CN115821426B - Crystalline bio-based low-melting-point polyester composite fiber with antibacterial function and preparation method thereof - Google Patents
Crystalline bio-based low-melting-point polyester composite fiber with antibacterial function and preparation method thereof Download PDFInfo
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- 229920000728 polyester Polymers 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 239000000835 fiber Substances 0.000 title claims abstract description 66
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 114
- 238000002844 melting Methods 0.000 claims abstract description 78
- 238000009987 spinning Methods 0.000 claims abstract description 40
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims abstract description 37
- 229920000903 polyhydroxyalkanoate Polymers 0.000 claims abstract description 37
- 230000032050 esterification Effects 0.000 claims abstract description 35
- 239000012792 core layer Substances 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 13
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 11
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 11
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 57
- 238000007664 blowing Methods 0.000 claims description 42
- 238000002788 crimping Methods 0.000 claims description 36
- 230000008018 melting Effects 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 24
- 239000002002 slurry Substances 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- 239000003381 stabilizer Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 229920000520 poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Polymers 0.000 claims description 9
- 229920001013 poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Polymers 0.000 claims description 9
- 241000222122 Candida albicans Species 0.000 claims description 8
- 241000588724 Escherichia coli Species 0.000 claims description 8
- 241000191967 Staphylococcus aureus Species 0.000 claims description 8
- 229940095731 candida albicans Drugs 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- FYSSBMZUBSBFJL-VIFPVBQESA-N (S)-3-hydroxydecanoic acid Chemical compound CCCCCCC[C@H](O)CC(O)=O FYSSBMZUBSBFJL-VIFPVBQESA-N 0.000 claims description 4
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 claims description 2
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920001020 poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Polymers 0.000 claims description 2
- 229920000071 poly(4-hydroxybutyrate) Polymers 0.000 claims description 2
- 229940094938 stannous 2-ethylhexanoate Drugs 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 239000000178 monomer Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 12
- 239000001361 adipic acid Substances 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 241001116389 Aloe Species 0.000 description 1
- 241000205585 Aquilegia canadensis Species 0.000 description 1
- 235000003261 Artemisia vulgaris Nutrition 0.000 description 1
- 240000006891 Artemisia vulgaris Species 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- 244000303040 Glycyrrhiza glabra Species 0.000 description 1
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 description 1
- 229920002752 Konjac Polymers 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 235000011399 aloe vera Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000000855 fermentation Methods 0.000 description 1
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- 229940046240 glucomannan Drugs 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- LPLVUJXQOOQHMX-QWBHMCJMSA-N glycyrrhizinic acid Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@H](O[C@@H]1O[C@@H]1C([C@H]2[C@]([C@@H]3[C@@]([C@@]4(CC[C@@]5(C)CC[C@@](C)(C[C@H]5C4=CC3=O)C(O)=O)C)(C)CC2)(C)CC1)(C)C)C(O)=O)[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O LPLVUJXQOOQHMX-QWBHMCJMSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
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Landscapes
- Polyesters Or Polycarbonates (AREA)
- Multicomponent Fibers (AREA)
Abstract
The invention discloses a crystalline bio-based low-melting point polyester composite fiber with an antibacterial function and a preparation method thereof, wherein the crystalline bio-based low-melting point polyester composite fiber with the antibacterial function is a sheath-core structure fiber, a sheath layer is low-melting point polyester containing bio-based polyhydroxyalkanoate oligomer chain segments, a core layer is polyethylene terephthalate, and the preparation method of the composite fiber comprises the following steps: firstly, using bio-based polyhydroxyalkanoate as a raw material, conducting alcoholysis to obtain a single-molecule monomer, then conducting esterification reaction on various dihydric alcohols and dibasic acids to obtain four esterification products, then conducting polycondensation on the obtained esterification products, and finally conducting melt composite spinning by using low-melting polyester and polyethylene terephthalate as raw materials of a skin layer and a core layer respectively to obtain the crystalline bio-based low-melting polyester composite fiber. The invention has the characteristics of high crystallinity, good antibacterial property and the like, and can be widely applied to the fields of high added value such as automotive interiors and the like.
Description
Technical Field
The invention belongs to the field of low-melting-point polyester composite fibers, relates to a low-melting-point polyester composite fiber and a preparation method thereof, and particularly relates to a crystalline bio-based low-melting-point polyester composite fiber with an antibacterial function and a preparation method thereof.
