CN103215685B - Preparation method of completely-biodegradable aliphatic copolyester monofilament - Google Patents
Preparation method of completely-biodegradable aliphatic copolyester monofilament Download PDFInfo
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Abstract
The invention discloses a preparation method of completely-biodegradable aliphatic copolyester monofilament. The preparation method comprises the following steps of: (1) preparation of an aliphatic copolyester melt: adopting succinic acid and ethylene glycol as raw materials and pentaerythritol as a modification monomer, adding an antimony catalyst, and beating into slurry in a beating kettle; continuously and stably conveying the slurry into a reaction kettle, and performing an esterification reaction to obtain an esterified product; and conveying the esterified product to a condensation polymerization section by a pump to perform condensation polymerization to obtain an aliphatic copolyester melt; and (2) preparation of aliphatic copolyester monofilament: enabling the aliphatic copolyester melt obtained by the step (1) to pass through melt conveying equipment, metering, extruding with a spinning jet, cooling and curing in a cooling water tank, and performing multi-level stretching and heat setting to obtain the completely-biodegradable aliphatic copolyester monofilament. The preparation method disclosed by the invention has the advantages of short flow, low cost, stable melt quality and good spinning performance; and physical indexes of the prepared monofilament meet the using requirements.
Description
Technical field
The present invention relates to a kind of preparation method of completely-biodegradaliphatic aliphatic copolyester monofilament, the preparation method of particularly a kind of continuous polymerization, fused mass directly spinning completely-biodegradaliphatic aliphatic copolyester monofilament, belongs to chemical fibre field.
Background technology
Along with becoming increasingly conspicuous of environmental problem, Biodegradable material more and more receives the concern of countries in the world.Ester bond containing facile hydrolysis in aliphatic polyester main chain, and main chain is submissive, is easy to be degraded by the catalysis of enzyme under the effect of microorganism, it has become the focus researched and developed in world wide as environment-friendly material.Wherein successful industrialization has PLA (PLA), polycaprolactone (PCL) and binary aliphatic alkyd polyester etc., if poly butylene succinate (PBS) is as the biodegradable aliphatic polyester of a quasi-representative, due to its excellent combination property, cost performance rationally enjoys favor, development was very fast in recent years, that Present Domestic is researched and developed at most outward, technology relative maturity, the biodegradation material that industrialized scale is maximum, also be one of kind come into the market the earliest, mainly for the production of packaging, film, agricultural aquatic products and building goods, materials and equipments etc., realize fully biodegradable, reduce the pollution to environment.But simultaneously because its production cost is higher, add that fusing point is lower, make the melt strength under high temperature spinning condition lower, therefore spinning properties is poor, seriously hinder its application in fiber art.
Polyethylene glycol succinate (PES) polyester is the homologous series polymer of PBS polyester, and be also crystalline polymer, its fusing point is about 104 DEG C, vitrification point is about-12.5 DEG C, and crystallization rate is very fast, better heat stability, biodegradable, and production cost is lower than PBS.About the synthesis of PES polyester, pertinent literature also has report.As carried out ring-opening polymerization with succinic anhydride and oxirane for raw material, obtain the PES that relative molecular mass is higher, but because of the toxicity of oxirane comparatively large, easy contaminated environment also endangers the healthy of operating personnel, needs very strict control to react.Take decahydronaphthalene as solvent, synthesized the polyethylene glycol succinate PES of higher relative molecular weight by polymerisation in solution, but solution polymerization speed is comparatively slow, and need solvent recovery process, production cost is higher, is difficult to obtain practical application.In addition, report and synthesize PES by melt-polycondensation, but its polycondensation reaction time is long.Number of patent application: 200810132792.2, patent name is: a kind of method for preparing poly (ethylene succinate), with succinic acid (SA) and ethylene glycol (EG) for raw material, with the method for polymerisation in solution first obtained performed polymer, then the PES of high molecular is obtained by the method for chain extension, for plastics-production, but the method existence needs the deficiency such as solvent recovery, reaction time length.Although just start the research of PES, not yet have the release of commercially produced product both at home and abroad, no matter from raw material sources, or from the performance of PES and cost angle, PES is all environment friendly polyester of a class great potential.
