CN102558527A - Method for preparing water-soluble polyester based on aluminum compound as catalyst - Google Patents
Method for preparing water-soluble polyester based on aluminum compound as catalyst Download PDFInfo
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- CN102558527A CN102558527A CN2011104278347A CN201110427834A CN102558527A CN 102558527 A CN102558527 A CN 102558527A CN 2011104278347 A CN2011104278347 A CN 2011104278347A CN 201110427834 A CN201110427834 A CN 201110427834A CN 102558527 A CN102558527 A CN 102558527A
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Abstract
The invention relates to a method for preparing water-soluble polyester based on an aluminum compound as a catalyst. The method comprises the following steps of: firstly, carrying out esterification reaction on terephthalic acid and glycol in a certain molar ratio; and after the esterification reaction is finished, carrying out condensation reaction by adding an ion type structure unit such as sodium dimethyl isophthalate-5-sulfonate or sodium bis(hydroxyl ethyl) isophthalate-5-sulfonate as a third monomer and polyethylene glycol as a fourth monomer and then adding the aluminum compound as the catalyst so as to finally obtain the water-soluble polyester. In the preparation method provided by the invention, a heavy metal compound such as an antimony compound is not used as the catalyst, so as to reduce the pollution of water quality and be beneficial to environment conservation; and the price of the catalyst is low, and the prepared water-soluble polyester can be used for producing sea-island filaments and the like.
Description
Technical field
The invention belongs to the preparation field of water-soluble polyester, particularly a kind of is the method for Preparation of Catalyst water-soluble polyester with the aluminum compound.
Background technology
Water-soluble polyester (or claiming alkali soluble polyester) is a kind of modified poly ester, and it is in polyethyleneterephthalate (PET) molecular chain, to introduce the unitary a kind of ion type copolyester of ionic structure.Report from domestic and foreign literature; Nearly all two the hydroxyl ethyl ester-5-sodium sulfonate (SIPE) is the 3rd monomer to its preparation method with the product m-phthalic acid after DMI dimethyl isophthalate-5-sodium sulfonate (SIPM) or itself and terepthaloyl moietie (EG) esterification; And in order to improve the rheological of melt; Improve spinning property, interpolation can improve flexible and further the 4th monomer that improves polymers swell property of macromole, mainly selects polyoxyethylene glycol (PEG) or glycol ether (DEG) etc. for use.Owing to introduced ionic groups in the structure of water-soluble polyester; Water-soluble polyester has in hot water or weak caustic solution dissolved characteristic rapidly, good hygroscopic property and ionic conductance performance, so it has a wide range of applications in fields such as man-made fiber, coating, sticker, printing ink.For example, water-soluble polyester is the sea component as sea-island fibre in an important application in chemical fibre field.Water-soluble polyester serves as marine facies in the process of conjugate spinning; Surround numerous islands phase, play a part isolation, protection and boundling island mutually, make sea and island form orderly integral body; Thereby make fiber keep certain fiber number; Be convenient to spinning, wovenly normally carry out, finally marine facies are dissolved and are left when opening fibre, and the island becomes ultra-fine fibre mutually.
Water-soluble polyester has been widely used in producing sea-island fibre at present, but also there is heavy metal pollution problem in it in production and subsequent processes.See that from the present disclosed water-soluble polyester synthetic patent documentation that relates to the catalyzer that is adopted in process of production mostly is the antimony based compound.For example, all adopt antimony-based catalyst etc. among the embodiment of patent CN1587297 and CN1383437 etc.Antimony is heavy metal element, and antimony-based catalyst has bigger toxicity.In polymerization process; Antimony-based catalyst meeting partial reduction, the synthetic polyester is in spinning, because the accumulation of heavy metal can increase the pressure of filament spinning component; Residual Sb can carry PET secretly and distil together when fusion, contained Sb can separate out in follow-up dyeing course and cause environmental pollution.In subsequent processes; The waste water that produces when sea-island fibre is opened fibre; Compare with the waste water of conventional polyester fiber dyeing and finishing process discharging, peeling process waste water is a kind of organic waste water of high density, and its pollutent mainly is the product that the water-soluble polyester dissolution process produces; Comprising terephthalic acid, terepthaloyl moietie, also has stibium heavy metal compound etc. in addition.
The production technique of polyester determined catalyzer to participate in the reaction rear section can be trapped in the product, thereby is one of focus of polyester technical study to the research of non-heavy metal catalyzer always.The stibium heavy metal compound is necessary the catalyzer that does not contain heavy metal element of development of new to the pollution of environment in the water-soluble polyester product in order to reduce, and this also meets production of polyester to cleaning Development Trend.