Background
With the rapid development of the nonwoven industry, special low-melting point polyester composite fibers for nonwoven are increasingly receiving attention from academia and industry. The low-melting-point polyester composite fiber generally exists in the form of a sheath-core structure, the sheath layer and the core layer are respectively low-melting-point polyester and conventional polyester, the sheath layer has a melting point lower than that of the core layer and good compatibility, the sheath layer is melted in the non-weaving processing process to play a role in adhesion, the core layer keeps the original structural form, and the low-melting-point polyester composite fiber has the characteristics of low hot-melt adhesion temperature, rapid adhesion and high adhesion strength, can replace a chemical adhesive, is environment-friendly and good in safety, and is mainly applied to the fields of silk-like cotton, non-collodion cotton, hard cotton, sound insulation boards, palm mattresses, automotive interiors, sports goods, medical sanitation and the like at present. The fiber is developed and researched in a large amount at home and abroad. However, there are few products for functional low-melting-point polyester composite fibers in the market, the demand of people for textiles with antibacterial functions is increasing, but up to now, only the excellent color environment-friendly resource science and technology Co discloses a preparation process (ZL 201910966661.2) of colored low-melting-point sheath-core antibacterial polyester staple fibers, konjak glucomannan, nano silver wires, bamboo charcoal powder and water are mixed, stirred vigorously, stood still, filtered, dried to constant weight to obtain an antibacterial agent, and then the low-melting-point polyester chips and the antibacterial agent are ground under high pressure to obtain skin raw materials, the antibacterial agent used by the method is mainly infusible nano silver wires and bamboo charcoal powder, and the problems that nano silver wires are difficult to uniformly disperse, a spinneret plate is easy to block during spinning and the like exist, and in addition, nano silver has certain toxicity; bighearted fiber technology Co.Ltd discloses a double-component melting point differential colored polyester fiber with a plant source antibacterial function and a preparation method (ZL 201710846179.6), plant source antibacterial agents (tea leaves, mugwort leaves, liquorice, honeysuckle, aloe and the like) and low-melting-point polyester chips are melted, blended and granulated to prepare antibacterial low-melting-point polyester chips, then the antibacterial low-melting-point polyester chips are subjected to composite spinning with common PET, and plant source antibacterial agents are added into spinning oil to prepare the low-melting-point polyester composite fiber with the antibacterial function. The method also has the problems of poor spinnability, unstable performance and the like because the dispersion uniformity of the plant source antibacterial agent is difficult to ensure.
In addition, the conventional low-melting point polyester composite fiber is low in crystallinity and unsuitable for use in the automotive interior field because the temperature in the automobile is relatively high when the automobile is directly exposed to direct irradiation of sunlight, and the conventional low-melting point polyester composite fiber is poor in heat resistance because of the low crystallinity, and therefore, the low-melting point polyester composite fiber for the automotive interior field is required to have not only an antibacterial function but also a certain crystallinity, and the heat content of fusion is not less than 12J/g, but to date, no related products have been found.
Disclosure of Invention
Aiming at the problems of the antibacterial low-melting-point polyester composite fiber for the automotive interior field, the invention develops the crystalline bio-based low-melting-point polyester composite fiber with an antibacterial function and provides a preparation method thereof.
The crystalline bio-based low-melting point polyester composite fiber with an antibacterial function is a sheath-core structure fiber, the sheath layer is low-melting point polyester containing bio-based polyhydroxyalkanoate oligomer chain segments, and the core layer is polyethylene terephthalate;
the low-melting-point polyester containing the biobased polyhydroxyalkanoate oligomer chain segment consists of repeated structural units I, II, III and IV;
（Ⅰ）
（Ⅱ）
Or (b)
（Ⅲ）
（Ⅳ）
P in the repeated structural unit II is an integer of 1-12; in the repeated structural unit III, q and R are integers of 1-12, x, y, m and n are integers of 0-100, x and y or m and n cannot be 0 at the same time, R is alkyl with 2-8 carbon atoms, and R' is alkyl with 1-8 carbon atoms; s is 1 or 2, R 'is methyl when s is 1, and R' is hydrogen when s is 2;
the molar ratio of the repeated structural units I, II, III and IV is 1:0.5-1.5:0.5-1.5:1.5-8.0;
The biobased polyhydroxyalkanoate oligomer chain segment is contained in a repeated structural unit III, and the biobased polyhydroxyalkanoate oligomer corresponding to the biobased polyhydroxyalkanoate oligomer chain segment is specifically poly (3-hydroxybutyrate) oligomer, poly (3-hydroxybutyrate-co-3-hydroxyvalerate) oligomer, poly (3-hydroxybutyrate-co-4-hydroxybutyrate) oligomer, poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) oligomer, poly (3-hydroxybutyrate-co-3-hydroxyoctanoate) oligomer, poly (3-hydroxybutyrate-co-3-hydroxydecanoate) oligomer, poly (3-hydroxybutyrate-co-3-hydroxyundecanoate) oligomer, poly (4-hydroxybutyrate) oligomer, poly (3-hydroxyvalerate) oligomer, poly (3-hydroxyhexanoate) oligomer, poly (3-hydroxybutyrate) oligomer, poly (3-hydroxydecanoate) oligomer or poly (3-hydroxydecanoate) oligomer;
The melting point of the low-melting-point polyester is 100-180 ℃, and the melting degree of the low-melting-point polyester is more than or equal to 75% when the temperature rising speed is 5 ℃/min and the melting point is within the range of 20 ℃ above the melting point; the viscosity of the low-melting-point polyester is 0.6-0.7 dL/g.
The breaking strength of the crystalline bio-based low-melting point polyester composite fiber with the antibacterial function is more than or equal to 2.5cN/dtex; the composite ratio of the sheath-core structure is 40-60: 60-40; the melting enthalpy of the crystalline bio-based low-melting point polyester composite fiber sheath low-melting point polyester with the antibacterial function is more than or equal to 15J/g; the antibacterial rate of the crystalline bio-based low-melting point polyester composite fiber with the antibacterial function on staphylococcus aureus, escherichia coli and candida albicans is more than 90 percent.
