CN103243413A - Preparation method of completely biodegradable aliphatic copolyester staple fiber - Google Patents
Preparation method of completely biodegradable aliphatic copolyester staple fiber Download PDFInfo
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- CN103243413A CN103243413A CN2013101453714A CN201310145371A CN103243413A CN 103243413 A CN103243413 A CN 103243413A CN 2013101453714 A CN2013101453714 A CN 2013101453714A CN 201310145371 A CN201310145371 A CN 201310145371A CN 103243413 A CN103243413 A CN 103243413A
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- aliphatic copolyester
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 92
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 78
- 239000000835 fiber Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 87
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims abstract description 74
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 36
- 239000001384 succinic acid Substances 0.000 claims abstract description 36
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 26
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000009998 heat setting Methods 0.000 claims abstract description 18
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000012856 packing Methods 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 claims description 35
- 230000035484 reaction time Effects 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 18
- 239000003381 stabilizer Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 238000010009 beating Methods 0.000 claims description 14
- 150000007942 carboxylates Chemical class 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000007664 blowing Methods 0.000 claims description 7
- 230000036760 body temperature Effects 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 5
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 abstract 3
- 238000004537 pulping Methods 0.000 abstract 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- 238000012545 processing Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 230000007812 deficiency Effects 0.000 description 10
- 229920000728 polyester Polymers 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000002074 melt spinning Methods 0.000 description 5
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 5
- 229920002961 polybutylene succinate Polymers 0.000 description 5
- 239000004631 polybutylene succinate Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000010036 direct spinning Methods 0.000 description 4
- 238000007380 fibre production Methods 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- DJIHQRBJGCGSIR-UHFFFAOYSA-N 2-methylidene-1,3-dioxepane-4,7-dione Chemical compound C1(CCC(=O)OC(=C)O1)=O DJIHQRBJGCGSIR-UHFFFAOYSA-N 0.000 description 1
- NDERRIHSWCOMJJ-UHFFFAOYSA-N C(C(=C)C)(=O)OC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.P(=O)(O)(O)O Chemical compound C(C(=C)C)(=O)OC(C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1.P(=O)(O)(O)O NDERRIHSWCOMJJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DJOWTWWHMWQATC-KYHIUUMWSA-N Karpoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1(O)C(C)(C)CC(O)CC1(C)O)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C DJOWTWWHMWQATC-KYHIUUMWSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- -1 poly butylene succinate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
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- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a preparation method of completely biodegradable aliphatic copolyester staple fiber. The preparation method comprises the following steps of: 1, preparation of an aliphatic copolyester fusant: pulping succinic acid, ethylene glycol, pentaerythritol and an antimony serial catalyst in a pulping kettle, wherein succinic acid and ethylene glycol serve as raw materials and pentaerythritol serves as a modified monomer, continuously and stably conveying the prepared pulp into a reaction kettle to carry out esterification reaction to produce an ester, conveying the prepared ester to a polycondensation section by a pump so that the prepared ester is poly-condensed into the aliphatic copolyester fusant; and 2, preparation of aliphatic copolyester staple fiber: metering, extruding, air-cooling and oiling the aliphatic copolyester fusant by fusant conveying equipment to form a concentrated beam, then carrying out drawing, heat setting, coiling, cutting and packing, to finally obtain the completely biodegradable aliphatic copolyester staple fiber. The preparation method has the advantages that the flow is short, the cost is low, the quality of the fusant is stable, spinnability is excellent, and the breaking strength and other indexes of the prepared staple fiber can meet the postprocessing requirements.
Description
Technical field
The present invention relates to the preparation method of a kind of preparation method of fully biodegradable aliphatic copolyester staple fibre, particularly a kind of continuous polymerization, fused mass directly spinning fully biodegradable aliphatic copolyester staple fibre, belong to the 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.The ester bond that contains facile hydrolysis in the aliphatic polyester main chain, and main chain is submissive is easy under action of microorganisms the catalysis by enzyme and degrades, and it has become the focus of researching and developing in the world wide as environment-friendly material.Wherein successful industrialization has a PLA (PLA), polycaprolactone (PCL) and binary aliphatic alkyd polyester etc., as the biodegradable aliphatic polyester of poly butylene succinate (PBS) as a quasi-representative, because its excellent combination property, cost performance rationally enjoys favor, development was very fast in recent years, be that current domestic and international research and development is maximum, technology is ripe relatively, the biodegradation material of industrialized scale maximum, it also is one of the kind the earliest that comes into the market, mainly for the production of packing, film, agricultural aquatic products and building goods, materials and equipments etc., realize fully biodegradable, reduce the pollution to environment.But simultaneously higher because of its production cost, add that fusing point is lower, make that the melt strength under the high temperature spinning condition is lower, so spinning properties is relatively poor, seriously hindered its application in fiber art, not seeing so far has the application report of PBS on textile fabric.