Therefore, overcome that the technological process that exists in the preparation method of above-mentioned PES is complicated, production cost is high, section crystallizing and drying is difficult, molecular weight and molecular weight is large after melting again, melt strength is low, being difficult to the deficiencies such as the processes requirement meeting high speed spinning, is the emphasis that the present invention breaks through.
the content of invention
The object of the present invention is to provide a kind of preparation method of completely-biodegradaliphatic aliphatic copolyester monofilament, have that flow process is short, cost is low, melt quality is stable, good spinning performance, the obtained every physical index of monofilament all can meet instructions for use, final products can after use be discarded, being decomposed into carbon dioxide and water by natural microorganism or enzyme, is a kind of fully biodegradable macromolecular material.
For achieving the above object, technical scheme of the present invention is:
A kind of preparation method of completely-biodegradaliphatic aliphatic copolyester monofilament, comprise the steps: 1) prepare aliphatic copolyester melt: with succinic acid and ethylene glycol for raw material, pentaerythrite is modified monomer, and adds antimony-based catalyst, in making beating still, break into slurry; Above-mentioned slurry continous-stable is delivered in reactor and carries out esterification and obtain carboxylate; Adopt transport pump to carry out polycondensation to polycondensation workshop section above-mentioned obtained carboxylate again and obtain aliphatic copolyester melt; 2) aliphatic copolyester monofilament is prepared: by aliphatic copolyester melt obtained for step 1) by melt Conveying equipment, through metering, spinning head extrudes, cooling curing in bosh, then through multistage stretching and HEAT SETTING, obtained completely-biodegradaliphatic aliphatic copolyester monofilament.
Described step 1) is specially with succinic acid and ethylene glycol for raw material, and pentaerythrite is modified monomer, and adds antimony-based catalyst, in making beating still, break into slurry; Be delivered to by above-mentioned slurry continous-stable in esterification-I reactor, controlled pressure is 0.12MPa, and temperature is 200.0 DEG C, and the reaction time is 2.5 hours; Material after the reaction of esterification-I reactor being terminated again is sent in esterification-II reactor, and adds stabilizing agent, and control temperature is 210 DEG C, and the reaction time is 0.5 hour, and controlling esterification yield is 97.0% ~ 98.5%; Adopt transport pump to carry out polycondensation reaction to polycondensation workshop section above-mentioned obtained carboxylate again, reaction temperature is 225 ~ 240 DEG C, and vacuum is 10 ~ 0.1KPa, and the reaction time is less than 200min, the aliphatic copolyester melt that obtained number-average molecular weight is greater than 50,000.
In described step 1), the mol ratio of succinic acid and ethylene glycol is 1:1.05 ~ 1.25; Described pentaerythrite and the molar percentage of succinic acid are 0.1 ~ 0.3%; It is the solution of 5% that described pentaerythrite is mixed with the molar percentage that pentaerythrite accounts for ethylene glycol; Described antimony-based catalyst and the percentage by weight of succinic acid are 500PPM; Described stabilizing agent and the percentage by weight of succinic acid are 200PPM.
In described step 1), antimony-based catalyst adopts the one in antimony glycol, antimonous oxide or antimony acetate (being Jiangxi Er Yuan chemical industry Co., Ltd to provide); Described stabilizing agent adopts the one in triphenyl phosphate (Er Yuan chemical industry Co., Ltd provides for Jiangxi), phosphorous acid (Er Yuan chemical industry Co., Ltd provides for Jiangxi), trimethyl phosphate (Er Yuan chemical industry Co., Ltd provides for Jiangxi).
The preferred antimony glycol of described antimony-based catalyst; Described stabilizing agent preferably phosphoric acid triphenylmethyl methacrylate.
Described step 2) in the temperature of melt Conveying pipeline be 200 ~ 210 DEG C; Spinning body temperature is 220 ~ 240 DEG C; Cooling water temperature is 10 ~ 30 DEG C; Drawing temperature is 40 ~ 50 DEG C; Heat setting temperature is 50 ~ 70 DEG C; Drafting multiple is 4.5 ~ 5.5; Winding speed is 50 ~ 200m/min; The filament number of obtained completely-biodegradaliphatic aliphatic copolyester monofilament is 50 ~ 250dtex.