The preparation method of the crystalline bio-based low-melting-point polyester composite fiber with the antibacterial function comprises the following steps:
1) Esterification reaction
(1) Preparing oxalic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is normal pressure to 0.3MPa, the temperature is 100 ℃ to 180 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a first esterification product;
(2) Preparing aliphatic dibasic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurization reaction under nitrogen atmosphere, wherein the pressurization pressure is normal pressure to 0.3MPa, the temperature is 160 ℃ to 240 ℃, and the esterification reaction is stopped when the distillation amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a second esterification product;
(3) The method comprises the steps of (1) performing alcoholysis on a biosynthesized high molecular weight polyhydroxyalkanoate under the protection of nitrogen at 110-160 ℃ by using dibutyl tin dilaurate as a catalyst and diethylene glycol dimethyl ether as a solvent, wherein the ratio of the volume L of propylene glycol to the weight kg of polyhydroxyalkanoate is 1: 1-5: 1, the reaction time is 2-20 hours; preparing aliphatic dibasic acid and polyhydroxyalkanoate macromer with two ends blocked by hydroxyl groups into slurry, performing esterification reaction, pressurizing under nitrogen atmosphere, wherein the pressurizing pressure is normal pressure to 0.3MPa, the temperature is 160 ℃ to 240 ℃, and the esterification reaction is stopped when the distillation amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a third esterification product, namely polyhydroxyalkanoate oligomer;
(4) Preparing terephthalic acid and ethylene glycol into slurry, performing esterification reaction, and performing pressurization reaction under nitrogen atmosphere, wherein the pressurization pressure is normal pressure to 0.3MPa, the temperature is 190 ℃ to 260 ℃, and the esterification reaction is stopped when the distillation amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a fourth esterification product;
2) Polymerization
Taking four synthesized esterification products as raw materials, and starting polycondensation reaction at a low vacuum stage under the condition of negative pressure under the action of a catalyst and a stabilizer; the pressure is smoothly pumped from normal pressure to absolute pressure below 500Pa, the temperature is controlled at 260-270 ℃, and the reaction time is 30-50 min; then continuously vacuumizing, and performing polycondensation reaction at a high vacuum stage to ensure that the reaction pressure is reduced to be less than 100Pa, the reaction temperature is controlled to be 275-280 ℃ and the reaction time is 50-90 min, so as to obtain low-melting-point polyester containing bio-based polyhydroxyalkanoate oligomer chain segments;
3) Spinning process
The pre-spinning adopts a sheath-core composite spinning process, wherein the bio-based polyhydroxyalkanoate oligomer chain segment is taken as a sheath layer, polyethylene terephthalate is taken as a core layer, the spinning temperatures of the sheath layer and the core layer are respectively 260-280 ℃ and 280-290 ℃, and the spinning speed is 500-1100 m/min; the air blowing is two cooling ring air blowing; the first circular blowing temperature is 50-80 ℃, and the circular blowing wind speed is 1.0-3.0 m/s; the second circular blowing air temperature is 14-20 ℃, and the circular blowing air speed is 2.0-4.0 m/s; the interval between two cooling ring air blowing is 30-50 cm;
The post spinning adopts a drafting-water washing process, and the crystalline bio-based low-melting point polyester composite fiber with an antibacterial function is obtained through crimping, cutting and drying; the drafting adopts oil bath drafting, 5-10wt% of sodium sulfite is added into the oil bath, the temperature of the oil bath is 65-75 ℃, the drafting multiple is 2.5-2.7 times, the crimping temperature is 50-60 ℃, the crimping main pressure is 0.4-0.6 MPa, the crimping back pressure is 0.2-0.4 MPa, the crimping number is 8-10/25 mm, and the crimping degree is 11-13%.
The catalyst is antimony trioxide, ethylene glycol antimony, antimony acetate, isopropyl titanate, tetrabutyl titanate, dibutyl tin oxide or stannous 2-ethyl hexanoate, and the addition amount of the catalyst is 0.01-0.05% of the total weight of the dibasic acid; the stabilizer is triphenyl phosphate and trimethyl phosphate, and the addition amount of the stabilizer is 0.01-0.05% of the total weight of the dibasic acid.
The invention has the beneficial effects that:
(1) The invention introduces renewable and biodegradable polyhydroxyalkanoate macromer with antibacterial function into the molecular chain of low-melting polyester, solving the problems of uneven mixing, poor spinnability, unstable performance and the like possibly existing in the prior art that nano silver wires or small molecular natural extracts are introduced into low-melting polyester chips; in addition, the polyhydroxyalkanoate is directly synthesized by taking corn or sugarcane containing polysaccharide and the like as raw materials through microbial fermentation, the resource is renewable and biodegradable, and the polyhydroxyalkanoate with low molecular weight has the characteristics of antibiosis, low carbon dioxide emission in the life cycle, low consumption of non-renewable energy sources and the like, and accords with the national environment-friendly concept of energy conservation and emission reduction. The antibacterial rate of the crystalline bio-based low-melting point polyester composite fiber with the antibacterial function on staphylococcus aureus, escherichia coli and candida albicans is more than 90 percent;
(2) The preparation process of the crystalline bio-based low-melting point polyester composite fiber with the antibacterial function uses bio-based 1, 3-propanediol, and has the characteristic of renewable resources;
(3) The low-melting-point polyester in the crystalline bio-based low-melting-point polyester composite fiber with the antibacterial function has certain crystallinity, has the melting enthalpy of more than 15J/g, has certain heat resistance, and can be used in the high-attachment fields such as automotive interiors and the like.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention.