Polyethylene glycol succinate (PES) polyester is the homologous series polymer of PBS polyester, also is crystalline polymer, and its fusing point is about 104 ℃, vitrification point is about-12.5 ℃, and crystallization rate is very fast, better heat stability, biodegradable, and production cost is lower than PBS.Synthesizing of relevant PES polyester, pertinent literature also has report.As being that raw material carries out ring-opening polymerization with succinic anhydride and oxirane, obtained the higher PES of relative molecular mass, but because the toxicity of oxirane is bigger, easy contaminated environment also endangers health of operators, needs very strict control reaction.Be solvent with the decahydronaphthalene, synthesized the polyethylene glycol succinate PES of higher relative molecular weight by polymerisation in solution, but solution polymerization speed be slower, and need handle solvent recovery that production cost is higher, is difficult to obtain practical application.In addition, report synthesizes 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), be raw material with succinic acid (SA) and ethylene glycol (EG), method with polymerisation in solution makes performed polymer earlier, make the PES of high molecular then by the method for chain extension, be used for plastics-production, but there is deficiencies such as needing solvent recovery, reaction time length in this method.Although both at home and abroad the research to PES just begins, the release of commercially produced product is not arranged as yet, no matter from raw material sources, still from performance and the cost angle of PES, PES all is environment friendly polyester that a class has potentiality.
Therefore, overcome the technological process complexity that exists among the preparation method of above-mentioned PES, production cost height, section crystallizing and drying difficulty, molecular weight and molecular weight is big after the fusion again, melt strength is low, being difficult to satisfy the deficiencies such as processes requirement of high speed spinning, must be the emphasis of research and breakthrough.
The content of invention
The object of the present invention is to provide a kind of preparation method of fully biodegradable aliphatic copolyester staple fibre, have that flow process is short, cost is low, melt quality is stable, good spinning performance, indexs such as the staple fibre strength and elongation that makes all can satisfy the requirement of back processing, final products can be 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 fully biodegradable aliphatic copolyester staple fibre, comprise the steps: 1) preparation aliphatic copolyester melt: be raw material with succinic acid and ethylene glycol, pentaerythrite is modified monomer, and adds antimony-based catalyst, breaks into slurry in the making beating still; Above-mentioned slurry continous-stable is delivered to carries out esterification in the reactor and make carboxylate; The above-mentioned carboxylate that makes being adopted pump to be transported to polycondensation workshop section carries out polycondensation and makes the aliphatic copolyester melt again; 2) preparation aliphatic copolyester staple fibre: the aliphatic copolyester melt that step 1) is made passes through melt Conveying equipment, through measure, extrude, dry cooling, boundling oils, drawing-off, HEAT SETTING, curl, cut off, packing, make fully biodegradable aliphatic copolyester staple fibre.
It is raw material that described step 1) is specially with succinic acid and ethylene glycol, and pentaerythrite is modified monomer, and adds antimony-based catalyst, breaks into slurry in the making beating still; Above-mentioned slurry continous-stable is delivered in esterification-I reactor, and controlled pressure is 0.12MPa, and temperature is 200.0 ℃, and the reaction time is 2.5 hours; The material after esterification-reaction of I reactor finishes is sent in esterification-II reactor again, and added stabilizing agent, the control temperature is 210 ℃, and the reaction time is 0.5 hour, and the control esterification yield is 97.0%～98.5%; Again with above-mentioned make carboxylate adopt pump to be transported to polycondensation workshop section to carry out polycondensation reaction, reaction temperature is 225～240 ℃, vacuum is 10～0.1KPa, the reaction time is less than 200min, makes number-average molecular weight greater than 50,000 aliphatic copolyester melt.
