CN101525472A - Alkali soluble polyester and method for preparing same - Google Patents
Alkali soluble polyester and method for preparing same Download PDFInfo
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- CN101525472A CN101525472A CN200810018611A CN200810018611A CN101525472A CN 101525472 A CN101525472 A CN 101525472A CN 200810018611 A CN200810018611 A CN 200810018611A CN 200810018611 A CN200810018611 A CN 200810018611A CN 101525472 A CN101525472 A CN 101525472A
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Abstract
The invention relates to an alkali soluble polyester and a method for preparing the same. The an alkali soluble polyester is prepared by ester exchange reaction or esterification reaction and polycondensation reaction of diprotic acid and dibasic alcohol, wherein the carbon element which is ethylene glycol in the raw material is sourced from biological materials. Simultaneously, 1 to 8mol percent of isophthalic acid glycol ester-5-sodium sulfonate and 1 to 5 weight percent of aliphatic dibasic alcohol are added in the synthetic process, and a compound thermal stabilizer formed by antioxidant, cobalt acetate, phosphoric acid or phosphoric acid ester is also added. The carbon element component in the dibasic alcohol component of the raw materials is sourced from the biological materials, but not from petroleum materials, thereby greatly reducing the emission of CO2 generated by petroleum oil refining; and the prepared polyester has the advantages of complete alkali solubility, good crystallinity and desirable and spinning operability.
Description
Technical field:
The present invention relates to a kind of alkali soluble polyester and preparation method thereof.
Background technology:
In recent years, along with going from bad to worse of environment for human survival, people more and more pay close attention to development environment friendly material and use renewable starting material.Oil is most important industrial chemicals as Nonrenewable resources, but because the discharging of a large amount of CO2 in using engineering and in final the discarding, a large amount of dischargings of CO2 have caused a series of problems such as global warming, and directly threaten human existence.How substituting and reduce and use oil as starting material, is one of important research problem of facing of people.
Alkali soluble polyester is the raw material of special fibres such as conjugated fibre and hygroscopic fibre.Make sea-island fibre with the alkali soluble polyester chip conjugate spinning, can dissolve away alkali soluble polyester through the thermokalite water treatment and make ultra-fine fibre.Alkali soluble polyester is made tubular fibre with conventional section co-blended spinning, can be made into the little multiporous fiber of hollow through suitable alkaline purification, has good moisture absorbing and sweat releasing.Alkali soluble polyester also is applied to fields such as tamanori, coating, has a extensive future.
At present, domestic sea-island fibre is compound spins that starting material are the processed goods that derive from oil in the used alkali soluble polyester.How using non-petroleum exploitation polyester product also is an important research project.
People use reproducible Biological resources, various novel polyester have been developed, for example E.I.Du Pont Company is by fermenting to corn, through biology and chemical process, prepare 1,3-PDO, and developed and contain that the 36wt% that has an appointment derives from biomaterial but not Poly(Trimethylene Terephthalate) (PTT) polymkeric substance of oil material.Natureworks company is raw material equally with farm crop, through biology and chemical process, has produced pure biogenetic derivation and has been easy to biodegradable poly(lactic acid) (PLA) polymkeric substance.
At present industrial many employing acetylene is that raw material or propylene oxide are that basic material is produced.Production stage is loaded down with trivial details, the cost height, and consume the great deal of raw materials and the energy, generate a lot of by products.Dibasic alcohol is by biomaterial production among the present invention, is that carbon source in the biomaterial is transferred in the ethylene glycol.
Farm crop are a kind of renewable resourcess, can be converted into various starch, carbohydrate, Mierocrystalline cellulose, xylogen etc. and store in farm crop fruit and stalk thereof with airborne CO2 by photosynthesis.