The invention has the beneficial effects as follows: the preparation method of a kind of completely-biodegradaliphatic aliphatic copolyester monofilament provided by the present invention, for the deficiencies in the prior art, adopt melt-polycondensation, with succinic acid and ethylene glycol for raw material, pentaerythrite is modified monomer, with antimony be catalyst, phosphoric acid ester for stabilizing agent, the continuity method polyester device of routine is prepared the PES copolyesters of high molecular; Again will the copolyesters of synthesis, directly by melt Conveying pipeline, to extrude through metering, spinning head, cooling curing in bosh, then through multistage stretching and HEAT SETTING, obtain completely-biodegradaliphatic aliphatic copolyester monofilament.The present invention has the following advantages: 1) by the pentaerythrite of introducing four degree of functionality, change general melt-polycondensation synthesis PES reaction time long deficiency, the introducing of pentaerythrite simultaneously, be equivalent to introduce long-chain branch in the molecule, improve melt strength, processability when improving high speed spinning and fibrous mechanical property; 2) adopt continuous polymerization to produce modified copolyester, further increase the quality of product, reduce production cost; 3) adopt melt direct spinning, avoid because PES fusing point is low, moisture is not easily removed, and when causing melt spinning, too large problem falls in viscosity, and production cost obviously declines; 4) have that flow process is short, cost is low, melt quality is stable, good spinning performance, the obtained every physical index of monofilament all can meet instructions for use, final products can after use be discarded, being decomposed into carbon dioxide and water by natural microorganism or enzyme, is a kind of macromolecular material of fully biodegradable.
Detailed description of the invention
Embodiment 1
The preparation method of a kind of completely-biodegradaliphatic aliphatic copolyester monofilament of the present embodiment indication, comprise the steps: 1) prepare aliphatic copolyester melt: on continuous polycondensation equipment, be succinic acid and the ethylene glycol of 1:1.25 by mol ratio, the molar percentage accounting for succinic acid is that the modified monomer pentaerythrite of 0.1 (pentaerythrite is mixed with the solution that pentaerythrite accounts for the molar percentage 5% of EG) adds in making beating still, pull an oar in still simultaneously and add the percentage by weight that 500ppm(accounts for succinic acid) antimony-based catalyst antimony glycol, in making beating still, break into slurry; Be delivered to by above-mentioned slurry continous-stable in esterification-I reactor, controlled pressure is 0.12MPa, and temperature is 200.0 DEG C, and the reaction time is 2.5 hours; Material after the reaction of esterification-I reactor being terminated again is sent in esterification-II reactor, and adds the stabilizing agent triphenyl phosphate accounting for succinic acid percentage by weight 200PPM, and control temperature is 210 DEG C, and the reaction time is 0.5 hour, and controlling esterification yield is 97.8%; Adopt transport pump to carry out polycondensation reaction to polycondensation workshop section above-mentioned obtained carboxylate again, reaction temperature is 235 ~ 240 DEG C, and vacuum is 10 ~ 0.1KPa, and the reaction time is 197min, the aliphatic copolyester melt that obtained number-average molecular weight is greater than 50,000.2) aliphatic copolyester monofilament is prepared: on corresponding melt directly spinning filament production equipment, by aliphatic copolyester melt obtained for step 1) by melt Conveying equipment, through metering, spinning head extrudes, cooling curing in bosh, then through multistage stretching and HEAT SETTING, the temperature controlling melt Conveying equipment (pipeline) is 200 DEG C; Spinning body temperature is 220 DEG C; Cooling water temperature 30 DEG C; Drawing temperature 40 DEG C; Heat setting temperature 50 DEG C; Drafting multiple 4.5; Winding speed 50m/min; The filament number of obtained completely-biodegradaliphatic aliphatic copolyester monofilament is 50dtex.
The inherent viscosity of the completely-biodegradaliphatic aliphatic copolyester obtained by the present embodiment, fusing point, number-average molecular weight are in table 1; The spinning operation performance of the completely-biodegradaliphatic aliphatic copolyester monofilament obtained by the present embodiment, fracture strength, elongation at break are in table 2.