The mol ratio of succinic acid and ethylene glycol is 1:1.05～1.25 in the described step 1); The molar percentage of described pentaerythrite and succinic acid is 0.1～0.3%; It is 5% solution that described pentaerythrite is mixed with molar percentage that pentaerythrite accounts for ethylene glycol; The percentage by weight of described antimony-based catalyst and succinic acid is 500PPM; The percentage by weight of described stabilizing agent and succinic acid is 200PPM.
Antimony-based catalyst adopts a kind of in antimony glycol, antimonous oxide or the antimony acetate (being Jiangxi Er Yuan chemical industry Co., Ltd provides) in the described step 1); Described stabilizing agent adopts triphenyl phosphate to provide for chemical reagent purchase and supply 5-linked chemical plant, Shanghai), phosphorous acid provides for chemical reagent purchase and supply 5-linked chemical plant, Shanghai), a kind of in the trimethyl phosphate (for chemical reagent purchase and supply 5-linked chemical plant, Shanghai provides).
The preferred antimony glycol of described antimony-based catalyst; Described stabilizing agent preferably phosphoric acid triphenylmethyl methacrylate.
Described step 2) temperature of melt Conveying pipeline is 200～210 ℃ in; Spinning body temperature is 220～240 ℃; The spinnerets hole count is 2960; Ring blowing blast is 300～350Pa; Spinning speed is 800～1200m/min; Drafting multiple is 3.0～4.0; The drawing and heat-setting temperature is 60～80 ℃.
The invention has the beneficial effects as follows: the preparation method of a kind of fully biodegradable aliphatic copolyester staple fibre provided by the present invention, at the deficiencies in the prior art, adopt melt-polycondensation, be raw material with succinic acid and ethylene glycol, pentaerythrite is modified monomer, be that catalyst, phosphoric acid ester are stabilizing agent with antimony, prepare the PES copolyesters of high molecular at the continuity method polyester device of routine; Again with synthetic copolyesters, directly by the melt Conveying pipeline, through measure, extrude, dry cooling, the boundling that oils, drawing-off, HEAT SETTING, curl, cut-out, pack, make fully biodegradable aliphatic copolyester staple fibre.The present invention has the following advantages: 1) by introducing the pentaerythrite of four degrees of functionality, changed the synthetic long deficiency of PES reaction time of general melt-polycondensation, the introducing of pentaerythrite simultaneously, be equivalent in molecule, introduce long-chain branch, improved melt strength, the processability when improving high speed spinning and fibrous mechanical property; 2) adopt continuous polymerization to produce modified copolyester, further improved product quality, reduced production cost; 3) adopt melt direct spinning, avoided because the PES fusing point is low, moisture is difficult for removing, and too big problem falls in viscosity when causing melt spinning, and production cost obviously descends; 4) have that flow process is short, cost is low, melt quality is stable, good spinning performance, indexs such as the staple fibre strength and elongation that makes all can satisfy the requirement of back processing, final products can be after use be discarded, being decomposed into carbon dioxide and water by natural microorganism or enzyme, is a kind of fully biodegradable macromolecular material.
