CN103668538B - A kind of ultraviolet-resisting biomass polyester fiber and preparation method thereof - Google Patents
A kind of ultraviolet-resisting biomass polyester fiber and preparation method thereof Download PDFInfo
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- CN103668538B CN103668538B CN201210339227.XA CN201210339227A CN103668538B CN 103668538 B CN103668538 B CN 103668538B CN 201210339227 A CN201210339227 A CN 201210339227A CN 103668538 B CN103668538 B CN 103668538B
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- 229920000728 polyester Polymers 0.000 title claims abstract description 83
- 239000002028 Biomass Substances 0.000 title claims abstract description 67
- 239000000835 fiber Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 11
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002074 melt spinning Methods 0.000 claims abstract description 8
- 238000009987 spinning Methods 0.000 claims description 21
- 238000005886 esterification reaction Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 230000032050 esterification Effects 0.000 claims description 16
- 238000006068 polycondensation reaction Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- -1 alkyl phosphoric acid diester Chemical class 0.000 claims description 9
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052787 antimony Inorganic materials 0.000 claims description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 238000005453 pelletization Methods 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 6
- 150000003077 polyols Chemical class 0.000 claims description 6
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012760 heat stabilizer Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- GPOGLVDBOFRHDV-UHFFFAOYSA-N (2-nonylphenyl) dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(O)O GPOGLVDBOFRHDV-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
- 239000003208 petroleum Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229920004934 Dacron® Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Abstract
The invention discloses a kind of ultraviolet-resisting biomass polyester fiber and preparation method thereof.Described ultraviolet-resisting biomass polyester fiber is characterized in that, this ultraviolet-resisting biomass polyester fibrous raw material comprises the biomass polyester section of ultraviolet-resisting master batch 1-5% by percentage to the quality and surplus.Preparation method is: ultraviolet-resisting master batch and biomass polyester section are carried out melt spinning, obtains ultraviolet-resisting biomass polyester fiber.Bio-based polyester raw material bio-based ethylene glycol in the present invention and bio-based 1,3-PD are obtained by biofermentation, purification, instead of traditional petroleum base ethylene glycol, are conducive to environmental protection and sustainable development; Nano titanium nitride, particle diameter is little, and specific area is large, has uvioresistant effect.
Description
Technical field
The present invention relates to a kind of ultraviolet-resisting biomass polyester fiber and preparation method thereof, belong to functional fibre technical field.
Background technology
Along with the development of global economy, the demand of oil is growing, and petroleum resources successively decrease day by day, and contradiction between oil supply and demand increasingly sharpens, and the war of contention oil grows in intensity.The whole world all for utilize living resources inexhaustible on the earth makes great efforts research, exploration.Utilize reproducible biomass resource, development bio-based chemical industry, petroleum replacing chemical products, being the only way solving resource and energy crisis, is the important channel of sustainable development.Therefore, exploitation can reduce or the raw material of petroleum replacing are very important research directions.
Polyester dacron fiber itself has excellent performance and cheap price, it is the fiber species that in the large synthetic fiber of China three, most is representative, output is maximum, and its main raw material ethylene glycol originally derives from petroleum industry product, therefore, from the angle of industry value chain, new material and the new technology of energy petroleum replacing ethyl glycol must be found, make PET industry effectively can evade the price risk of petrochemical material continuous rise.
Polyethylene terephthalate (PET) has application widely in fields such as packaging material, film, engineering plastics, clothes, because the raw material producing PET all derives from the processed goods of oil, not only bring environmental problem, and along with the rise of oil price, the increasing pressure of China's chemical fibre industry is large.Therefore, develop a kind of living beings raw material of oil that replace and seem most important.Due to bio-based 2,5-furans diacid can be obtained by catalytic cracking reaction after the biomass ferments such as maize straw, and bio-based 2, the chemical constitution of 5-furans diacid and the structure of terephthalic acid (TPA) closely similar, therefore can terephthalic acid (TPA) be replaced to carry out polymerisation bio-based 2,5-furans diacid.In addition, E.I.Du Pont Company by fermenting to corn, through biological and chemical process, obtained 1, ammediol, have developed the polytrimethylene terephthalate (PTT) deriving from living beings containing the 36wt% that has an appointment, and successful application is to fields such as clothes, film, engineering plastics.And at present, the report about functional biological matter polyester fiber is less.