In addition, in the prior art, the preparation alkali soluble polyester normally uses terephthalic acid, ethylene glycol as two major ingredient, with the two hydroxyl ethyl esters of m-phthalic acid-5-sulfonate or m-phthalic acid-5-sulfonate as the 3rd component, as the 4th component, adopt " direct esterification method " or " ester-interchange method " these two kinds of operational paths to make with polyoxyethylene glycol.The purpose that adds the two hydroxyl ethyl esters of m-phthalic acid-5-sulfonate or m-phthalic acid-5-sulfonate is in order to make product meet alkali-soluble requirement.Because the introducing of sulfonic acid group, make the change of sterically hindered and phenyl ring cloud density between macromole, promoted the macromole macromolecule alkali for hydrolysis.The introducing of ehter bond helps the carrying out of macromolecule alkali for hydrolysis, and the superpolymer crystal performance is improved.
Summary of the invention:
The invention provides a kind of biological ethylene glycol that utilizes and be alkali soluble polyester of raw material and preparation method thereof.
Technical solution of the present invention is:
A kind of alkali soluble polyester and preparation method thereof is characterized in that being made through over-churning or transesterification reaction, polycondensation by diprotic acid and glycol; Its preparation raw material ethylene glycol is for carbon wherein is the ethylene glycol that derives from biomaterial.In building-up process, add simultaneously the A component of 1～8 mole of %, the B component of 0～5 weight %; And contain one package stabilizer.Wherein: the A component is ethylene isophthalate-5-sodium sulfonate (SIPE), and the B component is an aliphatic dihydroxy alcohol.
Preparation method of the present invention: earlier pure terephthalic acid, ethylene glycol are added the making beating still, the mol ratio of ethylene glycol and terephthalic acid is controlled at 1.1～1.5, adds conventional catalyst, enters esterifying kettle continuously, carries out esterification at 240 ℃～260 ℃; Enter polymeric kettle after the esterification, add the A component, add the B component after the stirred for several minute, and add catalyzer and one package stabilizer, under the vacuum pump effect, keep vacuum tightness below 200Pa, to carry out polyreaction.
Ethylene glycol content is 95%～99.9% in the raw material ethylene glycol of the present invention.The limiting viscosity of this alkali soluble polyester is 0.60～0.90.
Biomaterial of the present invention is the stalk of corn, sugarcane, wheat or other farm crop.Wherein said corn, wheat are its seed and/or stalk.The carbon of ethylene glycol derives from biological raw material in the product.
Biomaterial of the present invention through biological and/chemical process obtains ethylene glycol.For example corn is through the bioprocess separating starch, obtain the sugar of 5 carbon and 6 carbon through processing, these sugars can be prepared multicomponent binary alcohol through the technology of hydrogenation catalyst, after the purifies and separates general procedure, just can obtain raw material ethylene glycol component of the present invention, this ethylene glycol carries out filtration treatment through 160 ℃ of-190 ℃ of heat treated with activated carbon, just obtain of the present invention in 190～350nm wavelength region transmitance be biological ethylene glycol more than 50%.
Among the present invention, polyethylene terephthalate is through being obtained by diacid and glycol reaction.Wherein diacid is the derivative of terephthalic acid and esterification thereof, can be terephthalic acid, dimethyl terephthalate (DMT), diethyl terephthalate etc.Diacid unit further among the present invention contains m-phthalic acid, m-phthalic acid-5-sulfonate, phthalic acid, the methyl terephthalic acid, the naphthalene diacid, the aryl dicarboxylic acid's class and the Succinic Acid of aromatic carboxylic acids such as biphenyl dicarboxylic acid and ester derivative thereof, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, aliphatic carboxylic acid and ester derivative and cyclohexane dicarboxylic acids such as dodecanedicarboxylic acid, the hexahydro-m-phthalic acid, alicyclic dicarboxylic acid and ester derivatives thereof such as hexahydro-phthalic acid.Be meant materials such as lower alkyl esters, acid anhydrides, acyl chlorides such as dimethyl ester in the described derivative.These dicarboxylic acid can two or more alone or in combination uses.