Example 1
1. Preparation of low melting polyesters containing biobased polyhydroxyalkanoate oligomer segments.
1) Esterification reaction
(1) Preparing oxalic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 160 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a first esterification product;
(2) Preparing succinic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 180 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a second reaction product;
(3) Performing alcoholysis on the biosynthesized high molecular weight poly (3-hydroxybutyrate-co-3-hydroxyvalerate) under the protection of nitrogen at 140 ℃ by taking dibutyl tin dilaurate as a catalyst and diethylene glycol dimethyl ether as a solvent to prepare a poly (3-hydroxybutyrate-co-3-hydroxyvalerate) macromer with two ends blocked by hydroxyl groups, wherein the weight ratio of the volume (L) of the propylene glycol to the weight (kg) of the poly (3-hydroxybutyrate-co-3-hydroxyvalerate) is 2:1, the reaction time is 10 hours; preparing succinic acid and poly (3-hydroxybutyrate-co-3-hydroxyvalerate) macromer with two ends blocked by hydroxyl into slurry, performing esterification reaction, pressurizing under nitrogen atmosphere, wherein the pressurizing pressure is 0.3MPa, the temperature is 160 ℃, and the esterification reaction is stopped when the distillation amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a third esterification product, namely poly (3-hydroxybutyrate-co-3-hydroxyvalerate) oligomer;
(4) Preparing terephthalic acid and ethylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 240 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a fourth esterification product;
2) Polymerization
Taking four synthesized esterification products as raw materials, wherein the mole ratio of the first, second, third and fourth esterification products is 1:0.5:0.5:8, and starting polycondensation reaction in a low vacuum stage under the action of a catalyst and a stabilizer under the condition of negative pressure; the pressure in the stage is smoothly pumped from normal pressure to absolute pressure below 500Pa, the temperature is controlled at 260 ℃, and the reaction time is 50min; then continuously vacuumizing, and performing polycondensation reaction at a high vacuum stage to ensure that the reaction pressure is reduced to be less than 100Pa, the reaction temperature is controlled at 275 ℃ and the reaction time is 90min, so as to prepare the low-melting-point polyester containing the biobased poly (3-hydroxybutyrate-co-3-hydroxyvalerate) oligomer chain segment; the catalyst and the stabilizer are respectively antimony trioxide and triphenyl phosphate, and the addition amounts of the catalyst and the stabilizer are respectively 0.01 percent of the total weight of the dibasic acid.
2. Composite spinning
The pre-spinning adopts a sheath-core composite spinning process, wherein the sheath layer is the oligomeric chain segment containing poly (3-hydroxybutyrate-co-3-hydroxyvalerate), the core layer is the polyethylene terephthalate, and the sheath-core composite ratio is 40:60, the spinning temperatures of the sheath layer and the core layer are 265 ℃ and 280 ℃ respectively, and the spinning speed is 600m/min; the air blowing is two cooling ring air blowing; the first circular blowing temperature is 50 ℃, and the circular blowing wind speed is 2.0m/s; the second circular blowing air temperature is 15 ℃, and the circular blowing air speed is 3.0m/s; the interval between two cooling ring air blowing is 40cm;
The post spinning adopts a drafting-water washing process, and the crystalline bio-based low-melting point polyester composite fiber with an antibacterial function is obtained through crimping, cutting and drying; the drafting adopts oil bath drafting, 5wt% of sodium sulfite is added into the oil bath, the temperature of the oil bath is 70 ℃, the drafting multiple is 2.5 times, the crimping temperature is 50 ℃, the crimping main pressure is 0.4MPa, the crimping back pressure is 0.2MPa, the crimping number is 8/25 mm, and the crimping degree is 11%.
The melting point of the low-melting-point polyester in the crystalline bio-based low-melting-point polyester composite fiber with the antibacterial function prepared by the steps is 176.5 ℃, the heating speed is 5 ℃/min, the melting degree of the low-melting-point polyester is 85% when the temperature is 20 ℃ above the melting point, the viscosity of the low-melting-point polyester is 0.65dL/g, and the melting enthalpy is 25J/g; the single filament number of the composite fiber is 1.8dtex, and the breaking strength is 3.48cN/dtex; the antibacterial rates of the composite fiber on staphylococcus aureus, escherichia coli and candida albicans are 95.2%, 93.3% and 91.7%, respectively.
Example 2
1. Preparation of low melting polyesters containing biobased polyhydroxyalkanoate oligomer segments.
1) Esterification reaction
(1) Preparing oxalic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 150 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a first esterification product;
(2) Preparing adipic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 180 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a second esterification product;
(3) The method comprises the steps of (1) carrying out alcoholysis on biosynthesized high molecular weight poly (3-hydroxybutyrate) under the protection of nitrogen at 140 ℃ by taking dibutyl tin dilaurate as a catalyst and diethylene glycol dimethyl ether as a solvent, wherein the ratio of the volume (L) of propylene glycol to the weight (kg) of poly (3-hydroxybutyrate) is 2:1, the reaction time is 15 hours; preparing adipic acid and poly (3-hydroxybutyrate) macromonomer with two ends blocked by hydroxyl groups into slurry, performing esterification reaction, pressurizing under nitrogen atmosphere, wherein the pressurizing pressure is 0.3MPa, the temperature is 160 ℃, and when the distillation amount of water in the esterification reaction is more than 90% of the theoretical value, the esterification reaction is stopped, so as to obtain a third esterification product, namely polyhydroxyalkanoate oligomer;
(4) Preparing terephthalic acid and ethylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 240 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a fourth esterification product;
2) Polymerization
Taking four synthesized esterification products as raw materials, wherein the mole ratio of the first, second, third and fourth esterification products is 1:2:2:5, under the action of a catalyst and a stabilizer, starting the polycondensation reaction in the low vacuum stage under the condition of negative pressure; the pressure in the stage is smoothly pumped from normal pressure to absolute pressure below 500Pa, the temperature is controlled at 260 ℃, and the reaction time is 50min; then continuously vacuumizing, and performing polycondensation reaction at a high vacuum stage to ensure that the reaction pressure is reduced to be less than 100Pa, the reaction temperature is controlled at 275 ℃, and the reaction time is 90min, so that the low-melting-point polyester containing the bio-based polyhydroxyalkanoate oligomer chain segments is prepared; the catalyst and the stabilizer are respectively antimony trioxide and triphenyl phosphate, and the addition amounts of the catalyst and the stabilizer are respectively 0.01 percent of the total weight of the dibasic acid.