Ethylene glycol is the important source material of synthesis PET, and current industrial oxirane direct hydration method or the ethylene synthase method of adopting is produced more.Production cost is high, and consumes a large amount of raw material and the energy, generates a lot of accessory substances.China is large agricultural country, has abundant living resources.Macromolecular polysaccharide chemical degradation in the renewable resources such as the plant residues such as agricultural crop straw, husk, corncob or biodegradable method are converted into the derivatives such as fermentable sugars, fermentation organic acid and biological multielement alcohol.Completely with these tunnings for starting monomer, the living beings macromolecular material of synthesis, can save more petroleum resources to greatest extent, promotes the development of recycling economy.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of ultraviolet-resisting biomass polyester fiber and preparation method thereof is provided.
In order to achieve the above object, the invention provides a kind of ultraviolet-resisting biomass polyester fiber, it is characterized in that, this ultraviolet-resisting biomass polyester fibrous raw material comprises the biomass polyester section of ultraviolet-resisting master batch 1-5% by percentage to the quality and surplus.
Preferably, described ultraviolet-resisting master batch passes through nano titanium oxide 1-5% by percentage to the quality, and after the biomass polyester section mixing of Nano titanium nitride 1-5% and surplus, melt pelletization obtains.
Preferably, described biomass polyester section is obtained by following steps:
The first step: by bio-based ethylene glycol and bio-based 1,3-PD according to 1: 0.1-10 mass ratio be mixed with bio-based polyols blend;
Second step: bio-based polyols blend bio-based 2,5-furans diacid and the first step obtained is mixed with slurry according to the mass ratio of 1: 1.05-1.5;
3rd step: the slurry obtained by second step adds reaction kettle of the esterification, carries out esterification;
4th step: the mixture that the 3rd step obtains is carried out polycondensation reaction, obtained biomass polyester; After section, obtain biomass polyester section.
Further, the bio-based ethylene glycol in the described first step comprises 1,2-PD 0.4-5% by percentage to the quality, 1,2-butanediol 0.2-2%, pentanediol 0.1-2%, the ethylene glycol of sorbierite 0.1-1% and surplus.
Further, the pressure of the esterification in described 3rd step calculates according to following formula:
P＝C
1+C
2X
1；
Wherein: C
1=0.3;
X
1for the mass fraction of bio-based ethylene glycol in bio-based polyols blend;
C
2determined by following formula:
C＝K
0+K
1ω
1+K
2ω
2+K
3ω
3+K
4ω
4；
Wherein:
K
0＝0.02；K
1＝0.3；K
2＝0.21；K
3＝0.17；K
4＝0.10；
ω 1 is the mass fraction of 1,2-PD in bio-based ethylene glycol;
ω 2 is the mass fraction of 1,2-butanediol in bio-based ethylene glycol;
ω 3 is the mass fraction of pentanediol in bio-based ethylene glycol;
ω 4 is the mass fraction of sorbierite in bio-based ethylene glycol.
Further, also add at least one in Titanium series catalyst and antimony-based catalyst in the esterification reaction process in described 3rd step, addition is 120-550ppm, and the radix of addition is the quality of described bio-based 2,5-furans diacid.
Further, described Titanium series catalyst is titanium dioxide or butyl titanate.
Further, described antimony-based catalyst is antimonous oxide, antimony acetate or antimony glycol.
Further, also add in the esterification reaction process in described 3rd step respectively with heat stabilizer 0.001-0.02% and antioxidant 0.001-0.03% that described bio-based 2,5-furans diacid is radix.
Further, described antioxidant is any one or a few the mixture in antioxidant 1010, antioxidant 168 and antioxidant 616.
Further, described heat stabilizer is any one or a few the mixture in trimethyl phosphate, alkyl phosphoric acid diester and three (nonyl phenyl) phosphite ester.
Further, the temperature of the polycondensation reaction in described 4th step is 260-290 DEG C, and the reaction time is 2-6h.