A component of the present invention is ethylene isophthalate-5-sodium sulfonate; The described aliphatic dihydroxy alcohol of B component can be pentanediol, 1,6-hexylene glycol, polyoxyethylene glycol etc.
One package stabilizer of the present invention is: antioxidant 1010, add-on are 0.01%～0.5% of weight polyester; Cobaltous diacetate, add-on are 0.01～0.05% of weight polyester; Phosphoric acid or its ester class, add-on is 0.01%～0.03% of a weight polyester.Described catalyzer is one or more in Sb, Ti, the Sn acetate, and its add-on is 20～500ppm of polyester gross weight.
The present invention also adds the anti-etherifying agent of one or more conducts in Li, Na, the K acetate in reaction process, its add-on is 0.01%～0.1% of a final polyester gross weight, and the joining day is before esterification begins.
Carbon composition in the glycol component in the product of the present invention derives from biomaterial but not petroleum, thereby significantly reduces owing to the smelting oil, and the amount of the CO2 that outwards discharges.
The adding of A component of the present invention has increased the unformed area in the supramolecular structure, and sulfonic existence has strengthened the caustic solubility energy of polyester.But the SIPE consumption increases, and polyester fondant is mobile poor, the spinning property variation.So the suitable addition of SIPE is 1～8 mole of %.
The adding of B component plays a part softener in reaction system, it can reduce the rigidity of high-polymer molecular and improve the crystal property of polyester, thereby melt-spinning is more prone to.In addition, the easy and carboxyl generation gel of the sulfonic group among the SIPE, and make spinning filter sieve pressure excessive, add aliphatic dihydroxy alcohol and can alleviate this situation.
The technical characterstic that the present invention gives prominence to is: with biological ethylene glycol replaced by petroleum process ethylene glycol, add aliphatic dihydroxy alcohol simultaneously, the rigidity that can reduce high-polymer molecular is improved the crystal property of polyester, and the polycondensation time shortens greatly, the tone of polymkeric substance also improves, and reduces fusing point simultaneously.Do not add this component, melt-spinning is difficulty relatively, the end breakage rate height, and lousiness is many, and draw ratio is not enough; Fibre-forming performance is good after adding this component, and spinning is evenly continuous.
The invention will be further described below by embodiment.
Embodiment:
Biogenetic derivation ethylene glycol: great achievement group in Changchun produces, and the carbon source is corn, purity: 97%.Filtration treatment is carried out with gac in above-mentioned ethylene glycol heating back, obtain transmitance at the 250nm wavelength and be 65%, the transmitance of 300nm wavelength is 90% ethylene glycol.
Terephthalic acid: sub-petrochemical iy produced, polymerization-grade are raised by China.
Oil source ethylene glycol: raise sub-petro-chemical corporation and produce, the carbon source is oil, purity: more than 99%.
Embodiment 1
Earlier pure terephthalic acid's 1000 weight parts, biological ethylene glycol 430 weight parts are added the making beating still, add anti-etherifying agent sodium-acetate 0.58 weight part, enter esterifying kettle continuously, carry out normal pressure esterification at 240 ℃～260 ℃; Stopping esterification to water outlet finishes.Polymeric kettle then adds EG solution 96.3 weight parts of ethylene isophthalate-5-sodium sulfonate, adds polyoxyethylene glycol 46.4 weight parts after the stirred for several minute, and adds catalyzer and contain Sb compound 0.35 weight part; And one package stabilizer: IR10100.23 weight part, Cobaltous diacetate 0.35 weight part, phosphoric acid 0.29 weight part; Under the vacuum pump effect, keep vacuum tightness below 200Pa, to carry out polyreaction, temperature is controlled at 270 ℃～280 ℃, and reaction finishes to spue, pelletizing.