2. Composite spinning
The pre-spinning adopts a sheath-core composite spinning process, wherein the bio-based polyhydroxyalkanoate oligomer chain segment is taken as a skin layer, polyethylene terephthalate is taken as a core layer, and the sheath-core composite ratio is 40:60, the spinning temperatures of the sheath layer and the core layer are 265 ℃ and 280 ℃ respectively, and the spinning speed is 600m/min; the air blowing is two cooling ring air blowing; the first circular blowing temperature is 50 ℃, and the circular blowing wind speed is 2.0m/s; the second circular blowing air temperature is 15 ℃, and the circular blowing air speed is 3.0m/s; the interval between two cooling ring air blowing is 40cm;
The post spinning adopts a drafting-water washing process, and the crystalline bio-based low-melting point polyester composite fiber with an antibacterial function is obtained through crimping, cutting and drying; the drafting adopts oil bath drafting, 5wt% of sodium sulfite is added into the oil bath, the temperature of the oil bath is 70 ℃, the drafting multiple is 2.5 times, the crimping temperature is 50 ℃, the crimping main pressure is 0.4MPa, the crimping back pressure is 0.2MPa, the crimping number is 8/25 mm, and the crimping degree is 11%.
The melting point of the low-melting-point polyester in the crystalline bio-based low-melting-point polyester composite fiber with the antibacterial function prepared by the steps is 149.6 ℃, the heating speed is 5 ℃/min, the melting degree of the low-melting-point polyester is 83% when the temperature is 20 ℃ above the melting point, the viscosity of the low-melting-point polyester is 0.65dL/g, and the melting enthalpy is 22J/g; the single filament number of the composite fiber is 1.8dtex, and the breaking strength is 3.23cN/dtex; the antibacterial rate of the composite fiber to staphylococcus aureus, escherichia coli and candida albicans is 99.3%, 98.9% and 97.8%, respectively.
Example 3
1. Preparation of low melting polyesters containing biobased polyhydroxyalkanoate oligomer segments.
1) Esterification reaction
(1) Preparing oxalic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 170 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a first esterification product;
(2) Preparing adipic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 180 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a second esterification product;
(3) The method comprises the steps of (1) carrying out alcoholysis on biosynthesized high molecular weight poly (3-hydroxybutyrate-co-4-hydroxybutyrate) under the protection of nitrogen at 130 ℃ by taking dibutyl tin dilaurate as a catalyst and diethylene glycol dimethyl ether as a solvent, wherein the propylene glycol is taken as an alcoholysis agent, so as to prepare a poly (3-hydroxybutyrate-co-4-hydroxybutyrate) macromer with hydroxyl end caps at two ends, and the weight ratio of the volume (L) of the propylene glycol to the weight (kg) of poly (3-hydroxybutyrate-co-4-hydroxybutyrate) is 2:1, the reaction time is 10 hours; preparing adipic acid and poly (3-hydroxybutyrate-co-4-hydroxybutyrate) macromer with two ends blocked by hydroxyl groups into slurry, performing esterification reaction, pressurizing under nitrogen atmosphere, wherein the pressurizing pressure is 0.3MPa, the temperature is 160 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to prepare a third reaction product, namely poly (3-hydroxybutyrate-co-4-hydroxybutyrate) oligomer;
(4) Preparing terephthalic acid and ethylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 250 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a fourth esterification product;
2) Polymerization
Taking four synthesized esterification products as raw materials, wherein the mole ratio of the first, second, third and fourth esterification products is 1:2:2:5, under the action of a catalyst and a stabilizer, starting the polycondensation reaction in the low vacuum stage under the condition of negative pressure; the pressure in the stage is smoothly pumped from normal pressure to absolute pressure below 500Pa, the temperature is controlled at 260 ℃, and the reaction time is 50min; then continuously vacuumizing, and performing polycondensation reaction at a high vacuum stage to ensure that the reaction pressure is reduced to be less than 100Pa, the reaction temperature is controlled at 275 ℃ and the reaction time is 90min, so as to prepare the low-melting-point polyester containing the biobased poly (3-hydroxybutyrate-co-4-hydroxybutyrate) oligomer chain segment; the catalyst and the stabilizer are respectively antimony trioxide and triphenyl phosphate, and the addition amounts of the catalyst and the stabilizer are respectively 0.01 percent of the total weight of the dibasic acid.