Present invention also offers the preparation method of above-mentioned ultraviolet-resisting biomass polyester fiber, it is characterized in that, ultraviolet-resisting master batch and biomass polyester section are carried out melt spinning, obtains ultraviolet-resisting biomass polyester fiber.
Preferably, the technological parameter of described spinning is: spinning temperature is 270-300 DEG C, and spinning speed is 800-1500m/min, draft temperature is 60-80 DEG C, predraft multiplying power is 1.02-1.10, and one stretching ratio is 2.80-3.20, and two road stretching ratios are 1.05-1.15.
The invention has the advantages that:
(1) the bio-based polyester raw material bio-based ethylene glycol in the present invention and bio-based 1,3-PD are obtained by biofermentation, purification, instead of traditional petroleum base ethylene glycol, are conducive to environmental protection and sustainable development.
(2) the bio-based polyester raw material bio-based ethylene glycol in the present invention contains a certain amount of bio-based 1, ammediol, 1, containing 1 methylene in ammediol, 1, the existence of ammediol adds the compliance of polyester macromolecule segment, reduces the fusing point of polyester, improves the hydrophily of polyester.
(3) nano titanium oxide (HTTi) in the present invention is company's independent development, and be divided into anatase and rutile two kinds of crystal formations, outward appearance is white powder, and average grain diameter is less than 100nm.Its hydrophilic (rutile-type) product has the ability of opposing ultraviolet screener comprehensively, and particle diameter is less than 20nm, and specific area is greater than 50m2/g, fine and smooth, the refreshing sense of feel is strong, for in the Polymer Industries such as Functional Chemical Fibers, enhancing anti-aging can be played, improve the effect of the performance of product.
(4) Nano titanium nitride in the present invention, particle diameter is little, and specific area is large, has uvioresistant effect.
(5) the present invention utilizes existing equipment to carry out large-scale production, expands economic benefit and social benefit.
Detailed description of the invention
For making the present invention become apparent, hereby with preferred embodiment, be described in detail below.
Embodiment 1
The first step: prepare biomass polyester section
Add bio-based 2, the 5-furans diacid of 160kg and the bio-based ethylene glycol of 65kg in a kettle., the bio-based 1 of 8kg, ammediol, the wherein component of bio-based ethylene glycol: the mass fraction of ethylene glycol is 90%, and 1,2-PD mass fraction is 5%, 1, the mass fraction of 2-butanediol is 2%, and the mass fraction of pentanediol is 2%, and the mass fraction of sorbierite is 1%, the amount adding catalyst is titanium dioxide and each 275ppm of antimonous oxide, is respectively 45.65g.Add 46g trimethyl phosphate and 69g antioxidant 1010.At 225 DEG C after mixing, carry out esterification under the pressure of 0.343MPa, the reaction time is 4h.After esterification, product is delivered to polycondensation vessel, is warming up to 260 DEG C simultaneously and carries out polycondensation reaction, the polycondensation time is 6h.Finally obtain described full bio-based polyester, then obtain polyester slice.
Second step: prepare ultraviolet-resisting master batch
After nano titanium oxide 1% by percentage to the quality, Nano titanium nitride 1% and biomass polyester section 98% mixing, carry out melt pelletization, melt temperature is 260-300 DEG C, obtains ultraviolet-resisting master batch.
3rd step: prepare ultraviolet-resisting biomass polyester fiber
Ultraviolet-resisting master batch 1% by percentage to the quality and biomass polyester section 99% are carried out melt spinning, obtains ultraviolet-resisting biomass polyester fiber.Wherein, spinning technology parameter is: spinning temperature is 270-300 DEG C, and spinning speed is 800-1500m/min, and draft temperature is 60-80 DEG C, and predraft multiplying power is 1.02-1.10, and one stretching ratio is 2.80-3.20, and two road stretching ratios are 1.05-1.15.