Embodiment 2
Earlier pure terephthalic acid's 1000 weight parts, biological ethylene glycol 430 weight parts are added the making beating still, add anti-etherifying agent sodium-acetate 0.58 weight part, enter esterifying kettle continuously, carry out normal pressure esterification at 240 ℃～260 ℃; Stopping esterification to water outlet finishes.Polymeric kettle then, EG solution 192.5 weight parts that add ethylene isophthalate-5-sodium sulfonate, add polyoxyethylene glycol 46.4 weight parts after the stirred for several minute, and the adding catalyzer contains Sb compound 0.35 weight part, and one package stabilizer IR10100.23 weight part, Cobaltous diacetate 0.35 weight part, phosphoric acid 0.29 weight part, under the vacuum pump effect, keep vacuum tightness below 200Pa, to carry out polyreaction, temperature is controlled at 270 ℃～280 ℃, and reaction finishes to spue, pelletizing.
Embodiment 3
Earlier pure terephthalic acid's 1000 weight parts, biological ethylene glycol 430 weight parts are added the making beating still, add anti-etherifying agent sodium-acetate 0.58 weight part, enter esterifying kettle continuously, carry out normal pressure esterification at 240 ℃～260 ℃; Stopping esterification to water outlet finishes.Polymeric kettle then, ethylene glycol (EG) solution 288.8 weight parts that add ethylene isophthalate-5-sodium sulfonate, add polyoxyethylene glycol 23.2 weight parts after the stirred for several minute, and the adding catalyzer contains Sb compound 0.35 weight part, and one package stabilizer IR10100.23 weight part, Cobaltous diacetate 0.35 weight part, phosphoric acid 0.29 weight part, under the vacuum pump effect, keep vacuum tightness below 200Pa, to carry out polyreaction, temperature is controlled at 270 ℃～280 ℃, and reaction finishes to spue, pelletizing.
Embodiment 4
Earlier pure terephthalic acid's 1000 weight parts, biological ethylene glycol 430 weight parts are added the making beating still, add anti-etherifying agent sodium-acetate 0.58 weight part, enter esterifying kettle continuously, carry out normal pressure esterification at 240 ℃～260 ℃; Stopping esterification to water outlet finishes.Polymeric kettle then, EG solution 385 weight parts that add ethylene isophthalate-5-sodium sulfonate, add polyoxyethylene glycol 58 weight parts after the stirred for several minute, and the adding catalyzer contains Sb compound 0.35 weight part, and one package stabilizer IR10100.23 weight part, Cobaltous diacetate 0.35 weight part, phosphoric acid 0.29 weight part, under the vacuum pump effect, keep vacuum tightness below 200Pa, to carry out polyreaction, temperature is controlled at 270 ℃～280 ℃, and reaction finishes to spue, pelletizing.
Comparative example
Earlier pure terephthalic acid's 1000 weight parts, oil source ethylene glycol 430 weight parts are added the making beating still, add anti-etherifying agent sodium-acetate 0.58 weight part, enter esterifying kettle continuously, carry out normal pressure esterification at 240 ℃～260 ℃; Stopping esterification to water outlet finishes.Polymeric kettle then, EG solution 385 weight parts that add ethylene isophthalate-5-sodium sulfonate, add polyoxyethylene glycol 58 weight parts after the stirred for several minute, and the adding catalyzer contains Sb compound 0.35 weight part, and one package stabilizer IR10100.23 weight part, Cobaltous diacetate 0.35 weight part, phosphoric acid 0.29 weight part, under the vacuum pump effect, keep vacuum tightness below 200Pa, to carry out polyreaction, temperature is controlled at 270 ℃～280 ℃, and reaction finishes to spue, pelletizing.
Table 1 is the synopsis of the embodiment of the invention and comparative example
The performance test methods of embodiment and comparative example
Stripping property:
Get section (1.000 ± 0.05) weight part of every part of shape, size, during alkaline purification, earlier the NaOH treatment solution with the 15wt% for preparing places thermostat water bath balance 10min, when pending liquid temp reaches the equilibrium temperature of setting, again section is put into and handles for some time, again with the ion-exchange clarification of water, clean section, use 100 ℃ dry 2 hours of hot air dryer again, weigh section weight=(test tube+section) weight-test tube weight after the normal temperature cooling.With dry 5 hours of the following vacuum of 130 ℃ in the test tube that section is housed, the section of weighing in second day, the weight of cutting into slices equally=(test tube+section) weight-test tube weight is carried out the neutralizing treatment of alkaline purification waste liquid at last.