2. Composite spinning
The pre-spinning adopts a sheath-core composite spinning process, wherein the sheath layer is the oligomeric chain segment containing poly (3-hydroxybutyrate-co-4-hydroxybutyrate), the core layer is the polyethylene terephthalate, and the sheath-core composite ratio is 50:50, the spinning temperatures of the sheath layer and the core layer are 265 ℃ and 280 ℃ respectively, and the spinning speed is 600m/min; the air blowing is two cooling ring air blowing; the first circular blowing temperature is 50 ℃, and the circular blowing wind speed is 2.0m/s; the second circular blowing air temperature is 15 ℃, and the circular blowing air speed is 3.0m/s; the interval between two cooling ring air blowing is 40cm;
The post spinning adopts a drafting-water washing process, and the crystalline bio-based low-melting point polyester composite fiber with an antibacterial function is obtained through crimping, cutting and drying; the drafting adopts oil bath drafting, 6wt% of sodium sulfite is added into the oil bath, the temperature of the oil bath is 70 ℃, the drafting multiple is 2.5 times, the crimping temperature is 50 ℃, the crimping main pressure is 0.4MPa, the crimping back pressure is 0.2MPa, the crimping number is 8/25 mm, and the crimping degree is 12%.
The melting point of the low-melting-point polyester in the crystalline bio-based low-melting-point polyester composite fiber with the antibacterial function prepared by the steps is 162.3 ℃, the temperature rising speed is 5 ℃/min, the melting degree of the low-melting-point polyester is 79% when the temperature is 20 ℃ above the melting point, the viscosity of the low-melting-point polyester is 0.63dL/g, and the melting enthalpy is 23J/g; the single filament number of the composite fiber is 1.8dtex, and the breaking strength is 3.08cN/dtex; the antibacterial rates of the composite fiber on staphylococcus aureus, escherichia coli and candida albicans are 98.2%, 97.3% and 96.5%, respectively.
Example 4
1. Preparation of low melting polyesters containing biobased polyhydroxyalkanoate oligomer segments.
1) Esterification reaction
(1) Preparing oxalic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 150 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a first esterification product;
(2) Preparing adipic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 180 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a second esterification product;
(3) The method comprises the steps of (1) carrying out alcoholysis on biosynthesized high molecular weight poly (3-hydroxybutyrate-co-3-hydroxycaproic acid ester) under the protection of nitrogen at 140 ℃ by taking dibutyl tin dilaurate as a catalyst and diethylene glycol dimethyl ether as a solvent, wherein the ratio of the volume (L) of propylene glycol to the weight (kg) of poly (3-hydroxybutyrate) is 2:1, the reaction time is 15 hours; preparing adipic acid and poly (3-hydroxybutyrate) macromonomer with two ends blocked by hydroxyl groups into slurry, performing esterification reaction, pressurizing under nitrogen atmosphere, wherein the pressurizing pressure is 0.3MPa, the temperature is 160 ℃, and when the distillation amount of water in the esterification reaction is more than 90% of the theoretical value, the esterification reaction is stopped, so as to obtain a third esterification product, namely polyhydroxyalkanoate oligomer;
(4) Preparing terephthalic acid and ethylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is 0.3MPa, the temperature is 240 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a fourth esterification product;
2) Polymerization
Taking four synthesized esterification products as raw materials, wherein the mole ratio of the first, second, third and fourth esterification products is 1:2:2:5, under the action of a catalyst and a stabilizer, starting the polycondensation reaction in the low vacuum stage under the condition of negative pressure; the pressure in the stage is smoothly pumped from normal pressure to absolute pressure below 500Pa, the temperature is controlled at 260 ℃, and the reaction time is 50min; then continuously vacuumizing, and performing polycondensation reaction at a high vacuum stage to ensure that the reaction pressure is reduced to be less than 100Pa, the reaction temperature is controlled at 275 ℃, and the reaction time is 90min, so that the low-melting-point polyester containing the bio-based polyhydroxyalkanoate oligomer chain segments is prepared; the catalyst and the stabilizer are respectively antimony trioxide and triphenyl phosphate, and the addition amounts of the catalyst and the stabilizer are respectively 0.01 percent of the total weight of the dibasic acid.
2. Composite spinning
The pre-spinning adopts a sheath-core composite spinning process, wherein the bio-based polyhydroxyalkanoate oligomer chain segment is taken as a skin layer, polyethylene terephthalate is taken as a core layer, and the sheath-core composite ratio is 40:60, the spinning temperatures of the sheath layer and the core layer are 265 ℃ and 280 ℃ respectively, and the spinning speed is 800m/min; the air blowing is two cooling ring air blowing; the first circular blowing temperature is 50 ℃, and the circular blowing wind speed is 2.5m/s; the second circular blowing air temperature is 15 ℃, and the circular blowing air speed is 3.0m/s; the interval between two cooling ring air blowing is 40cm;
The post spinning adopts a drafting-water washing process, and the crystalline bio-based low-melting point polyester composite fiber with an antibacterial function is obtained through crimping, cutting and drying; the drafting adopts oil bath drafting, 5wt% of sodium sulfite is added into the oil bath, the temperature of the oil bath is 70 ℃, the drafting multiple is 2.5 times, the crimping temperature is 50 ℃, the crimping main pressure is 0.4MPa, the crimping back pressure is 0.2MPa, the crimping number is 8/25 mm, and the crimping degree is 11%.