The specific embodiment
Embodiment 1
The preparation method of a kind of fully biodegradable aliphatic copolyester of present embodiment indication staple fibre, comprise the steps: 1) preparation aliphatic copolyester melt: on continuous polycondensation equipment, be succinic acid and the ethylene glycol of 1:1.25 with mol ratio, the molar percentage that accounts for succinic acid is that 0.1 modified monomer pentaerythrite (pentaerythrite is mixed with the solution that pentaerythrite accounts for the molar percentage 5% of EG) adds in the making beating still, pull an oar simultaneously and add the percentage by weight that 500ppm(accounts for succinic acid in the still) the antimony-based catalyst antimony glycol,, in the making beating still, break into slurry; Above-mentioned slurry continous-stable is delivered in esterification-I reactor, and controlled pressure is 0.12MPa, and temperature is 200.0 ℃, and the reaction time is 2.5 hours; The material after esterification-reaction of I reactor finishes is sent in esterification-II reactor again, and added the stabilizing agent triphenyl phosphate that accounts for succinic acid percentage by weight 200PPM, the control temperature is 210 ℃, and the reaction time is 0.5 hour, and the control esterification yield is 97.8%; Adopt pump to be transported to polycondensation workshop section the above-mentioned carboxylate that makes again and carry out polycondensation reaction, reaction temperature is 235～240 ℃, and vacuum is 10～0.1KPa, and the reaction time is 197min, makes number-average molecular weight greater than 50,000 aliphatic copolyester melt.2) preparation aliphatic copolyester staple fibre: on corresponding fused mass directly spinning staple fibre production equipment, the aliphatic copolyester melt that step 1) is made passes through melt Conveying equipment, through measure, extrude, dry cooling, boundling oils, drawing-off, HEAT SETTING, curl, cut off, packing, the temperature of control melt Conveying equipment (pipeline) is 200 ℃; Spinning body temperature is 220 ℃; The spinnerets hole count is 2960 holes; Ring blowing blast is 300Pa; Spinning speed is 800m/min; Drafting multiple is 4.0; The drawing and heat-setting temperature is 60 ℃, makes fully biodegradable aliphatic copolyester staple fibre (the thin dawn short fiber of 1.44dtex/38mm).
Inherent viscosity, fusing point, the number-average molecular weight of the fully biodegradable aliphatic copolyester that makes by present embodiment see Table 1; Processing characteristics, fracture strength, the elongation at break of the fully biodegradable aliphatic copolyester monofilament that makes by present embodiment see Table 2.
The preparation method of a kind of fully biodegradable aliphatic copolyester staple fibre that provides by present embodiment, at the deficiencies in the prior art, adopt melt-polycondensation, be raw material with succinic acid and ethylene glycol, pentaerythrite is modified monomer, be that catalyst, phosphoric acid ester are stabilizing agent with antimony, prepare the PES copolyesters of high molecular at the continuity method polyester device of routine; Again with synthetic copolyesters, directly by the melt Conveying pipeline, through measure, extrude, dry cooling, the boundling that oils, drawing-off, HEAT SETTING, curl, cut-out, pack, make fully biodegradable aliphatic copolyester staple fibre.Present embodiment has the following advantages: 1) by introducing the pentaerythrite of four degrees of functionality, changed the synthetic long deficiency of PES reaction time of general melt-polycondensation, the introducing of pentaerythrite simultaneously, be equivalent in molecule, introduce long-chain branch, improved melt strength, the processability when improving high speed spinning and fibrous mechanical property; 2) adopt continuous polymerization to produce modified copolyester, further improved product quality, reduced production cost; 3) adopt melt direct spinning, avoided because the PES fusing point is low, moisture is difficult for removing, and too big problem falls in viscosity when causing melt spinning, and production cost obviously descends; 4) have that flow process is short, cost is low, melt quality is stable, good spinning performance, indexs such as the staple fibre strength and elongation that makes all can satisfy the requirement of back processing, final products can be after use be discarded, being decomposed into carbon dioxide and water by natural microorganism or enzyme, is a kind of fully biodegradable macromolecular material.
Embodiment 2
The preparation method of a kind of fully biodegradable aliphatic copolyester of present embodiment indication staple fibre, comprise the steps: 1) preparation aliphatic copolyester melt: on continuous polycondensation equipment, be succinic acid and the ethylene glycol of 1:1.15 with mol ratio, the molar percentage that accounts for succinic acid is that 0.2% modified monomer pentaerythrite (pentaerythrite is mixed with the solution that pentaerythrite accounts for the molar percentage 5% of EG) adds in the making beating still, pull an oar simultaneously and add the percentage by weight that 500ppm(accounts for succinic acid in the still) the antimony-based catalyst antimonous oxide, in the making beating still, break into slurry; Above-mentioned slurry continous-stable is delivered in esterification-I reactor, and controlled pressure is 0.12MPa, and temperature is 200.0 ℃, and the reaction time is 2.5 hours; The material after esterification-reaction of I reactor finishes is sent in esterification-II reactor again, and added the stabilizing agent phosphorous acid that accounts for succinic acid percentage by weight 200PPM, the control temperature is 210 ℃, and the reaction time is 0.5 hour, and recording esterification yield is 98.1%; Adopt pump to be transported to polycondensation workshop section the above-mentioned carboxylate that makes again and carry out polycondensation reaction, reaction temperature is 230～235 ℃, and vacuum is 10～0.1KPa, and the reaction time is 185min, makes number-average molecular weight greater than 50,000 aliphatic copolyester melt.2) preparation aliphatic copolyester staple fibre: on corresponding fused mass directly spinning staple fibre production equipment, the aliphatic copolyester melt that step 1) is made passes through melt Conveying equipment, through measure, extrude, dry cooling, boundling oils, drawing-off, HEAT SETTING, curl, cut off, packing, the temperature of control melt Conveying equipment (pipeline) is 205 ℃; Spinning body temperature is 230 ℃; The spinnerets hole count is 2960 holes; Ring blowing blast is 325Pa; Spinning speed 1000m/min; Drafting multiple 3.5; 70 ℃ of drawing and heat-setting temperature; Make fully biodegradable aliphatic copolyester staple fibre (the thin dawn short fiber of 1.44dtex/38mm).
