CN103435786B - A kind of liquid polyesters Catalysts and its preparation method and application - Google Patents
A kind of liquid polyesters Catalysts and its preparation method and application Download PDFInfo
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- CN103435786B CN103435786B CN201310406280.1A CN201310406280A CN103435786B CN 103435786 B CN103435786 B CN 103435786B CN 201310406280 A CN201310406280 A CN 201310406280A CN 103435786 B CN103435786 B CN 103435786B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 28
- 229920000728 polyester Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 77
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 77
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 claims abstract description 13
- 150000001463 antimony compounds Chemical class 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 23
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 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 13
- 239000004310 lactic acid Substances 0.000 claims description 11
- 235000014655 lactic acid Nutrition 0.000 claims description 11
- 229940059574 pentaerithrityl Drugs 0.000 claims description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 11
- 229960004106 citric acid Drugs 0.000 claims description 10
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- 229940095064 tartrate Drugs 0.000 claims description 5
- 229960000448 lactic acid Drugs 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- 229920000139 polyethylene terephthalate Polymers 0.000 description 15
- 239000005020 polyethylene terephthalate Substances 0.000 description 15
- 238000001914 filtration Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- UUDLQDCYDSATCH-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;hydrate Chemical compound O.OC(=O)C(O)C(O)C(O)=O UUDLQDCYDSATCH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PFZWDJVEHNQTJI-UHFFFAOYSA-N antimony titanium Chemical compound [Ti].[Sb] PFZWDJVEHNQTJI-UHFFFAOYSA-N 0.000 description 1
- 229960002303 citric acid monohydrate Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- -1 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
The invention relates to a kind of liquid polyesters Catalysts and its preparation method and application, this liquid antimony catalyst is the homogeneous phase solution generated by antimony compounds and properties-correcting agent and glycol reaction, wherein antimony content is 2.0 ~ 6.0%, non-crystallizable under normal temperature, can be directly used in the catalyzer of polyester polycondensation reaction.Synthesis technique of the present invention is simple, easy to operate, cost is low, can save the heating modulation insulating process using solid antimony-based catalyst, apply efficient and convenient, reduce production of polyester cost.
Description
Technical field
The present invention relates to a kind of synthesizing polyester (polyethylene terephthalate, be called for short PET) Catalysts and its preparation method and applied technical field, be by antimony compounds and modifier combination in more detail and be dissolved in ethylene glycol, liquid antimony catalyst stable under preparing normal temperature, and the field this catalyzer being used for polyester synthesis.
Background technology
At present, during PET produces, custom catalysts is solid antimonous oxide, crystal antimony acetate or crystal antimony glycol, wherein antimony acetate and antimony glycol by antimonous oxide respectively with aceticanhydride and glycol reaction, through process manufactures such as crystallization, separation, dryings, when applying above-mentioned three kinds of solid chemical compounds as catalyst to synthesize ester, need again to be heated to be dissolved in ethylene glycol, and insulation stores.Its disadvantage existed is: one, because antimonous oxide, crystal antimony acetate or crystal antimony glycol under normal temperature are insoluble to ethylene glycol, hot digestion is needed to dissolve, and antimony acetate and glycol antimony catalyst in preparation process through heating for dissolving, crystallization, be separated, the process such as dry, need when synthesizing for polyester to reheat dissolving again, therefore the manufacture of prior art catalyzer and use procedure exist that energy consumption is high, high in cost of production defect; Two, in dissolution process, solid-state antimonous oxide, antimony acetate, antimony glycol easily deposit in dissolution equipment, local superheating disproportionation occurs and decomposes flavescence blackening, cause residual toxicity more than Sb in catalytic activity decline, polyester
3+sb
0and affect polyester quality; Three, easy crystallization after heating for dissolving, makes troubles to application, and for preventing crystallization, the concentration of antimony generally needs to control below 1%, and simultaneous temperature needs to maintain 90 ~ 120 DEG C; Four, the antimony catalyst after dissolving at high temperature is placed for a long time, both wastes energy, and also easily disproportionation reaction occurs, and caused catalytic activity reduction etc.
Summary of the invention
Object of the present invention is exactly the disadvantage overcoming prior art existence, adopts new technical characteristic, provides liquid antimony catalyst of a kind of normal temperature and its preparation method and application.
In order to reach object of the present invention, the present invention passes through antimony compounds and modifier combination and is dissolved in ethylene glycol, make the antimony compounds of dissolving no longer easily occur crystallization, the liquid antimony-based catalyst of non-crystallizable precipitation under preparing a kind of normal temperature, and this kind of catalyzer is used for polyester synthesis.