The preparation method of a kind of completely-biodegradaliphatic aliphatic copolyester monofilament provided by the present embodiment, for the deficiencies in the prior art, adopt melt-polycondensation, with succinic acid and ethylene glycol for raw material, pentaerythrite is modified monomer, with antimony be catalyst, phosphoric acid ester for stabilizing agent, the continuity method polyester device of routine is prepared the PES copolyesters of high molecular; Again will the copolyesters of synthesis, directly by melt Conveying pipeline, to extrude through metering, spinning head, cooling curing in bosh, then through multistage stretching and HEAT SETTING, obtain completely-biodegradaliphatic aliphatic copolyester monofilament.Have the following advantages: 1) by the pentaerythrite of introducing four degree of functionality, change general melt-polycondensation synthesis PES reaction time long deficiency, the introducing of pentaerythrite simultaneously, be equivalent to introduce long-chain branch in the molecule, improve melt strength, processability when improving high speed spinning and fibrous mechanical property; 2) adopt continuous polymerization to produce modified copolyester, further increase the quality of product, reduce production cost; 3) adopt melt direct spinning, avoid because PES fusing point is low, moisture is not easily removed, and when causing melt spinning, too large problem falls in viscosity, and production cost obviously declines; 4) have that flow process is short, cost is low, melt quality is stable, good spinning performance, the obtained every physical index of monofilament all can meet instructions for use, final products can after use be discarded, being decomposed into carbon dioxide and water by natural microorganism or enzyme, is a kind of macromolecular material of fully biodegradable.
Embodiment 2
The preparation method of a kind of completely-biodegradaliphatic aliphatic copolyester monofilament of the present embodiment indication, comprise the steps: 1) prepare aliphatic copolyester melt: on continuous polycondensation equipment, be succinic acid and the ethylene glycol of 1:1.15 by mol ratio, the molar percentage accounting for succinic acid is that the modified monomer pentaerythrite of 0.2% (pentaerythrite is mixed with the solution that pentaerythrite accounts for the molar percentage 5% of EG) adds in making beating still, pull an oar in still simultaneously and add the percentage by weight that 500ppm(accounts for succinic acid) antimony-based catalyst antimonous oxide, in making beating still, break into slurry; Be delivered to by above-mentioned slurry continous-stable in esterification-I reactor, controlled pressure is 0.12MPa, and temperature is 200.0 DEG C, and the reaction time is 2.5 hours; Material after the reaction of esterification-I reactor being terminated again is sent in esterification-II reactor, and adds the stabilizing agent phosphorous acid accounting for succinic acid percentage by weight 200PPM, and control temperature is 210 DEG C, and the reaction time is 0.5 hour, and recording esterification yield is 98.1%; Adopt transport pump to carry out polycondensation reaction to polycondensation workshop section above-mentioned obtained carboxylate again, reaction temperature is 230 ~ 235 DEG C, and vacuum is 10 ~ 0.1KPa, and the reaction time is 185min, the aliphatic copolyester melt that obtained number-average molecular weight is greater than 50,000.2) aliphatic copolyester monofilament is prepared: on corresponding melt directly spinning filament production equipment, by aliphatic copolyester melt obtained for step 1) by melt Conveying equipment, through metering, spinning head extrudes, cooling curing in bosh, then through multistage stretching and HEAT SETTING, the temperature controlling melt Conveying equipment (pipeline) is 205 DEG C; Spinning body temperature is 230 DEG C; Cooling water temperature 20 DEG C; Drawing temperature 45 DEG C; Heat setting temperature 60 DEG C; Drafting multiple 5.0; Winding speed 125m/min; The filament number of obtained completely-biodegradaliphatic aliphatic copolyester monofilament is 150dtex.
The inherent viscosity of the completely-biodegradaliphatic aliphatic copolyester obtained by the present embodiment, fusing point, number-average molecular weight are in table 1; The spinning operation performance of the completely-biodegradaliphatic aliphatic copolyester monofilament obtained by the present embodiment, fracture strength, elongation at break are in table 2.