Aluminum compound has bibliographical information as polyester polycondensation catalyst.Yet still there are problems such as active deficiency, the inclined to one side Huang of synthetic product appearance luster in the aluminum compound catalyzer that polycondensation is used as normal polyester, and this has limited its industrial applications.So the research emphasis to aluminum-based catalyst still is how to improve on its activity at present.For example; Patent CN1373780 provides a kind of new polyester catalyzer that contains aluminum compound and phosphorus compound; But phosphorus compound related in this patent has suitable toxicity mostly, and this has all brought bigger problem and inconvenience for production, transportation, storage, polyester.
The aluminum current compound still can not replace the polycondensation catalyst of antimony compounds as normal polyester.Yet; Think after our research; When the water-soluble polyester product is used as the marine facies of sea-island fibre; Finally dissolved from falling, so the requirement of indexs such as its appearance luster is not had the normal polyester strictness, whether to have eco-friendly characteristics will be a problem that more merits attention to employed catalyzer when preparing water-soluble polyester.Because the price of aluminum compound is low than antimony-based catalyst, and aluminium element do not belong to heavy metal, thus be necessary to inquire into the feasibility of aluminum compound as the water-soluble polyester polycondensation catalyst, with the minimizing environmental pollution.
Summary of the invention
It is the method for Preparation of Catalyst water-soluble polyester with the aluminum compound that technical problem to be solved by this invention provides a kind of; This method is used nontoxic or low toxicity, the lower-cost aluminum compound catalyzer as the preparation water-soluble polyester, generally uses the stibium heavy metal compound as problem of environmental pollution that catalyzer was produced in the present water-soluble poly ester production process to solve.
There is active not enough, the synthetic product appearance luster problem applied at polyester industrial of Huang and being difficult to partially in the present invention in order to solve when aluminum compound is used for the preparation of conventional polyester as catalyzer.We with water-soluble polyester as research object; Through preferred some aluminum compound and after adjusting corresponding polymerization technique; Find that some aluminum compound can be used for preparing water-soluble polyester; Prepared product performance viscosity can reach the requirement of water-soluble polyester chip spinning to indexs such as limiting viscosities, and this helps aluminum-based catalyst applying in polyester industrial.
Of the present invention a kind of be the method for Preparation of Catalyst water-soluble polyester with the aluminum compound, comprising:
Terephthalic acid and terepthaloyl moietie are carried out esterification by 1.1～1.8 molar ratio, obtain carboxylate; After treating that esterification is accomplished, add the two hydroxyl ethyl esters of dimethyl isophthalate-5-sodium sulfonate or m-phthalic acid-5-sodium sulfonate etc. as the 3rd monomer, polyoxyethylene glycol as the 4th monomer, and add aluminum compound and carry out polycondensation as catalyzer.
Described aluminum compound catalyzer is one or more the mixture in ALUMINUM CARBOXYLIC salt, aluminate, al oxide, inorganic aluminate, the aluminum alkoxide.
Described aluminum compound catalyzer is the compound that contains aluminate, and wherein the general formula of the aluminate ion of aluminate is AlO
2 -Or Al (OH)
4 -
Described aluminum compound catalyzer is sodium metaaluminate (or claiming sodium aluminate).Sodium aluminate can be by Al (OH)
3Get with the excess NaOH reaction.
The addition of described aluminum compound catalyzer and the mass percent of terephthalic acid be 0.01%～0.5% (be 100ppm～5000ppm) promptly with respect to the consumption of terephthalic acid, preferred 0.02%～0.3% (promptly the consumption with respect to terephthalic acid is 200ppm to 3000ppm).
The two hydroxyl ethyl esters of described dimethyl isophthalate-5-sodium sulfonate or the m-phthalic acid-addition of 5-sodium sulfonate and the mass percent of terephthalic acid are 1.0%～15.0%.
The addition of described polyoxyethylene glycol and the mass percent of terephthalic acid are 0.5%～15.0%, preferred 1.0%～12.0%.
The number-average molecular weight of said polyoxyethylene glycol is 600～8000, preferred 800～4000.
When the present invention is used to prepare water-soluble polyester as catalyzer with aluminum compound; Except first monomers terephthalic acid and the second monomer terepthaloyl moietie are undertaken the esterification by 1.1～1.8 mol ratio earlier, the 3rd monomer component that adds during to follow-up polycondensation is like the two hydroxyl ethyl esters of m-phthalic acid-5-sodium sulfonate (SIPE); The mass percent of its addition and terephthalic acid is 1.0%～15.0%; The 4th monomer component that adds is like polyoxyethylene glycol (number-average molecular weight 600～8000, preferred 800～4000); The mass percent of its addition and terephthalic acid is 0.5%～15.0%, preferred 1.0%～12.0%.The aluminum compound addition is 100ppm to 5000ppm (with respect to the consumption of terephthalic acid), the addition of preferred 200ppm to 3000ppm.