The raw material antimony compounds of Kaolinite Preparation of Catalyst used in the present invention is antimonous oxide, antimony acetate and antimony glycol, due to the antimony compounds that antimonous oxide is the most basic, antimony acetate and antimony glycol are also all adopt antimonous oxide as raw material production, and also there is the pollutions such as toluene in antimony acetate production process, therefore, the preferred antimonous oxide of the present invention is as the raw material of Kaolinite Preparation of Catalyst.
In the present invention, the content of concentration in the liquid antimony catalyst solution made of antimony controls 2.0 ~ 6.0%; When antimony content is less than 2.0%, increase storage package transportation cost; When antimony content higher than 6.0% time, catalyzer stability in storage be deteriorated, easily separate out white depositions.
The properties-correcting agent selected in the present invention is lactic acid, citric acid, tartrate, tetramethylolmethane, both can be used alone in use, also can arbitrary combination use, conflict effect is not each other found in test, conveniently apply, the present invention preferably uses one wherein, and forms according to the mol ratio adjustment reactant of correspondence; Properties-correcting agent both can add with raw material before the reaction together, and also can add after antimony compounds and glycol reaction complete, the present invention preferably adds before the reaction together with raw material again, and experiment finds that the liquid catalyst stability of preparation is like this better than the latter; When preparing liquid catalyst, according to the difference of properties-correcting agent used, properties-correcting agent is different from the mol ratio of antimony, and wherein the mol ratio of lactic acid and antimony is preferably 0.84 ~ 3.37:1.0; The mol ratio of citric acid and antimony is preferably 0.32 ~ 1.9:1.0; The mol ratio of tartrate and antimony is preferably 0.24 ~ 3.0:1.0; The mol ratio of tetramethylolmethane and antimony is preferably 0.33 ~ 2.2:1.0; Find in application, when the mol ratio of properties-correcting agent and antimony is less than lower bound, the liquid catalyst made is unstable, easy precipitation white solid, along with the rising of properties-correcting agent and antimony mol ratio, make liquid catalyst stability also better, consider that cost factor and properties-correcting agent consumption too much also can bring disadvantageous effect to the molecular structure of polyester synthesis or polyester, the preferred aforementioned proportion scope of the present invention, and polymerization experiment investigation has been carried out to the liquid catalyst made.
In the preparation process of catalyzer of the present invention, when using antimonous oxide as raw material, itself and glycol reaction can produce water byproduct; When using antimony acetate as raw material, itself and glycol reaction can produce acetic acid; Using during antimony glycol does not then have by product to produce.Reaction dehydration or de-process of acetic acid both can at ambient pressure, and also can under reduced pressure carry out, the present invention preferably carries out at ambient pressure, and temperature of reaction is solution boiling temperature.
In the present invention, polyester inherent viscosity (η) represents the extent of polymerization of polyester, unit is the shorthand of dl/g(deciliters/grams), along with viscosity raises in aggregation test, power of agitator can raise or mixing speed can reduce, and determines reaction end accordingly; The test of η is by polyester being adopted Ben Fen ﹕ tetrachloroethane=1 ﹕ 1(mass ratio) mixed solution carry out dissolving and pass through determination of ubbelohde viscometer at 25 DEG C.
Embodiment
The present invention is further illustrated below by embodiment:
Embodiment 1:
Be in the reactor of 1000ml at volume, add 12g antimonous oxide, 440g ethylene glycol, heat and deviate to react the water produced, after solids all dissolves, filter, add the lactic acid that 17.5g content is 85%, spent glycol adjustment solution gross weight is 500g, namely obtains liquid antimony catalyst solution, wherein containing antimony 2.0%, the mol ratio of antimony and lactic acid is 1:2.0, and it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 2:
Be in the reactor of 1000ml at volume, add 36g antimonous oxide, 88.24g content be 85% lactic acid, 380g ethylene glycol, heat and deviate to react the water produced, after solids all dissolves, filtering, spent glycol adjustment solution gross weight is 500g, namely obtain liquid antimony catalyst solution, wherein containing antimony 6.0%, the mol ratio of antimony and lactic acid is 1:3.37, it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 3:
Be in the reactor of 1000ml at volume, add 24g antimonous oxide, 14.68g content be 85% lactic acid and 450g ethylene glycol, heat and deviate to react the water produced, after solids all dissolves, filtering, spent glycol adjustment solution gross weight is 500g, namely obtain liquid antimony catalyst solution, wherein containing antimony 4.0%, the mol ratio of antimony and lactic acid is about 1:0.84, it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 4:
Be in the reactor of 1000ml at volume, add 12.0g antimonous oxide, 5.5g Citric acid monohydrate Food grade and 480g ethylene glycol, heat and deviate to react the water produced, after solids all dissolves, filtering, spent glycol adjustment solution gross weight is 500g, namely obtain liquid antimony catalyst solution, wherein containing antimony 2.0%, the mol ratio of antimony and citric acid is 1:0.32, it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 5:
Be in the reactor of 1000ml at volume, adding 35.0g antimony content is 57.5% crystal antimony glycol, 38.0g Citric Acid, usp, Anhydrous Powder and 420g ethylene glycol, heating, after solids all dissolves, filters, spent glycol adjustment solution gross weight is 500g, namely obtain liquid antimony catalyst solution, wherein containing antimony 4.03%, the mol ratio of antimony and citric acid is 1:1.2, it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 6:
Be in the reactor of 1000ml at volume, add 24.0g antimonous oxide, 60.0g Citric Acid, usp, Anhydrous Powder and 410g ethylene glycol, heat and deviate to react the water produced, after solids all dissolves, filtering, spent glycol adjustment solution gross weight is 500g, namely obtain liquid antimony catalyst solution, wherein containing antimony 4.0%, the mol ratio of antimony and citric acid is 1:1.9, it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 7:
Be in the reactor of 1000ml at volume, add 12g antimonous oxide, the acid of 37.0g anhydrous and 450g ethylene glycol, heat and deviate to react the water produced, after solids all dissolves, filtering, spent glycol adjustment solution gross weight is 500g, namely obtain liquid antimony catalyst solution, wherein containing antimony 2.0%, antimony and tartaric mol ratio are 1:3.0, it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 8:
Be in the reactor of 1000ml at volume, add 73.2g containing the crystal antimony acetate of antimony 41.2%, 10.0g mono-water tartrate and 410g ethylene glycol, heat and deviate to react the acetic acid produced, after solids all dissolves, filtering, spent glycol adjustment solution gross weight is 500g, namely obtain liquid antimony catalyst solution, wherein containing antimony 6.03%, antimony and tartaric mol ratio are 1:0.24, it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 9:
Be in the reactor of 1000ml at volume, add 36g antimonous oxide, add 104g mono-water tartrate and 355g ethylene glycol, heat and deviate to react the water produced, after solids all dissolves, filtering, spent glycol adjustment solution gross weight is 500g, namely obtain liquid antimony catalyst solution, wherein containing antimony 6.0%, antimony and tartaric mol ratio are 1:2.5, it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 10:
Be in the reactor of 1000ml at volume, add 12g antimonous oxide, add 3.75g tetramethylolmethane and 380g ethylene glycol, heat and deviate to react the water produced, after solids all dissolves, spent glycol adjustment solution gross weight is 500g, namely obtains liquid antimony catalyst solution, wherein containing antimony 2.0%, the mol ratio of antimony and tetramethylolmethane is 1:0.33, and it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 11:
Be in the reactor of 1000ml at volume, add 24g antimonous oxide, 33.6g tetramethylolmethane and 430g ethylene glycol, heat and deviate to react the water produced, after solids all dissolves, filtering, spent glycol adjustment solution gross weight is 500g, namely obtain liquid antimony catalyst solution, wherein containing antimony 4.0%, the mol ratio of antimony and tetramethylolmethane is 1:1.5, it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 12:
Be in the reactor of 1000ml at volume, add crystal antimony acetate, 74.1g tetramethylolmethane, the 370g ethylene glycol of 73.2g containing antimony 41.2%, heat and deviate to react the acetic acid produced, after solids all dissolves, filtering, spent glycol adjustment solution gross weight is 500g, namely obtain liquid antimony catalyst solution, wherein containing antimony 6.03%, the mol ratio of antimony and tetramethylolmethane is 1:2.2, it is non-crystallizable that this solution is cooled to normal temperature, can be directly used in the catalyzer of synthesis PET.
Embodiment 13:
In 2.5 liters of stainless steel cauldrons, add the obtained antimony titanium composition of 1.0kg terephthalic acid, 465g ethylene glycol and embodiment 1 ~ 12 as catalyzer (catalyst levels is see table 1), at 0.5 ~ 3.0kg/cm
2esterification is carried out under G condition, and the water of reaction generation is sloughed by rectifier unit, when temperature rise to 255 DEG C, be depressurized to normal pressure, then continue to be warming up to 260 ~ 270 DEG C, until anhydrous discharge, reaction times about needs 2h, after this vacuumize decompression and be decompressed to below 100Pa gradually in 45min, control temperature is 285 ~ 288 DEG C, polyreaction terminal is judged according to agitator speed or power of motor, when corresponding polymer viscosity is 0.660dl/g (permissible error 0.01), vacuum is removed with nitrogen, stopped reaction, record polycondensation total time, polymkeric substance is extruded with shredded forms, cooling, pelletizing, test its b value, adopt antimony glycol to do comparative catalyst to carry out testing according to said process and as comparative example, test result is in table 1.