Method of calculation are as follows:
Not dry sliced dry weight (g)=(test tube+section) weight-test tube weight
Dry weight decrement (%)=[(not dry sliced weight-dry weight)/not dry sliced weight] * 100
The dry sliced weight of not dry sliced dry weight (g)=not * (100-dry weight decrement)/100
Slice surface amasss (mm
2)=2 * 3.14 * radius * height+2 * 3.14 * radius * radius
=bottom surface girth * height+2 * floorage
Stripping property (mg/mm
2Section weight/surface-area after not dry sliced dry weight of)=(-the deduct alkaline purification
During alkaline purification, the design alkali concn is 15wt%, and treatment temp is 60 ℃, and the treatment time is 120min.
Intrinsic viscosity
With 0.5 gram polyester/milliliter phenol and sym.-tetrachloroethane etc. in the solution of weight mixture, in 25 ℃ of its intrinsic viscosity of mensuration IV values down.
Carry out the thermal property test with differential scanning calorimeter (DSC)
Fusing point: (DSC) tests with differential scanning calorimeter.
Spinning operation: use this alkali to contain intermingle with the conjugate spinning that ester and conventional polyester are carried out sea-island fibre, from the degree that filament spinning component pressure rises, the fracture of wire number of times is estimated, make good use of, can, the difference expression.
Claims (8)
1, a kind of alkali soluble polyester is characterized in that: made through over-churning or transesterification reaction, polycondensation by diprotic acid and glycol; Its preparation raw material ethylene glycol is for carbon wherein is the ethylene glycol that derives from biomaterial; In building-up process, add simultaneously the A component of 1～8 molar weight %, the B component of 0～5 weight %, and add one package stabilizer; Wherein: the A component is ethylene isophthalate-5-sodium sulfonate, and the B component is an aliphatic dihydroxy alcohol.
2, alkali soluble polyester according to claim 1 is characterized in that: described biomaterial is the stalk of corn, sugarcane, wheat or other farm crop.
3, alkali soluble polyester according to claim 1 and 2 is characterized in that: ethylene glycol content is 95%～99.9% in the raw material ethylene glycol, and biological ethylene glycol transmitance in 190～350nm wavelength region is more than 50%.
4, alkali soluble polyester according to claim 1 and 2 is characterized in that: described aliphatic dihydroxy alcohol is a pentanediol, 1,6-hexylene glycol or polyoxyethylene glycol.
5, alkali soluble polyester according to claim 1 and 2 and preparation method thereof is characterized in that: described one package stabilizer is: antioxidant 1010, add-on are 0.01%～0.5% of weight polyester; Cobaltous diacetate, add-on are 0.01～0.05% of weight polyester; Phosphoric acid or its ester class, add-on is 0.01%～0.03% of a weight polyester.
6, alkali soluble polyester according to claim 1 and 2 is characterized in that: the intrinsic viscosity of described alkali soluble polyester is 0.60～0.90dl/g, and fusing point Tm is 210 ℃～250 ℃.
7, the preparation method of the described alkali soluble polyester of a kind of claim 1, it is characterized in that: earlier pure terephthalic acid, ethylene glycol are added the making beating still, the mol ratio of ethylene glycol and terephthalic acid is controlled at 1.1～1.5, add catalyzer, anti-etherifying agent, enter esterifying kettle continuously, carry out esterification at 240 ℃～260 ℃; Enter polymeric kettle after the esterification, add ethylene isophthalate-5-sodium sulfonate, stir the back add polyoxyethylene glycol and add catalyzer, one package stabilizer reacts, product.