Inherent viscosity, fusing point, the number-average molecular weight of the fully biodegradable aliphatic copolyester that makes by present embodiment see Table 1; Processing characteristics, fracture strength, the elongation at break of the fully biodegradable aliphatic copolyester monofilament that makes by present embodiment see Table 2.
The preparation method of a kind of fully biodegradable aliphatic copolyester staple fibre that provides by present embodiment, at the deficiencies in the prior art, adopt melt-polycondensation, be raw material with succinic acid and ethylene glycol, pentaerythrite is modified monomer, be that catalyst, phosphoric acid ester are stabilizing agent with antimony, prepare the PES copolyesters of high molecular at the continuity method polyester device of routine; Again with synthetic copolyesters, directly by the melt Conveying pipeline, through measure, extrude, dry cooling, the boundling that oils, drawing-off, HEAT SETTING, curl, cut-out, pack, make fully biodegradable aliphatic copolyester staple fibre.Present embodiment has the following advantages: 1) by introducing the pentaerythrite of four degrees of functionality, changed the synthetic long deficiency of PES reaction time of general melt-polycondensation, the introducing of pentaerythrite simultaneously, be equivalent in molecule, introduce long-chain branch, improved melt strength, the processability when improving high speed spinning and fibrous mechanical property; 2) adopt continuous polymerization to produce modified copolyester, further improved product quality, reduced production cost; 3) adopt melt direct spinning, avoided because the PES fusing point is low, moisture is difficult for removing, and too big problem falls in viscosity when causing melt spinning, and production cost obviously descends; 4) have that flow process is short, cost is low, melt quality is stable, good spinning performance, indexs such as the staple fibre strength and elongation that makes all can satisfy the requirement of back processing, final products can be after use be discarded, being decomposed into carbon dioxide and water by natural microorganism or enzyme, is a kind of fully biodegradable macromolecular material.
Embodiment 3
The preparation method of a kind of fully biodegradable aliphatic copolyester of present embodiment indication staple fibre, comprise the steps: 1) preparation aliphatic copolyester melt: on continuous polycondensation equipment, be succinic acid and the ethylene glycol of 1:1.05 with mol ratio, the molar percentage that accounts for succinic acid is that 0.3% modified monomer pentaerythrite (pentaerythrite is mixed with the solution that pentaerythrite accounts for the molar percentage 5% of EG) adds in the making beating still, pull an oar simultaneously and add the percentage by weight that 500ppm(accounts for succinic acid in the still) the antimony-based catalyst antimony acetate, in the making beating still, break into slurry; Above-mentioned slurry continous-stable is delivered in esterification-I reactor, and controlled pressure is 0.12MPa, and temperature is 200.0 ℃, and the reaction time is 2.5 hours; The material after esterification-reaction of I reactor finishes is sent in esterification-II reactor again, and added the stabilizing agent trimethyl phosphate that accounts for succinic acid percentage by weight 200PPM, the control temperature is 210 ℃, and the reaction time is 0.5 hour, and the control esterification yield is 98.5%; Adopt pump to be transported to polycondensation workshop section the above-mentioned carboxylate that makes again and carry out polycondensation reaction, reaction temperature is 225～230 ℃, vacuum is 10～0.1KPa, and the reaction time is 175min, makes number-average molecular weight greater than 50,000 fully biodegradable aliphatic copolyester melt.2) preparation aliphatic copolyester staple fibre: on corresponding fused mass directly spinning staple fibre production equipment, the aliphatic copolyester melt that step 1) is made passes through melt Conveying equipment, through measure, extrude, dry cooling, boundling oils, drawing-off, HEAT SETTING, curl, cut off, packing, the temperature of control melt Conveying equipment (pipeline) is 210 ℃; Spinning body temperature is 240 ℃; The spinnerets hole count is 2960 holes; Ring blowing blast is 350Pa; Spinning speed is 1200m/min; Drafting multiple is 3.0; 80 ℃ of drawing and heat-setting temperature; Make fully biodegradable aliphatic copolyester staple fibre (the thin dawn short fiber of 1.44dtex/38mm).