As the purpose of improving the water-soluble polyester product quality, can add typical additives in the preparation process of the water-soluble polyester that the present invention mentions, like anti-ether agent, stablizer etc.
Beneficial effect of the present invention:
(1) polycondensation catalyst that uses of the present invention has and does not contain heavy metal element, characteristics favourable to environment protection, is a kind of polycondensation catalyst of novel compliance with environmental protection requirements, and the catalyzer raw material is easy to get, and price is lower;
(2) water-soluble polyester of the present invention preparation has short, characteristics such as product performance viscosity is suitable with the antimony-based catalyst that uses at present of alkaline hydrolysis time, and this helps application and the popularization etc. of subsequent slice spinning.
Embodiment
Following examples are merely preferred embodiment of the present invention; But not optimum craft embodiment; Any simple modification that every foundation technical spirit of the present invention is done; As adding anti-ether agent or add oxidation inhibitor etc., all belong in the scope of technical scheme of the present invention for suppressing thermooxidative degradation for reducing glycol ether content.
Following embodiment explains embodiment of the present invention, and some parameters among the embodiment are measured by following method.
(1) intrinsic viscosity (IV): adopt Ubbelohde viscometer to measure, during measurement the 0.125g sample is dissolved in 25ml phenol/tetrachloroethane (1/1wt) mixed solvent, in 25 ℃ of measurements.
(2) fusing point
Measure with DSC DSC (Differential scanning calorimetry), take by weighing example weight 5～10mg, at nitrogen atmosphere, gas flow rate 40ml/min records under the condition of 10 ℃/min of temperature rise rate.
(3) colourity b, L value
Sample is placed in the cuvette, use color difference meter to measure.
(4) the alkali dissolution time
Sample boiled with 5% sodium hydroxide solution carry out alkali dissolution test, test its whole dissolved times.
Embodiment 1
Take by weighing 25 gram NaOH, using deionized water dissolving to be made into mass concentration is 35% alkaline solution, contains in heating container and heats, and when solution during near boiling, adds 37 gram Al (OH)
3, after stirring, being warming up to about 120 ℃, reaction 2-3h obtains sodium aluminate solution, continues heating, makes the self-evaporatint n. of solution atmospheric boiling.When evaporation concentration when solution temperature is 150 ℃ of left and right sides, thereby make its crystallisation by cooling, fragmentation obtain the product that staple is a sodium metaaluminate (catalyst A).
With 250 gram terephthalic acids, 121.5 gram terepthaloyl moietie join in the polymeric kettle, and add the sodium acetate, anhydrous of 0.0375g weight; Carry out esterification, esterification temperature is 230～255 ℃, discharges the water that reaction generates through rectifier unit; Esterification is reduced to normal pressure after finishing; Ethylene glycol solution 86.7 grams, the number-average molecular weight that add mass concentration and be the two hydroxyl ethyl esters of m-phthalic acid-5-sodium sulfonate (SIPE) of 20% are 4000 polyoxyethylene glycol 8.7 grams and 0.3 gram catalyst A (consumption with respect to terephthalic acid is 1200ppm), vacuumize to be decompressed to system pressure and to be lower than 130Pa, and temperature of reaction rises to about 280 ℃ gradually simultaneously; When system reaction stopped reaction after reach required viscosity; Afterwards reaction product is extruded with bar shaped from the polymeric kettle bottom continuously, cooling, pelletizing supply performance test.
Embodiment 2
With 250 gram terephthalic acids, 121.5 gram terepthaloyl moietie join in the polymeric kettle, and add the sodium acetate, anhydrous of 0.0375g weight; Carry out esterification, esterification temperature is 230～255 ℃, discharges the water that reaction generates through rectifier unit; Esterification is reduced to normal pressure after finishing; Ethylene glycol solution 115.5 grams, the number-average molecular weight that adds mass concentration and be the two hydroxyl ethyl esters of m-phthalic acid-5-sodium sulfonate (SIPE) of 20% is 4000 polyoxyethylene glycol 8.7 grams and the catalyst A (consumption with respect to terephthalic acid is 1500ppm) of 0.375 gram weight, vacuumizes to be decompressed to system pressure and to be lower than 130Pa, and temperature of reaction rises to about 280 ℃ gradually simultaneously; When system reaction stopped reaction after reach required viscosity; Afterwards reaction product is extruded with bar shaped from the polymeric kettle bottom continuously, cooling, pelletizing supply performance test.
