable polymer monofilaments and producing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10190236B2 (en) | High strength and high modulus ultra-high molecular weight polyethylene fibers | |
| CN103572502B (en) | Ultra-high molecular weight polyethylene monofilaments has knot fishing net preparation method | |
| CN103443339A (en) | Biodegradable polyester fiber having excellent thermal stability and strength, and method for producing same | |
| JP6708813B2 (en) | Polylactic acid resin fiber, polylactic acid long fiber, polylactic acid short fiber and polylactic acid fiber | |
| CN104975370A (en) | Melt-spun polyvinylidene fluoride filament and production method thereof | |
| CN107338490B (en) | A kind of production method of fine denier lustrous flame-resistant terylene FDY filament | |
| CN103757736A (en) | Large-diameter melt-spun polyvinylidene fluoride monofilament and production method thereof | |
| CN108866704B (en) | High-strength corrosion-resistant aging-resistant fishing net thread | |
| CN105200549A (en) | Biodegradable polymer monofilament and production method thereof | |
| CN103757739A (en) | Biodegradable polymer monofilament and production method thereof | |
| JP4773290B2 (en) | Polylactic acid composite fiber | |
| CN101255612B (en) | Production technique of shockproof polyester industrial filament yarn | |
| WO2014195963A2 (en) | Compact polymeric gel and fibers made therefrom | |
| CN105200552B (en) | Acid fiber by polylactic of high heat-resistant high-strength and preparation method thereof | |
| CN106048771A (en) | Biodegradable polymer monofilaments and producing method thereof | |
| KR101235255B1 (en) | Manufacturing method of high strength polyethylene multifilament drawn fibers containing nano silica particles | |
| CN108130612A (en) | The polymer filament and its production method of environmental protection | |
| KR20090072050A (en) | A method for producing high modulus - low shrinkage polyester multifilament yarn | |
| CN107805850A (en) | A kind of high-strength and high-modulus polyformaldehyde fibre and preparation method thereof | |
| CN107447285A (en) | A kind of graphene in-situ polymerization modified polyamide 6 high oriented yarn and preparation method thereof | |
| CN109295537B (en) | Flexible wear-resistant antibacterial flat filament and wire drawing process thereof | |
| CN207294963U (en) | A kind of ring blowing device for polyamide staple fibre production | |
| CN108411396A (en) | Degradable silk and its production method | |
| CN106032581A (en) | A preparation method for degradable polymer monofilaments | |
| CN106032582A (en) | A preparation method for degradable polymer monofilaments |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20140430 |