Embodiment 2
The first step: prepare biomass polyester section
Add bio-based 2, the 5-furans diacid of 166kg and the bio-based ethylene glycol of 93kg in a kettle., the bio-based 1 of 11kg, ammediol, wherein the component of bio-based ethylene glycol is: the mass fraction of ethylene glycol is 99.2%, and 1,2-PD mass fraction is 0.4%, 1, the mass fraction of 2-butanediol is 0.2%, and the mass fraction of pentanediol is 0.1%, and the mass fraction of sorbierite is 0.1%, the catalyst added is butyl titanate 120ppm, is 19.92g.Add 52g trimethyl phosphate, at 280 DEG C after mixing, carry out esterification under 0.323MP, the reaction time is 0.5h.After esterification, product is delivered to polymeric kettle, is warming up to 290 DEG C simultaneously and carries out polycondensation reaction, the polycondensation time is 2h.Finally obtain described full bio-based polyester, then obtain polyester slice.
Second step: prepare ultraviolet-resisting master batch
By nano titanium oxide 2% by percentage to the quality, after Nano titanium nitride 2% and biomass polyester section 96% mix, carry out melt pelletization, melt temperature is 260-300 DEG C, obtains ultraviolet-resisting master batch.
3rd step: prepare ultraviolet-resisting biomass polyester fiber
Ultraviolet-resisting master batch 2% by percentage to the quality and biomass polyester section 98% are carried out melt spinning, obtains ultraviolet-resisting biomass polyester fiber.Wherein, spinning technique is: wherein spinning temperature is 270-300 DEG C, and spinning speed is 800-1500m/min, and draft temperature is 60-80 DEG C, and predraft multiplying power is 1.02-1.10, and one stretching ratio is 2.80-3.20, and two road stretching ratios are 1.05-1.15.
Embodiment 3
The first step: prepare biomass polyester section
Add bio-based 2, the 5-furans diacid of 166kg and the bio-based ethylene glycol of 80kg in a kettle., the bio-based 1 of 9kg, ammediol, wherein the component of bio-based ethylene glycol is: the mass fraction of ethylene glycol is 95%, 1, the mass fraction of 2-propylene glycol is 2%, the mass fraction of 1,2-butanediol is 1.5%, and the mass fraction of pentanediol is 1%, the mass fraction of sorbierite is 0.5%, the catalyst added is antimonous oxide, 550ppm, is 91.3g.Add the alkyl phosphoric acid diester of 49g and the antioxidant 168 of 49g.At 240 DEG C after mixing, carry out esterification under the pressure of 0.443MPa, the reaction time is 1.5h.After esterification, product is delivered to polymeric kettle, is warming up to 280 DEG C simultaneously and carries out polycondensation reaction, the polycondensation time is 5h.Finally obtain described full bio-based polyester, then obtain polyester slice.
Second step: prepare ultraviolet-resisting master batch
By nano titanium oxide 3% by percentage to the quality, after Nano titanium nitride 3% and biomass polyester section 94% mix, carry out melt pelletization, melt temperature is 260-300 DEG C, obtains ultraviolet-resisting master batch.
3rd step: prepare ultraviolet-resisting biomass polyester fiber
Ultraviolet-resisting master batch 3% by percentage to the quality and biomass polyester section 97% are carried out melt spinning, obtains ultraviolet-resisting biomass polyester fiber.Wherein, spinning technique is: wherein spinning temperature is 270-300 DEG C, and spinning speed is 800-1500m/min, and draft temperature is 60-80 DEG C, and predraft multiplying power is 1.02-1.10, and one stretching ratio is 2.80-3.20, and two road stretching ratios are 1.05-1.15.
Embodiment 4
The first step: prepare biomass polyester section
Add bio-based 2, the 5-furans diacid of 166kg and the bio-based ethylene glycol of 80kg in a kettle., the bio-based 1 of 9kg, ammediol, the wherein component of bio-based ethylene glycol: the mass fraction of ethylene glycol is 95%, and 1,2-PD mass fraction is 2.5%, 1, the mass fraction of 2-butanediol is 1.0%, and the mass fraction of pentanediol is 1.25%, and the mass fraction of sorbierite is 0.25%, the amount adding catalyst is butyl titanate 200ppm, 33.2g; Antimony glycol 100ppm, 26g.Add the alkyl phosphoric acid diester of 49g and the mixture (alkyl phosphoric acid diester and each 29.5g of trimethyl phosphate) of trimethyl phosphate, then add the antioxidant 168 of 49g and the mixture (antioxidant 168 and each 29.5g of antioxidant 616) of antioxidant 616.At 250 DEG C after mixing, carry out esterification under the pressure of 0.341MPa, the reaction time is 2h.After esterification, product is delivered to polymeric kettle, is warming up to 280 DEG C simultaneously and carries out polycondensation reaction, the polycondensation time is 4h.Finally obtain described full bio-based polyester, then obtain polyester slice.