Embodiment 3
With 250 gram terephthalic acids, 121.5 gram terepthaloyl moietie join in the polymeric kettle, and add the sodium acetate, anhydrous of 0.0375g weight; Carry out esterification, esterification temperature is 230～255 ℃, discharges the water that reaction generates through rectifier unit; Esterification is reduced to normal pressure after finishing; Ethylene glycol solution 100.1 grams, the number-average molecular weight that adds mass concentration and be the two hydroxyl ethyl esters of m-phthalic acid-5-sodium sulfonate (SIPE) of 20% is 4000 polyoxyethylene glycol 8.7 grams and the catalyst A (consumption with respect to terephthalic acid is 1400ppm) of 0.35 gram weight, vacuumizes to be decompressed to system pressure and to be lower than 130Pa, and temperature of reaction rises to about 280 ℃ gradually simultaneously; When system reaction stopped reaction after reach required viscosity; Afterwards reaction product is extruded with bar shaped from the polymeric kettle bottom continuously, cooling, pelletizing supply performance test.
Embodiment 4
With 250 gram terephthalic acids, 121.5 gram terepthaloyl moietie join in the polymeric kettle, and add the sodium acetate, anhydrous of 0.0375g weight; Carry out esterification, esterification temperature is 230～255 ℃, discharges the water that reaction generates through rectifier unit; Esterification is reduced to normal pressure after finishing; Ethylene glycol solution 100.1 grams, the number-average molecular weight that adds mass concentration and be the two hydroxyl ethyl esters of m-phthalic acid-5-sodium sulfonate (SIPE) of 20% is 4000 polyoxyethylene glycol 8.7 grams and the aluminium sesquioxide (catalyst B) of 0.35 gram weight (consumption with respect to terephthalic acid is 1400ppm), vacuumizes to be decompressed to system pressure and to be lower than 130Pa, and temperature of reaction rises to about 280 ℃ gradually simultaneously; When system reaction stopped reaction after reach required viscosity; Afterwards reaction product is extruded with bar shaped from the polymeric kettle bottom continuously, cooling, pelletizing supply performance test.
Comparative example 1
With 250 gram terephthalic acids, 121.5 gram terepthaloyl moietie join in the polymeric kettle, and add the sodium acetate, anhydrous of 0.0375g weight; Carry out esterification, esterification temperature is 230～255 ℃, discharges the water that reaction generates through rectifier unit; Esterification is reduced to normal pressure after finishing; Ethylene glycol solution 115.5 grams, the number-average molecular weight that adds mass concentration and be the two hydroxyl ethyl esters of m-phthalic acid-5-sodium sulfonate (SIPE) of 20% is 4000 polyoxyethylene glycol 8.7 grams and the Antimony Trioxide: 99.5Min catalyzer of 0.1 gram weight (consumption with respect to terephthalic acid is 400ppm), vacuumizes to be decompressed to system pressure and to be lower than 130Pa, and temperature of reaction rises to about 280 ℃ gradually simultaneously; When system reaction stopped reaction after reach required viscosity; Afterwards reaction product is extruded with bar shaped from the polymeric kettle bottom continuously, cooling, pelletizing supply performance test.
Test result is seen table 1.
Table 1
Claims (9)
1. one kind with the method for aluminum compound as the Preparation of Catalyst water-soluble polyester, comprising:
Terephthalic acid and terepthaloyl moietie are carried out esterification by 1.1～1.8 molar ratio, obtain carboxylate; After treating that esterification is accomplished; Add the two hydroxyl ethyl esters of dimethyl isophthalate-5-sodium sulfonate or m-phthalic acid-5-sodium sulfonate etc. as the 3rd monomer, polyoxyethylene glycol as the 4th monomer; And add aluminum compound and carry out polycondensation as catalyzer, promptly get water-soluble polyester.
2. according to claim 1 a kind of with the method for aluminum compound as the Preparation of Catalyst water-soluble polyester, it is characterized in that: described aluminum compound is one or more the mixture in ALUMINUM CARBOXYLIC salt, aluminate, al oxide, inorganic aluminate, the aluminum alkoxide.
3. according to claim 1 a kind of with the method for aluminum compound as the Preparation of Catalyst water-soluble polyester, it is characterized in that: described aluminum compound is the compound that contains aluminate, and the general formula of its aluminate ion is AlO
2 -Or Al (OH)
4 -
4. according to claim 1 a kind of with the method for aluminum compound as the Preparation of Catalyst water-soluble polyester, it is characterized in that: described aluminum compound is sodium metaaluminate or sodium aluminate.