The preparation method of a kind of completely-biodegradaliphatic aliphatic copolyester monofilament provided by the present embodiment, for the deficiencies in the prior art, adopt melt-polycondensation, with succinic acid and ethylene glycol for raw material, pentaerythrite is modified monomer, with antimony be catalyst, phosphoric acid ester for stabilizing agent, the continuity method polyester device of routine is prepared the PES copolyesters of high molecular; Again will the copolyesters of synthesis, directly by melt Conveying pipeline, to extrude through metering, spinning head, cooling curing in bosh, then through multistage stretching and HEAT SETTING, obtain completely-biodegradaliphatic aliphatic copolyester monofilament.Have the following advantages: 1) by the pentaerythrite of introducing four degree of functionality, change general melt-polycondensation synthesis PES reaction time long deficiency, the introducing of pentaerythrite simultaneously, be equivalent to introduce long-chain branch in the molecule, improve melt strength, processability when improving high speed spinning and fibrous mechanical property; 2) adopt continuous polymerization to produce modified copolyester, further increase the quality of product, reduce production cost; 3) adopt melt direct spinning, avoid because PES fusing point is low, moisture is not easily removed, and when causing melt spinning, too large problem falls in viscosity, and production cost obviously declines; 4) have that flow process is short, cost is low, melt quality is stable, good spinning performance, the obtained every physical index of monofilament all can meet instructions for use, final products can after use be discarded, being decomposed into carbon dioxide and water by natural microorganism or enzyme, is a kind of macromolecular material of fully biodegradable.
Embodiment 3
The preparation method of a kind of completely-biodegradaliphatic aliphatic copolyester monofilament of the present embodiment indication, comprise the steps: 1) prepare aliphatic copolyester melt: on continuous polycondensation equipment, be succinic acid and the ethylene glycol of 1:1.05 by mol ratio, the molar percentage accounting for succinic acid is that the modified monomer pentaerythrite of 0.3% (pentaerythrite is mixed with the solution that pentaerythrite accounts for the molar percentage 5% of EG) adds in making beating still, pull an oar in still simultaneously and add the percentage by weight that 500ppm(accounts for succinic acid) antimony-based catalyst antimony acetate, in making beating still, break into slurry; Be delivered to by above-mentioned slurry continous-stable in esterification-I reactor, controlled pressure is 0.12MPa, and temperature is 200.0 DEG C, and the reaction time is 2.5 hours; Material after the reaction of esterification-I reactor being terminated again is sent in esterification-II reactor, and adds the stabilizing agent trimethyl phosphate accounting for succinic acid percentage by weight 200PPM, and control temperature is 210 DEG C, and the reaction time is 0.5 hour, and controlling esterification yield is 98.5%; Transport pump is adopted to carry out polycondensation reaction to polycondensation workshop section above-mentioned obtained carboxylate again, reaction temperature is 225 ~ 230 DEG C, vacuum is 10 ~ 0.1KPa, and the reaction time is 175min, the completely-biodegradaliphatic aliphatic copolyester melt that obtained number-average molecular weight is greater than 50,000.2) aliphatic copolyester monofilament is prepared: on corresponding melt directly spinning filament production equipment, by aliphatic copolyester melt obtained for step 1) by melt Conveying equipment, through metering, spinning head extrudes, cooling curing in bosh, then through multistage stretching and HEAT SETTING, the temperature controlling melt Conveying equipment (pipeline) is 210 DEG C; Spinning body temperature is 240 DEG C; Cooling water temperature 10 DEG C; Drawing temperature 50 DEG C; Heat setting temperature 70 DEG C; Drafting multiple 5.5; Winding speed 200m/min; The filament number of obtained completely-biodegradaliphatic aliphatic copolyester monofilament is 250dtex.
The inherent viscosity of the completely-biodegradaliphatic aliphatic copolyester obtained by the present embodiment, fusing point, number-average molecular weight are in table 1; The spinning operation performance of the completely-biodegradaliphatic aliphatic copolyester monofilament obtained by the present embodiment, fracture strength, elongation at break are in table 2.