The melting point of the low-melting-point polyester in the crystalline bio-based low-melting-point polyester composite fiber with the antibacterial function prepared by the steps is 158.2 ℃, the temperature rising speed is 5 ℃/min, the melting degree of the low-melting-point polyester is 77% when the temperature is 20 ℃ above the melting point, the viscosity of the low-melting-point polyester is 0.65dL/g, and the melting enthalpy is 19J/g; the single filament number of the composite fiber is 1.8dtex, and the breaking strength is 3.02cN/dtex; the antibacterial rates of the composite fiber on staphylococcus aureus, escherichia coli and candida albicans are 98.6%, 97.2% and 96.5%, respectively.
Examples 5 to 10
According to the preparation method of example 2, various crystalline bio-based low-melting polyester composite fibers with antibacterial function are prepared by only changing the molar ratio of the first, second, third and fourth esterification products.
Comparative example 1
According to the preparation method of example 2, a crystalline low-melting polyester composite fiber was prepared without introducing a third reaction product.
Performance test:
The mechanical properties, antibacterial properties, linear density and melting point, melting degree, melting enthalpy, viscosity and the like of the low-melting polyester composite fibers of examples 5 to 10 and comparative example 1 were tested, and specific test results are shown in table 1 below:
table 1 shows the results of structural and performance tests of the respective low-melting polyester composite fibers
As can be seen from table 1 above:
(1) Example 2 compared to control 1, the low-melting polyester conjugate fibers prepared from the low-melting polyester containing poly (3-hydroxybutyrate) oligomer segments all had better mechanical properties, antibacterial properties and crystallization ability, and the antibacterial rate against staphylococcus aureus, escherichia coli and candida albicans was more than 95%, while the low-melting polyester conjugate fibers in the control did not contain poly (3-hydroxybutyrate) oligomer segments, so as not to have antibacterial function.
While the invention has been described with reference to the preferred embodiments, it is not limited thereto, and various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A crystalline bio-based low-melting point polyester composite fiber with an antibacterial function is characterized in that: the crystalline bio-based low-melting point polyester composite fiber with an antibacterial function is a sheath-core structure fiber, the sheath layer is low-melting point polyester containing bio-based polyhydroxyalkanoate oligomer chain segments, and the core layer is polyethylene terephthalate;
the low-melting-point polyester containing the biobased polyhydroxyalkanoate oligomer chain segment consists of repeated structural units I, II, III and IV;
（Ⅰ）
（Ⅱ）
Or (b)
（Ⅲ）
（Ⅳ）
P in the repeated structural unit II is an integer of 1-12; in the repeated structural unit III, q and R are integers of 1-12, x, y, m and n are integers of 0-100, x and y or m and n cannot be 0 at the same time, R is alkyl with 2-8 carbon atoms, and R' is alkyl with 1-8 carbon atoms; s is 1 or 2, R 'is methyl when s is 1, and R' is hydrogen when s is 2;
the molar ratio of the repeated structural units I, II, III and IV is 1:0.5-1.5:0.5-1.5:1.5-8.0;
The biobased polyhydroxyalkanoate oligomer chain segment is contained in a repeated structural unit III, and the biobased polyhydroxyalkanoate oligomer corresponding to the biobased polyhydroxyalkanoate oligomer chain segment is specifically poly (3-hydroxybutyrate) oligomer, poly (3-hydroxybutyrate-co-3-hydroxyvalerate) oligomer, poly (3-hydroxybutyrate-co-4-hydroxybutyrate) oligomer, poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) oligomer, poly (3-hydroxybutyrate-co-3-hydroxyoctanoate) oligomer, poly (3-hydroxybutyrate-co-3-hydroxydecanoate) oligomer, poly (3-hydroxybutyrate-co-3-hydroxyundecanoate) oligomer, poly (4-hydroxybutyrate) oligomer, poly (3-hydroxyvalerate) oligomer, poly (3-hydroxyhexanoate) oligomer, poly (3-hydroxybutyrate) oligomer, poly (3-hydroxydecanoate) oligomer or poly (3-hydroxydecanoate) oligomer;
The melting point of the low-melting-point polyester is 100-180 ℃, and the melting degree of the low-melting-point polyester is more than or equal to 75% when the temperature rising speed is 5 ℃/min and the melting point is within the range of 20 ℃ above the melting point; the viscosity of the low-melting-point polyester is 0.6-0.7 dL/g.
2. The crystalline bio-based low-melting point polyester composite fiber with an antibacterial function according to claim 1, wherein the breaking strength of the crystalline bio-based low-melting point polyester composite fiber with an antibacterial function is more than or equal to 2.5cN/dtex; the composite ratio of the sheath-core structure is 40-60: 60-40; the melting enthalpy of the crystalline bio-based low-melting point polyester composite fiber sheath low-melting point polyester with the antibacterial function is more than or equal to 15J/g; the antibacterial rate of the crystalline bio-based low-melting point polyester composite fiber with the antibacterial function on staphylococcus aureus, escherichia coli and candida albicans is more than 90 percent.