8, alkali soluble polyester according to claim 7 gets the preparation method, it is characterized in that: anti-etherifying agent is one or more in Li, Na, the K acetate, and its add-on is 0.01%～0.1% of a final polyester gross weight.
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| CN2008100186113A CN101525472B (en) | 2008-03-04 | 2008-03-04 | Alkali soluble polyester and method for preparing same |
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| CN2008100186113A CN101525472B (en) | 2008-03-04 | 2008-03-04 | Alkali soluble polyester and method for preparing same |
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| CN101525472A true CN101525472A (en) | 2009-09-09 |
| CN101525472B CN101525472B (en) | 2012-04-11 |
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| CN2008100186113A Expired - Fee Related CN101525472B (en) | 2008-03-04 | 2008-03-04 | Alkali soluble polyester and method for preparing same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130996A (en) * | 2011-11-29 | 2013-06-05 | 东丽纤维研究所（中国）有限公司 | Polyester easy to dissolve in alkali and preparation method thereof |
| CN103382290A (en) * | 2013-06-26 | 2013-11-06 | 安徽祈艾特电子科技有限公司 | Flame-retardant automobile distributor cover |
| CN103993378A (en) * | 2014-05-30 | 2014-08-20 | 东华大学 | Method for preparing lignin-modified polyethylene glycol terephthalate (PET) fiber |
| CN104231249A (en) * | 2013-06-21 | 2014-12-24 | 东丽纤维研究所（中国）有限公司 | Modified polyester as well as preparation method and application thereof |
| CN105579527A (en) * | 2013-12-17 | 2016-05-11 | 尤尼吉可株式会社 | Polyester resin composition, and molding obtained using same |
| CN112708960A (en) * | 2020-12-24 | 2021-04-27 | 创姿服饰(上海)有限公司 | Polyester fiber fabric and application thereof in clothing |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1219116C (en) * | 2003-03-20 | 2005-09-14 | 济南正昊化纤新材料有限公司 | Soluble thermokalite polyester fibre preparation |
| CN1317315C (en) * | 2004-07-08 | 2007-05-23 | 厦门翔鹭化纤股份有限公司 | Modified poly ester and its preparing method |
-
2008
- 2008-03-04 CN CN2008100186113A patent/CN101525472B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130996A (en) * | 2011-11-29 | 2013-06-05 | 东丽纤维研究所（中国）有限公司 | Polyester easy to dissolve in alkali and preparation method thereof |
| CN104231249A (en) * | 2013-06-21 | 2014-12-24 | 东丽纤维研究所（中国）有限公司 | Modified polyester as well as preparation method and application thereof |
| CN104231249B (en) * | 2013-06-21 | 2018-05-18 | 东丽纤维研究所（中国）有限公司 | A kind of modified poly ester and its preparation method and application |
| CN103382290A (en) * | 2013-06-26 | 2013-11-06 | 安徽祈艾特电子科技有限公司 | Flame-retardant automobile distributor cover |
| CN105579527A (en) * | 2013-12-17 | 2016-05-11 | 尤尼吉可株式会社 | Polyester resin composition, and molding obtained using same |
| CN103993378A (en) * | 2014-05-30 | 2014-08-20 | 东华大学 | Method for preparing lignin-modified polyethylene glycol terephthalate (PET) fiber |
| CN103993378B (en) * | 2014-05-30 | 2017-01-04 | 东华大学 | A kind of preparation method of lignin modification pet fiber |
| CN112708960A (en) * | 2020-12-24 | 2021-04-27 | 创姿服饰(上海)有限公司 | Polyester fiber fabric and application thereof in clothing |
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| CN101525472B (en) | 2012-04-11 |
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Effective date of registration: 20160608 Address after: Japan Tokyo central Nihonbashi Muromachi 2-1-1 Patentee after: Toray Industries, Inc. Address before: 226009 Nantong Province Economic and Technological Development Zone, the New South Road, No. 58, No. Patentee before: Toray Fiber Research Institute (China) Co., Ltd. |
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