Table 1: catalyst application contrasts
Nomenclature is used in the present invention:
Pa is handkerchief, and ml is milliliter, and h is hour, and min is minute, and % is mass percent, and g is gram, and kg is kilogram, cm
2be square centimeter, G represents gauge pressure.
The stoichiometric equation of chemical reaction related in the present invention is:
(1)Sb
2O
3(S)+3HOCH
2CH
2OH(L)=Sb
2(OCH
2CH
2O)
3(L)+3H
2O(L)
(2)2Sb(CH
3COO)
3(S)+3HOCH
2CH
2OH(L)=Sb
2(OCH
2CH
2O)
3(L)+6CH
3COOH(L)
In equation bracket, S represents solid; L represents liquid.
Claims (7)
1. a polyester catalyst, it is the homogeneous phase solution generated by antimony compounds, properties-correcting agent and ethylene glycol hybrid reaction, it is characterized in that adding antimony compounds, properties-correcting agent and ethylene glycol in the reactor, carry out heating for dissolving reaction, when having low molecule product water or acetic acid produces, deviate from by water distilling apparatus, after solids all dissolves, cooling is filtered, and namely obtains a kind of homogeneous phase solution, the antimony content that spent glycol adjusts in liquid antimony catalyst solution is 2.0 ~ 6.0%, namely obtains polyester catalyst; Described properties-correcting agent is lactic acid, citric acid, tartrate or tetramethylolmethane.
2. a kind of polyester catalyst according to claim 1, is characterized in that described antimony compounds is antimonous oxide, antimony acetate, antimony glycol.
3. the preparation method of a polyester catalyst according to claim 1, it is characterized in that adding antimony compounds, properties-correcting agent and ethylene glycol in the reactor, carry out heating for dissolving reaction, when having low molecule product water or acetic acid produces, deviate from by water distilling apparatus, after solids all dissolves, cooling is filtered, namely obtain a kind of homogeneous phase solution, the antimony content that spent glycol adjusts in liquid antimony catalyst solution is 2.0 ~ 6.0%, namely obtains polyester catalyst; Described properties-correcting agent is lactic acid, citric acid, tartrate or tetramethylolmethane.
4. the preparation method of polyester catalyst according to claim 3, is characterized in that the mol ratio of lactic acid and antimony is 0.84 ~ 3.37:1.0; The mol ratio of citric acid and antimony is 0.32 ~ 1.9:1.0; The mol ratio of tartrate and antimony is 0.24 ~ 3.0:1.0; The mol ratio of tetramethylolmethane and antimony is 0.33 ~ 2.2:1.0.
5. the preparation method of polyester catalyst according to claim 3, is characterized in that described heating for dissolving reaction, deviates from low molecule product water or the acetic acid of reaction generation, is for the low molecule product generated during antimonous oxide is water when the antimony compounds used; When the antimony compounds used for the low molecule product generated during antimony acetate is acetic acid.
6. the preparation method of polyester catalyst according to claim 5, is characterized in that heating for dissolving process is carried out under solution boiling state.
7. polyester catalyst according to claim 1 application in polyester synthesis.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235148A (en) * | 1999-04-16 | 1999-11-17 | 无锡市正茂化工厂 | Preparation of high purity antimony glycol |
| CN1270158A (en) * | 2000-01-12 | 2000-10-18 | 曹善文 | Process for preparing antimony compound of binary alcohol |
| CN2820864Y (en) * | 2005-05-26 | 2006-09-27 | 曹善文 | Polyester catalyst mixing device |
-
2013
- 2013-09-10 CN CN201310406280.1A patent/CN103435786B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235148A (en) * | 1999-04-16 | 1999-11-17 | 无锡市正茂化工厂 | Preparation of high purity antimony glycol |
| CN1270158A (en) * | 2000-01-12 | 2000-10-18 | 曹善文 | Process for preparing antimony compound of binary alcohol |
| CN2820864Y (en) * | 2005-05-26 | 2006-09-27 | 曹善文 | Polyester catalyst mixing device |
Non-Patent Citations (1)
| Title |
|---|
| 聚酯装置自行制备乙二醇锑溶液;刘浩等;《聚酯工业》;20050331;第18卷(第2期);第37-39页 * |
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