Second step: prepare ultraviolet-resisting master batch
By nano titanium oxide 4% by percentage to the quality, after Nano titanium nitride 4% and biomass polyester section 92% mix, carry out melt pelletization, melt temperature is 260-300 DEG C, obtains ultraviolet-resisting master batch.
3rd step: prepare ultraviolet-resisting biomass polyester fiber
Ultraviolet-resisting master batch 4% by percentage to the quality and biomass polyester section 96% are carried out melt spinning, obtains ultraviolet-resisting biomass polyester fiber.Wherein, spinning technique is: wherein spinning temperature is 270-300 DEG C, and spinning speed is 800-1500m/min, and draft temperature is 60-80 DEG C, and predraft multiplying power is 1.02-1.10, and one stretching ratio is 2.80-3.20, and two road stretching ratios are 1.05-1.15.
Embodiment 5
The first step: prepare biomass polyester section
Add bio-based 2, the 5-furans diacid of 166kg and the bio-based ethylene glycol of 88kg in a kettle., the bio-based 1 of 10kg, ammediol, wherein the component of living beings ethylene glycol is: the mass fraction of ethylene glycol is 96%, and 1,2-PD mass fraction is 2%, 1, the mass fraction of 2-butanediol is 1.0%, and the mass fraction of pentanediol is 0.5%, and the mass fraction of sorbierite is 0.5%, the amount adding catalyst is antimony glycol 300ppm, is 49.8g.Add the alkyl phosphoric acid diester of 51g and mixture (the alkyl phosphoric acid diester 20g of trimethyl phosphate, the each 31g of trimethyl phosphate), then add the antioxidant 168 of 46g and the mixture (antioxidant 168 is 20g and antioxidant 616 is 26g) of antioxidant 616.At 260 DEG C after mixing, carry out esterification under the pressure of 0.320MPa, the reaction time is 2.5h.After esterification, product is delivered to polymeric kettle, is warming up to 275 DEG C simultaneously and carries out polycondensation reaction, the polycondensation time is 4.5h.Finally obtain described full bio-based polyester, then obtain polyester slice.
Second step: prepare ultraviolet-resisting master batch
By nano titanium oxide 5% by percentage to the quality, after Nano titanium nitride 5% and biomass polyester section 90% mix, carry out melt pelletization, melt temperature is 260-300 DEG C, obtains ultraviolet-resisting master batch.
3rd step: prepare ultraviolet-resisting biomass polyester fiber
Ultraviolet-resisting master batch 5% by percentage to the quality and biomass polyester section 95% are carried out melt spinning, obtains ultraviolet-resisting biomass polyester fiber.Wherein, spinning technique is: wherein spinning temperature is 270-300 DEG C, and spinning speed is 800-1500m/min, and draft temperature is 60-80 DEG C, and predraft multiplying power is 1.02-1.10, and one stretching ratio is 2.80-3.20, and two road stretching ratios are 1.05-1.15.
Claims (12)
1. a ultraviolet-resisting biomass polyester fiber, is characterized in that, this ultraviolet-resisting biomass polyester fibrous raw material comprises the biomass polyester section of ultraviolet-resisting master batch 1-5% by percentage to the quality and surplus;
Described biomass polyester section is obtained by following steps:
The first step: bio-based ethylene glycol and bio-based 1,3-PD are mixed with bio-based polyols blend according to the mass ratio of 1:0.1-10;
Second step: the bio-based polyols blend that bio-based 2,5-furans diacid and the first step obtain is mixed with slurry according to the mass ratio of 1:1.05-1.5;
3rd step: the slurry obtained by second step adds reaction kettle of the esterification, carries out esterification;
4th step: the mixture that the 3rd step obtains is carried out polycondensation reaction, obtained biomass polyester; After section, obtain biomass polyester section;
The pressure of the esterification in described 3rd step calculates according to following formula:
P=C
1+C
2X
1；
Wherein: C
1=0.3;
X
1for the mass fraction of bio-based ethylene glycol in bio-based polyols blend;
C
2determined by following formula:
C=K
0+K
1ω
1+K
2ω
2+K
3ω
3+K
4ω
4；
Wherein:
K
0=0.02；K
1=0.3；K
2=0.21；K
3=0.17；K
4=0.10；
ω 1 is the mass fraction of 1,2-PD in bio-based ethylene glycol;
ω 2 is the mass fraction of 1,2-butanediol in bio-based ethylene glycol;
ω 3 is the mass fraction of pentanediol in bio-based ethylene glycol;
ω 4 is the mass fraction of sorbierite in bio-based ethylene glycol.