The preparation method of a kind of completely-biodegradaliphatic aliphatic copolyester monofilament provided by the present embodiment, for the deficiencies in the prior art, adopt melt-polycondensation, with succinic acid and ethylene glycol for raw material, pentaerythrite is modified monomer, with antimony be catalyst, phosphoric acid ester for stabilizing agent, the continuity method polyester device of routine is prepared the PES copolyesters of high molecular; Again will the copolyesters of synthesis, directly by melt Conveying pipeline, to extrude through metering, spinning head, cooling curing in bosh, then through multistage stretching and HEAT SETTING, obtain completely-biodegradaliphatic aliphatic copolyester monofilament.Have the following advantages: 1) by the pentaerythrite of introducing four degree of functionality, change general melt-polycondensation synthesis PES reaction time long deficiency, the introducing of pentaerythrite simultaneously, be equivalent to introduce long-chain branch in the molecule, improve melt strength, processability when improving high speed spinning and fibrous mechanical property; 2) adopt continuous polymerization to produce modified copolyester, further increase the quality of product, reduce production cost; 3) adopt melt direct spinning, avoid because PES fusing point is low, moisture is not easily removed, and when causing melt spinning, too large problem falls in viscosity, and production cost obviously declines; 4) have that flow process is short, cost is low, melt quality is stable, good spinning performance, the obtained every physical index of monofilament all can meet instructions for use, final products can after use be discarded, being decomposed into carbon dioxide and water by natural microorganism or enzyme, is a kind of macromolecular material of fully biodegradable.
Comparing embodiment 1
1) aliphatic copolyester melt is prepared: on continuous polycondensation equipment, be that the succinic acid of 1:1.25 and ethylene glycol add and pulls an oar in still by mol ratio, pull an oar in still simultaneously and add the percentage by weight that 500ppm(accounts for succinic acid) antimony-based catalyst antimony glycol, in making beating still, break into slurry; Be delivered to by above-mentioned slurry continous-stable in esterification-I reactor, controlled pressure is 0.12MPa, and temperature is 200.0 DEG C, and the reaction time is 2.5 hours; Material after the reaction of esterification-I reactor being terminated again is sent in esterification-II reactor, and adds the stabilizing agent triphenyl phosphate accounting for succinic acid percentage by weight 200PPM, and control temperature is 210 DEG C, and the reaction time is 0.5 hour, and controlling esterification yield is 97.8%; Adopt transport pump to carry out polycondensation reaction to polycondensation workshop section above-mentioned obtained carboxylate again, reaction temperature is 235 ~ 240 DEG C, and vacuum is 10 ~ 0.1KPa, and the reaction time is 247min, obtained completely-biodegradaliphatic aliphatic copolyester.2) aliphatic copolyester monofilament is prepared: on corresponding melt directly spinning filament production equipment, by aliphatic copolyester melt obtained for step 1) by melt Conveying equipment, through metering, spinning head extrudes, cooling curing in bosh, then through multistage stretching and HEAT SETTING, the temperature controlling melt Conveying equipment (pipeline) is 200 DEG C; Spinning body temperature is 220 DEG C; Cooling water temperature 30 DEG C; Drawing temperature 40 DEG C; Heat setting temperature 50 DEG C; Drafting multiple 4.5; Winding speed 50m/min; The filament number of obtained completely-biodegradaliphatic aliphatic copolyester monofilament is 50dtex.
The inherent viscosity of the completely-biodegradaliphatic aliphatic copolyester obtained by this comparing embodiment, fusing point, number-average molecular weight are in table 1; The spinning operation performance of the completely-biodegradaliphatic aliphatic copolyester monofilament obtained by the present embodiment, fracture strength, elongation at break are in table 2.