3. The method for preparing the crystalline bio-based low-melting point polyester composite fiber with an antibacterial function according to claim 1, which is characterized by comprising the following steps:
1) Esterification reaction
(1) Preparing oxalic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurized reaction under nitrogen atmosphere, wherein the pressurized pressure is normal pressure to 0.3MPa, the temperature is 100 ℃ to 180 ℃, and the esterification reaction is stopped when the distilled amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a first esterification product;
(2) Preparing aliphatic dibasic acid and propylene glycol into slurry, performing esterification reaction, and performing pressurization reaction under nitrogen atmosphere, wherein the pressurization pressure is normal pressure to 0.3MPa, the temperature is 160 ℃ to 240 ℃, and the esterification reaction is stopped when the distillation amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a second esterification product;
(3) The method comprises the steps of (1) performing alcoholysis on a biosynthesized high molecular weight polyhydroxyalkanoate under the protection of nitrogen at 110-160 ℃ by using dibutyl tin dilaurate as a catalyst and diethylene glycol dimethyl ether as a solvent, wherein the ratio of the volume L of propylene glycol to the weight kg of polyhydroxyalkanoate is 1: 1-5: 1, the reaction time is 2-20 hours; preparing aliphatic dibasic acid and polyhydroxyalkanoate macromer with two ends blocked by hydroxyl groups into slurry, performing esterification reaction, pressurizing under nitrogen atmosphere, wherein the pressurizing pressure is normal pressure to 0.3MPa, the temperature is 160 ℃ to 240 ℃, and the esterification reaction is stopped when the distillation amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a third esterification product, namely polyhydroxyalkanoate oligomer;
(4) Preparing terephthalic acid and ethylene glycol into slurry, performing esterification reaction, and performing pressurization reaction under nitrogen atmosphere, wherein the pressurization pressure is normal pressure to 0.3MPa, the temperature is 190 ℃ to 260 ℃, and the esterification reaction is stopped when the distillation amount of water in the esterification reaction is more than 90% of the theoretical value, so as to obtain a fourth esterification product;
2) Polymerization
Taking four synthesized esterification products as raw materials, and starting polycondensation reaction at a low vacuum stage under the condition of negative pressure under the action of a catalyst and a stabilizer; the pressure is smoothly pumped from normal pressure to absolute pressure below 500Pa, the temperature is controlled at 260-270 ℃, and the reaction time is 30-50 min; then continuously vacuumizing, and performing polycondensation reaction at a high vacuum stage to ensure that the reaction pressure is reduced to be less than 100Pa, the reaction temperature is controlled to be 275-280 ℃ and the reaction time is 50-90 min, so as to obtain low-melting-point polyester containing bio-based polyhydroxyalkanoate oligomer chain segments;
3) Spinning process
The pre-spinning adopts a sheath-core composite spinning process, wherein the bio-based polyhydroxyalkanoate oligomer chain segment is taken as a sheath layer, polyethylene terephthalate is taken as a core layer, the spinning temperatures of the sheath layer and the core layer are respectively 260-280 ℃ and 280-290 ℃, and the spinning speed is 500-1100 m/min; the air blowing is two cooling ring air blowing; the first circular blowing temperature is 50-80 ℃, and the circular blowing wind speed is 1.0-3.0 m/s; the second circular blowing air temperature is 14-20 ℃, and the circular blowing air speed is 2.0-4.0 m/s; the interval between two cooling ring air blowing is 30-50 cm;
The post spinning adopts a drafting-water washing process, and the crystalline bio-based low-melting point polyester composite fiber with an antibacterial function is obtained through crimping, cutting and drying; the drafting adopts oil bath drafting, 5-10wt% of sodium sulfite is added into the oil bath, the temperature of the oil bath is 65-75 ℃, the drafting multiple is 2.5-2.7 times, the crimping temperature is 50-60 ℃, the crimping main pressure is 0.4-0.6 MPa, the crimping back pressure is 0.2-0.4 MPa, the crimping number is 8-10/25 mm, and the crimping degree is 11-13%.
4. The method for preparing the crystalline bio-based low-melting point polyester composite fiber with an antibacterial function according to claim 3, wherein the catalyst is antimony trioxide, ethylene glycol antimony, antimony acetate, isopropyl titanate, tetrabutyl titanate, dibutyl tin oxide or stannous 2-ethylhexanoate, and the addition amount of the catalyst is 0.01-0.05% of the total weight of the dibasic acid; the stabilizer is triphenyl phosphate and trimethyl phosphate, and the addition amount of the stabilizer is 0.01-0.05% of the total weight of the dibasic acid.
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| CN108285531A (en) * | 2018-02-02 | 2018-07-17 | 东华大学 | A kind of preparation method of antibacterial polyester |
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| KR20200113473A (en) * | 2019-03-25 | 2020-10-07 | 주식회사 휴비스 | Thermally Fusible Composite Binder Fiber Having Biodegradation |
| WO2022152867A1 (en) * | 2021-01-15 | 2022-07-21 | Indorama Ventures Public Company Ltd | Biologically degradable multi-component polymer fibres |
| CN115094541A (en) * | 2022-07-27 | 2022-09-23 | 东华大学 | Low-cohesiveness biodegradable sheath-core composite copolyester fiber and preparation method thereof |
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| JP2008195815A (en) * | 2007-02-13 | 2008-08-28 | Toyobo Co Ltd | Fiber-reinforced polyhydroxybutyrate resin composition |
| CN106521701A (en) * | 2016-09-22 | 2017-03-22 | 江南大学 | Skin-core structure poly(3-hydroxybutyrate-co-3-hydroxyvalerate)fiber, nonwoven material and preparation methods of skin-core structure poly(3-hydroxybutyrate-co-3-hydroxyvalerate)fibers and nonwoven material |
| CN108285531A (en) * | 2018-02-02 | 2018-07-17 | 东华大学 | A kind of preparation method of antibacterial polyester |
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| KR20200113473A (en) * | 2019-03-25 | 2020-10-07 | 주식회사 휴비스 | Thermally Fusible Composite Binder Fiber Having Biodegradation |
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| CN115821426A (en) | 2023-03-21 |
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