2. a kind of ultraviolet-resisting biomass polyester fiber according to claim 1, it is characterized in that, described ultraviolet-resisting master batch passes through nano titanium oxide 1-5% by percentage to the quality, and after the biomass polyester section mixing of Nano titanium nitride 1-5% and surplus, melt pelletization obtains.
3. a kind of ultraviolet-resisting biomass polyester fiber according to claim 1, it is characterized in that, bio-based ethylene glycol in the described first step comprises by percentage to the quality 1,2-propylene glycol 0.4-5%, 1,2-butanediol 0.2-2%, pentanediol 0.1-2%, the ethylene glycol of sorbierite 0.1-1% and surplus.
4. a kind of ultraviolet-resisting biomass polyester fiber according to claim 1, it is characterized in that, the at least one in Titanium series catalyst and antimony-based catalyst is also added in esterification reaction process in described 3rd step, addition is 120-550ppm, the radix of addition is the quality of described bio-based 2,5-furans diacid.
5. a kind of ultraviolet-resisting biomass polyester fiber according to claim 4, it is characterized in that, described Titanium series catalyst is titanium dioxide or butyl titanate.
6. a kind of ultraviolet-resisting biomass polyester fiber according to claim 4, it is characterized in that, described antimony-based catalyst is antimonous oxide, antimony acetate or antimony glycol.
7. a kind of ultraviolet-resisting biomass polyester fiber according to claim 1 or 4, it is characterized in that, also add in esterification reaction process in described 3rd step respectively with heat stabilizer 0.001-0.02% and antioxidant 0.001-0.03% that described bio-based 2,5-furans diacid is radix.
8. a kind of ultraviolet-resisting biomass polyester fiber according to claim 7, is characterized in that, described antioxidant is any one or a few the mixture in antioxidant 1010, antioxidant 168 and antioxidant 616.
9. a kind of ultraviolet-resisting biomass polyester fiber according to claim 7, is characterized in that, described heat stabilizer is any one or a few the mixture in trimethyl phosphate, alkyl phosphoric acid diester and three (nonyl phenyl) phosphite ester.
10. a kind of ultraviolet-resisting biomass polyester fiber according to claim 1, is characterized in that, the temperature of the polycondensation reaction in described 4th step is 260-290 DEG C, and the reaction time is 2-6h.
The preparation method of 11. a kind of ultraviolet-resisting biomass polyester fibers according to claim 1, is characterized in that, ultraviolet-resisting master batch and biomass polyester section is carried out melt spinning, obtains ultraviolet-resisting biomass polyester fiber.
The preparation method of 12. a kind of ultraviolet-resisting biomass polyester fibers according to claim 11, it is characterized in that, the technological parameter of described spinning is: spinning temperature is 270-300 DEG C, spinning speed is 800-1500m/min, draft temperature is 60-80 DEG C, predraft multiplying power is 1.02-1.10, and one stretching ratio is 2.80-3.20, and two road stretching ratios are 1.05-1.15.
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| CN108070075A (en) | 2016-11-09 | 2018-05-25 | 可口可乐公司 | Biology base MEG and polyester fiber composition and the method for manufacturing them |
| CN111118661A (en) * | 2019-12-18 | 2020-05-08 | 晋江市远祥服装织造有限公司 | Biomass ultraviolet-proof fabric and preparation method and product thereof |
| CN112745076B (en) * | 2021-01-06 | 2022-08-26 | 北京市高强混凝土有限责任公司 | Concrete doped with dolomite powder and preparation method thereof |
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