Comparing embodiment 2
1) aliphatic copolyester melt is prepared: on continuous polycondensation equipment, be succinic acid and the ethylene glycol of 1:1.15 by mol ratio, the molar percentage accounting for succinic acid is that the modified monomer pentaerythrite of 0.2% (pentaerythrite is mixed with the solution that pentaerythrite accounts for the molar percentage 5% of EG) adds in making beating still, pull an oar in still simultaneously and add the percentage by weight that 500ppm(accounts for succinic acid) antimony-based catalyst antimonous oxide, in making beating still, break into slurry; Be delivered to by above-mentioned slurry continous-stable in esterification-I reactor, controlled pressure is 0.12MPa, and temperature is 200.0 DEG C, and the reaction time is 2.5 hours; Material after the reaction of esterification-I reactor being terminated again is sent in esterification-II reactor, and adds the stabilizing agent phosphorous acid accounting for succinic acid percentage by weight 200PPM, and control temperature is 210 DEG C, and the reaction time is 0.5 hour, and recording esterification yield is 98.1%; Adopt transport pump to carry out polycondensation reaction to polycondensation workshop section above-mentioned obtained carboxylate again, reaction temperature is 230 ~ 235 DEG C, and vacuum is 10 ~ 0.1KPa, and the reaction time is 185min, the aliphatic copolyester melt that obtained number-average molecular weight is greater than 50,000.2) by aliphatic copolyester melt obtained for step 1) through water-cooled, pelletizing, obtained section particle, then spin on monofilament equipment by chip drying and in routine section and carry out melt spinning; Section at 65 DEG C dry 24 hours, spinning body temperature is 230 DEG C, cooling water temperature 20 DEG C; Drawing temperature 45 DEG C; Heat setting temperature 60 DEG C; Drafting multiple 5.0; Winding speed 125m/min; The filament number of obtained completely-biodegradaliphatic aliphatic copolyester monofilament is 150dtex.
Because drying condition is wayward in comparing embodiment 2, the viscosity without silk noil drops to 0.647dl/g, and the silk that wafts during spinning increases, mechanical properties decrease.
The inherent viscosity of the completely-biodegradaliphatic aliphatic copolyester obtained by this comparing embodiment, fusing point, number-average molecular weight are in table 1; The spinning operation performance of the completely-biodegradaliphatic aliphatic copolyester monofilament obtained by the present embodiment, fracture strength, elongation at break are in table 2.
The mensuration of embodiment 1-3 and comparing embodiment 1,2 middle-molecular-weihydroxyethyl adopts PL company gel permeation chrommatograph (GPC), and chloroform is mobile phase, and concentration is 0.3%, flow velocity 1ml/min, temperature 40 DEG C, and standard sample is the polystyrene of narrow ditribution.Intrinsic viscosity, with reference to GB/T14190-93 standard, is that solvent is tested with chloroform.In embodiment 1-3 and comparing embodiment 1,2 aliphatic copolyester melt synthesis condition with the results are shown in Table 1; In embodiment 1-3 and comparing embodiment 1,2 completely-biodegradaliphatic aliphatic copolyester pre-oriented yarn (POY) long filament (120dtex/48fPOY) preparation condition with the results are shown in Table 2.
As shown in table 1, embodiment 1 ~ 3 can be seen, the PES that the present invention obtains makes the time shorten of polycondensation reaction by adding pentaerythrite, production efficiency improves, and the PES molecular weight simultaneously obtained is higher; And do not add the comparing embodiment 1 of penta tetrol, then the time of polycondensation reaction extends greatly, and the PES molecular weight obtained is lower.
As shown in table 2, can be seen by embodiment 1 ~ 3, the PES copolyesters obtained by table 1 embodiment 1 ~ 3, by the monofilament that fused mass directly spinning is obtained, spinnability and fibrous physics index excellent; Do not add pentaerythrite when namely comparing embodiment 1 prepares PES copolyesters with the difference of embodiment 1, even if by the fused mass directly spinning technology of table 2 comparing embodiment 1, also cannot well meet aft-loaded airfoil and performance requirement, spinnability and fibrous physics index poor.It is identical that comparing embodiment 2 and embodiment 2 prepare PES copolyesters method, subsequently through the monofilament that spins of cutting into slices, spinnability and fibrous physics index poor.