Inherent viscosity, fusing point, the number-average molecular weight of the fully biodegradable aliphatic copolyester that makes by present embodiment see Table 1; Processing characteristics, fracture strength, the elongation at break of the fully biodegradable aliphatic copolyester monofilament that makes by present embodiment see Table 2.
The preparation method of a kind of fully biodegradable aliphatic copolyester staple fibre that provides by present embodiment, at the deficiencies in the prior art, adopt melt-polycondensation, be raw material with succinic acid and ethylene glycol, pentaerythrite is modified monomer, be that catalyst, phosphoric acid ester are stabilizing agent with antimony, prepare the PES copolyesters of high molecular at the continuity method polyester device of routine; Again with synthetic copolyesters, directly by the melt Conveying pipeline, through measure, extrude, dry cooling, the boundling that oils, drawing-off, HEAT SETTING, curl, cut-out, pack, make fully biodegradable aliphatic copolyester staple fibre.Present embodiment has the following advantages: 1) by introducing the pentaerythrite of four degrees of functionality, changed the synthetic long deficiency of PES reaction time of general melt-polycondensation, the introducing of pentaerythrite simultaneously, be equivalent in molecule, introduce long-chain branch, improved melt strength, the processability when improving high speed spinning and fibrous mechanical property; 2) adopt continuous polymerization to produce modified copolyester, further improved product quality, reduced production cost; 3) adopt melt direct spinning, avoided because the PES fusing point is low, moisture is difficult for removing, and too big problem falls in viscosity when causing melt spinning, and production cost obviously descends; 4) have that flow process is short, cost is low, melt quality is stable, good spinning performance, indexs such as the staple fibre strength and elongation that makes all can satisfy the requirement of back processing, final products can be after use be discarded, being decomposed into carbon dioxide and water by natural microorganism or enzyme, is a kind of fully biodegradable macromolecular material.
Comparing embodiment 1
1) preparation aliphatic copolyester melt: on continuous polycondensation equipment, be that the succinic acid of 1:1.25 and ethylene glycol add in the making beating still with mol ratio, pull an oar simultaneously and add the percentage by weight that 500ppm(accounts for succinic acid in the still) the antimony-based catalyst antimony glycol,, in the making beating still, break into slurry; Above-mentioned slurry continous-stable is delivered in esterification-I reactor, and controlled pressure is 0.12MPa, and temperature is 200.0 ℃, and the reaction time is 2.5 hours; The material after esterification-reaction of I reactor finishes is sent in esterification-II reactor again, and added the stabilizing agent triphenyl phosphate that accounts for succinic acid percentage by weight 200PPM, the control temperature is 210 ℃, and the reaction time is 0.5 hour, and the control esterification yield is 97.8%; Adopt pump to be transported to polycondensation workshop section the above-mentioned carboxylate that makes again and carry out polycondensation reaction, reaction temperature is 235～240 ℃, and vacuum is 10～0.1KPa, and the reaction time is 247min, makes the fully biodegradable aliphatic copolyester.2) preparation aliphatic copolyester staple fibre: on corresponding fused mass directly spinning staple fibre production equipment, the aliphatic copolyester melt that step 1) is made passes through melt Conveying equipment, through measure, extrude, dry cooling, boundling oils, drawing-off, HEAT SETTING, curl, cut off, packing, the temperature of control melt Conveying equipment (pipeline) is 200 ℃; Spinning body temperature is 220 ℃; The spinnerets hole count is 2960 holes; Ring blowing blast is 300Pa; Spinning speed is 800m/min; Drafting multiple is 4.0; The drawing and heat-setting temperature is 60 ℃, makes fully biodegradable aliphatic copolyester staple fibre (the thin dawn short fiber of 1.44dtex/38mm).