5. according to claim 1 and 2 a kind of with the method for aluminum compound as the Preparation of Catalyst water-soluble polyester, it is characterized in that: the consumption of said aluminum compound and the mass percent of terephthalic acid are 0.01%～0.5%.
6. according to claim 1 and 2 a kind of with the method for aluminum compound as the Preparation of Catalyst water-soluble polyester, it is characterized in that: the two hydroxyl ethyl esters of described dimethyl isophthalate-5-sodium sulfonate or the m-phthalic acid-addition of 5-sodium sulfonate and the mass percent of terephthalic acid are 1.0%～15.0%.
7. according to claim 1 and 2 a kind of with the method for aluminum compound as the Preparation of Catalyst water-soluble polyester, it is characterized in that: the addition of described polyoxyethylene glycol and the mass percent of terephthalic acid are 0.5%～15.0%.
8. according to claim 1 and 2 a kind of with the method for aluminum compound as the Preparation of Catalyst water-soluble polyester, it is characterized in that: the number-average molecular weight of described polyoxyethylene glycol is 600～8000.
9. according to claim 1 and 2 a kind of with the method for aluminum compound as the Preparation of Catalyst water-soluble polyester, it is characterized in that: the mass percent that the consumption of described aluminum compound accounts for terephthalic acid is 0.02%～0.3%; The addition of described polyoxyethylene glycol and the mass percent of terephthalic acid are 1.0%～12.0%; The number-average molecular weight of said polyoxyethylene glycol is 800～4000.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086759A (en) * | 2013-04-01 | 2014-10-08 | 东丽纤维研究所（中国）有限公司 | Alkali-soluble copolyester and its production method and use |
| CN106674508A (en) * | 2016-12-13 | 2017-05-17 | 厦门翔鹭化纤股份有限公司 | Preparation method of pure water-soluble antimony-free modified polyester |
| CN107778978A (en) * | 2016-08-26 | 2018-03-09 | 中国石化仪征化纤有限责任公司 | Environment-friendly type tin printing ink copolyesters and preparation method thereof |
| CN112725932A (en) * | 2020-12-29 | 2021-04-30 | 浙江恒逸石化有限公司 | Preparation method of antimony-free polyester POY (polyester pre-oriented yarn) filament with high moisture absorption and sweat releasing performance |
| CN113372545A (en) * | 2021-06-29 | 2021-09-10 | 宜昌中盈科技发展有限公司 | Low-melting-point water-soluble polyester and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587297A (en) * | 2004-07-08 | 2005-03-02 | 厦门翔鹭化纤股份有限公司 | Modified poly ester and its preparing method |
| JP2006176628A (en) * | 2004-12-22 | 2006-07-06 | Teijin Fibers Ltd | Cation-dyeable polyester and high-tenacity cation-dyeable polyester fiber |
-
2011
- 2011-12-19 CN CN2011104278347A patent/CN102558527B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587297A (en) * | 2004-07-08 | 2005-03-02 | 厦门翔鹭化纤股份有限公司 | Modified poly ester and its preparing method |
| JP2006176628A (en) * | 2004-12-22 | 2006-07-06 | Teijin Fibers Ltd | Cation-dyeable polyester and high-tenacity cation-dyeable polyester fiber |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086759A (en) * | 2013-04-01 | 2014-10-08 | 东丽纤维研究所（中国）有限公司 | Alkali-soluble copolyester and its production method and use |
| CN107778978A (en) * | 2016-08-26 | 2018-03-09 | 中国石化仪征化纤有限责任公司 | Environment-friendly type tin printing ink copolyesters and preparation method thereof |
| CN106674508A (en) * | 2016-12-13 | 2017-05-17 | 厦门翔鹭化纤股份有限公司 | Preparation method of pure water-soluble antimony-free modified polyester |
| CN106674508B (en) * | 2016-12-13 | 2019-05-10 | 厦门翔鹭化纤股份有限公司 | A kind of preparation method of the molten no antimony modified poly ester of pure water |
| CN112725932A (en) * | 2020-12-29 | 2021-04-30 | 浙江恒逸石化有限公司 | Preparation method of antimony-free polyester POY (polyester pre-oriented yarn) filament with high moisture absorption and sweat releasing performance |
| CN113372545A (en) * | 2021-06-29 | 2021-09-10 | 宜昌中盈科技发展有限公司 | Low-melting-point water-soluble polyester and preparation method thereof |
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