Table 1
Table 2
Claims (4)
1.
oneplant the preparation method of completely-biodegradaliphatic aliphatic copolyester monofilament, it is characterized in that comprising the steps: 1) prepare aliphatic copolyester melt: with succinic acid and ethylene glycol for raw material, pentaerythrite is modified monomer, and adds antimony-based catalyst, in making beating still, break into slurry; Above-mentioned slurry continous-stable is delivered in reactor and carries out esterification and obtain carboxylate; Adopt transport pump to carry out polycondensation to polycondensation workshop section above-mentioned obtained carboxylate again and obtain aliphatic copolyester melt; 2) aliphatic copolyester monofilament is prepared: by aliphatic copolyester melt obtained for step 1) by melt Conveying equipment, through metering, spinning head extrudes, cooling curing in bosh, then through multistage stretching and HEAT SETTING, obtained completely-biodegradaliphatic aliphatic copolyester monofilament; Described step 1) is specially with succinic acid and ethylene glycol for raw material, and pentaerythrite is modified monomer, and adds antimony-based catalyst, in making beating still, break into slurry; Be delivered to by above-mentioned slurry continous-stable in esterification-I reactor, controlled pressure is 0.12MPa, and temperature is 200.0 DEG C, and the reaction time is 2.5 hours; Material after the reaction of esterification-I reactor being terminated again is sent in esterification-II reactor, and adds stabilizing agent, and control temperature is 210 DEG C, and the reaction time is 0.5 hour, and controlling esterification yield is 97.0% ~ 98.5%; Adopt transport pump to carry out polycondensation reaction to polycondensation workshop section above-mentioned obtained carboxylate again, reaction temperature is 225 ~ 240 DEG C, and vacuum is 10 ~ 0.1KPa, and the reaction time is less than 200min, the aliphatic copolyester melt that obtained number-average molecular weight is greater than 50,000; Described step 2) in the temperature of melt Conveying pipeline be 200 ~ 210 DEG C; Spinning body temperature is 220 ~ 240 DEG C; Cooling water temperature is 10 ~ 30 DEG C; Drawing temperature is 40 ~ 50 DEG C; Heat setting temperature is 50 ~ 70 DEG C; Drafting multiple is 4.5 ~ 5.5; Winding speed is 50 ~ 200 m/min; The filament number of obtained completely-biodegradaliphatic aliphatic copolyester monofilament is 50 ~ 250dtex.
2. the preparation method of a kind of completely-biodegradaliphatic aliphatic copolyester monofilament according to claim 1, is characterized in that the mol ratio of succinic acid and ethylene glycol in described step 1) is 1:1.05 ~ 1.25; Described pentaerythrite and the molar percentage of succinic acid are 0.1 ~ 0.3%; It is the solution of 5% that described pentaerythrite is made into the molar percentage that pentaerythrite accounts for ethylene glycol in advance; Described antimony-based catalyst and the percentage by weight of succinic acid are 500PPM; Described stabilizing agent and the percentage by weight of succinic acid are 200PPM.
3. the preparation method of a kind of completely-biodegradaliphatic aliphatic copolyester monofilament according to claim 1 and 2, is characterized in that in described step 1), antimony-based catalyst adopts the one in antimony glycol, antimonous oxide or antimony acetate; Described stabilizing agent adopts the one in triphenyl phosphate, phosphorous acid, trimethyl phosphate.
4. the preparation method of a kind of completely-biodegradaliphatic aliphatic copolyester monofilament according to claim 3, is characterized in that described antimony-based catalyst is antimony glycol; Described stabilizing agent is triphenyl phosphate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR0163495B1 (en) * | 1996-02-27 | 1998-12-01 | 박홍기 | Method of manufacturing polyester flat yarn |
| CN101498058A (en) * | 2009-02-24 | 2009-08-05 | 江苏盛虹化纤有限公司 | Superfine flat terylene low elater and technique for producing the same |
| CN102807669A (en) * | 2012-08-09 | 2012-12-05 | 宜兴市光辉包装材料有限公司 | Method for preparing polyester for films |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0163495B1 (en) * | 1996-02-27 | 1998-12-01 | 박홍기 | Method of manufacturing polyester flat yarn |
| CN101498058A (en) * | 2009-02-24 | 2009-08-05 | 江苏盛虹化纤有限公司 | Superfine flat terylene low elater and technique for producing the same |
| CN102807669A (en) * | 2012-08-09 | 2012-12-05 | 宜兴市光辉包装材料有限公司 | Method for preparing polyester for films |
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