Inherent viscosity, fusing point, the number-average molecular weight of the fully biodegradable aliphatic copolyester that makes by this comparing embodiment see Table 1; Processing characteristics, fracture strength, the elongation at break of the fully biodegradable aliphatic copolyester monofilament that makes by present embodiment see Table 2.
Comparing embodiment 2
1) preparation aliphatic copolyester melt: on continuous polycondensation equipment, be succinic acid and the ethylene glycol of 1:1.15 with mol ratio, the molar percentage that accounts for succinic acid is that 0.2% modified monomer pentaerythrite (pentaerythrite is mixed with the solution that pentaerythrite accounts for the molar percentage 5% of EG) adds in the making beating still, pull an oar simultaneously and add the percentage by weight that 500ppm(accounts for succinic acid in the still) the antimony-based catalyst antimonous oxide, in the making beating still, break into slurry; Above-mentioned slurry continous-stable is delivered in esterification-I reactor, and controlled pressure is 0.12MPa, and temperature is 200.0 ℃, and the reaction time is 2.5 hours; The material after esterification-reaction of I reactor finishes is sent in esterification-II reactor again, and added the stabilizing agent phosphorous acid that accounts for succinic acid percentage by weight 200PPM, the control temperature is 210 ℃, and the reaction time is 0.5 hour, and recording esterification yield is 98.1%; Adopt pump to be transported to polycondensation workshop section the above-mentioned carboxylate that makes again and carry out polycondensation reaction, reaction temperature is 230～235 ℃, and vacuum is 5KPa, and the reaction time is 185min, makes number-average molecular weight greater than 50,000 aliphatic copolyester melt.2) the aliphatic copolyester melt that step 1) is made makes the section particle through water-cooled, pelletizing, again with chip drying and spin short fiber equipment in routine section and carry out melt spinning; Section was descended dry 24 hours at 65 ℃, and spinning body temperature is 230 ℃; The spinnerets hole count is 2960 holes; Ring blowing blast is 325Pa; Spinning speed 1000m/min; Drafting multiple 3.5; 70 ℃ of drawing and heat-setting temperature; Make fully biodegradable aliphatic copolyester staple fibre (the thin dawn short fiber of 1.44dtex/38mm).
Wayward because of drying condition in the present embodiment, the viscosity of not having the oil silk drops to 0.651dl/g, and the silk that wafts during spinning increases, even can't spinning.
Inherent viscosity, fusing point, the number-average molecular weight of the fully biodegradable aliphatic copolyester that makes by this comparing embodiment see Table 1; Processing characteristics, fracture strength, the elongation at break of the fully biodegradable aliphatic copolyester monofilament that makes by present embodiment see Table 2.
The mensuration of molecular weight adopts PL company's gel permeation chrommatograph (GPC) in embodiment 1-3 and the comparing embodiment 1,2, and chloroform is the phase that flows, and concentration is 0.3%, flow velocity 1ml/min, and 40 ℃ of temperature, standard sample is the polystyrene of narrow distribution.Intrinsic viscosity is that solvent is tested with reference to the GB/T14190-93 standard with the chloroform.In embodiment 1-3 and the comparing embodiment 1,2 synthesis condition of aliphatic copolyester melt with the results are shown in Table 1; In embodiment 1-3 and the comparing embodiment 1,2 fully biodegradable aliphatic copolyester staple fibre preparation condition with the results are shown in Table 2.
As shown in table 1, can see that by embodiment 1～3 PES that the present invention obtains shortens the time of polycondensation reaction by adding pentaerythrite, production efficiency improves, and the PES molecular weight that obtains simultaneously is higher; And the comparing embodiment 1 of not adding penta tetrol, then the time of polycondensation reaction prolongs greatly, and the PES molecular weight that obtains is lower.
As shown in table 2, can see that by table 2 embodiment 1～3 with the PES copolyesters that table 1 embodiment 1～3 obtains, by the staple fibre that fused mass directly spinning makes, spinnability and fibrous physics index are good; When namely preparing the PES copolyesters, the difference of comparing embodiment 1 and embodiment 1 do not add pentaerythrite, even the fused mass directly spinning technology by table 2 comparing embodiment 1, also can't well satisfy back processing and performance requirement, staple fibre spinnability and fibrous physics index are relatively poor.Comparing embodiment 2 and embodiment 2 preparation PES copolyesters methods are identical, follow-up by section spin staple fibre, spinnability and fibrous physics index are relatively poor.
Table 1
Table 2
Claims (6)
1. the preparation method of a fully biodegradable aliphatic copolyester staple fibre, it is characterized in that comprising the steps: 1) preparation aliphatic copolyester melt: be raw material with succinic acid and ethylene glycol, pentaerythrite is modified monomer, and adds antimony-based catalyst, breaks into slurry in the making beating still; Above-mentioned slurry continous-stable is delivered to carries out esterification in the reactor and make carboxylate; The above-mentioned carboxylate that makes being adopted pump to be transported to polycondensation workshop section carries out polycondensation and makes the aliphatic copolyester melt again; 2) preparation aliphatic copolyester staple fibre: the aliphatic copolyester melt that step 1) is made passes through melt Conveying equipment, through measure, extrude, dry cooling, boundling oils, drawing-off, HEAT SETTING, curl, cut off, packing, make fully biodegradable aliphatic copolyester staple fibre.
2. the preparation method of a kind of fully biodegradable aliphatic copolyester staple fibre according to claim 1, it is characterized in that it is raw material that described step 1) is specially with succinic acid and ethylene glycol, pentaerythrite is modified monomer, and adds antimony-based catalyst, breaks into slurry in the making beating still; Above-mentioned slurry continous-stable is delivered in esterification-I reactor, and controlled pressure is 0.12MPa, and temperature is 200.0 ℃, and the reaction time is 2.5 hours; The material after esterification-reaction of I reactor finishes is sent in esterification-II reactor again, and added stabilizing agent, the control temperature is 210 ℃, and the reaction time is 0.5 hour, and the control esterification yield is 97.0% ~ 98.5%; Again with above-mentioned make carboxylate adopt pump to be transported to polycondensation workshop section to carry out polycondensation reaction, reaction temperature is 225 ~ 240 ℃, vacuum is 10 ~ 0.1KPa, the reaction time is less than 200min, makes number-average molecular weight greater than 50,000 aliphatic copolyester melt.
3. the preparation method of a kind of fully biodegradable aliphatic copolyester staple fibre according to claim 2 is characterized in that the mol ratio of succinic acid and ethylene glycol is 1:1.05～1.25 in the described step 1); The molar percentage of described pentaerythrite and succinic acid is 0.1～0.3%; It is 5% solution that described pentaerythrite is mixed with molar percentage that pentaerythrite accounts for ethylene glycol; Described antimony-based catalyst is 500PPM with the percentage by weight that accounts for succinic acid; The percentage by weight of described stabilizing agent and succinic acid is 200PPM.
4. according to the preparation method of claim 2 or 3 described a kind of fully biodegradable aliphatic copolyester staple fibres, it is characterized in that antimony-based catalyst in the described step 1) adopts a kind of in antimony glycol, antimonous oxide or the antimony acetate; Described stabilizing agent adopts a kind of in triphenyl phosphate, phosphorous acid, the trimethyl phosphate.
5. the preparation method of a kind of fully biodegradable aliphatic copolyester staple fibre according to claim 4 is characterized in that described antimony-based catalyst is antimony glycol; Described stabilizing agent is triphenyl phosphate.
6. the preparation method of a kind of fully biodegradable aliphatic copolyester staple fibre according to claim 1 is characterized in that described step 2) in the temperature of melt Conveying pipeline be 200 ~ 210 ℃; Spinning body temperature is 220 ~ 240 ℃; The spinnerets hole count is 2960; Ring blowing blast is 300 ~ 350Pa; Spinning speed is 800 ~ 1200 m/min; Drafting multiple is 3.0 ~ 4.0; The drawing and heat-setting temperature is 60 ~ 80 ℃.
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