CN1088452C - Process for preparing glycol antimony as polyester catalyst - Google Patents
Process for preparing glycol antimony as polyester catalyst Download PDFInfo
- Publication number
- CN1088452C CN1088452C CN99117315A CN99117315A CN1088452C CN 1088452 C CN1088452 C CN 1088452C CN 99117315 A CN99117315 A CN 99117315A CN 99117315 A CN99117315 A CN 99117315A CN 1088452 C CN1088452 C CN 1088452C
- Authority
- CN
- China
- Prior art keywords
- antimony
- ethylene glycol
- glycol
- polyester catalyst
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention provides a method for preparing glycol antimony of a polyester catalyst. In the method, antimonous oxide is added into ethylene glycol solution to be stirred and heated to 150 to 197 DEG C for 10 to 50 hours, solids in the solution are removed, and the temperature of clear liquid keeps higher than 100 DEG C; then, the temperature is dropped to be lower than 30 DEG C in 10 to 80 hours, ethylene glycol antimony crystals are centrifugally separated, free ethylene glycol is eliminated, the treated ethylene glycol antimony crystals are dried for 3 to 40 hours under conditions that temperature is from 50 to 90 DEG C, and vacuum degree is from 2 to 20 mmHg to obtained the ethylene glycol antimony of a polyester catalyst. The method is simple, the produced ethylene glycol antimony of a polyester catalyst has high catalytic activity, and the quality of diglycol terephthalate is improved.
Description
What the present invention relates to is a kind of Preparation of catalysts method, particularly be a kind of preparation method of glycol antimony as polyester catalyst.
Generally adopt antimonous oxide (Sb in the present domestic production of polyester
2O
3) or antimony acetate make catalyzer, the performance of its product such as viscosity, color and luster, thermostability and by-products content can satisfy the requirement of different purposes polyester.But still there is following shortcoming:
1, Sb
2O
3Solvability is relatively poor in second two ferment (EG), needs heat temperature raising during preparation;
2, reductibility by products such as the acetaldehyde that produces in the polycondensation process can be with Sb
3+Be reduced to metallic antimony, and make goods often show the photographic fog look;
3, Sb
2O
3Problems such as caused dust pollution, filter blocks;
4, antimony acetate has been introduced unnecessary OAc in the pet reaction system and in the polyethylene terephthalate (PET)
-Foreign ion;
5, in the manufacturing processed of antimony acetate, to use carcinogens dimethylbenzene.
In order to overcome the above-mentioned drawback of catalyzer, scientific and technical personnel are devoted to always to seek that a kind of activity is higher, the product form and aspect are better, do not introduce the catalyzer of other foreign ion.Doctor M.Stershic of Elf Atochem company has invented a kind of antimony organic catalyzer---antimony glycol, though at Deutsches Wirtschafts Patent DD227,710 (1985), European patent EP 61,414 (nineteen eighty-twos) and Du Pont company are published in J.Pdym.Sci., Polym.Chem.Ed[17 (12): 4033-40,1979] article in, all once mentioned antimony glycol, but all do not relate to its preparation method.And U.S. Pat 4,169,104 (1979) is though mention with Cu[Sb (OH) 6]
2Can get the quinquevalence antimony acid esters salt of ethylene glycol with the ethylene glycol thermal dehydration, but this compounds or unstable or have color, its purposes is non-catalytic as pressing down fumicants.
In view of above reason, the objective of the invention is to improve the preparation method of the glycol antimony as polyester catalyst of polyethylene terephthalate PET quality for a kind of energy production catalytic activity height is provided.
The object of the present invention is achieved like this:
Preparation method of the present invention adds antimonous oxide in ethylene glycol solution, stirring is warming up to 150-197 ℃, kept 10～50 hours, and removed the solid substance in the solution, clear liquid maintains more than 100 ℃, in 10～80 hours, cool the temperature to below 30 ℃ then, centrifugation goes out the antimony glycol crystal, sloughs free ethylene glycol, under 50～90 ℃, vacuum tightness 2～20mmHg condition, promptly got glycol antimony as polyester catalyst in dry 3～40 hours, solid substance is Sb
2O
3Impurity, dissolved Sb in middle impurity, the ethylene glycol
2O
3And the Sb class material of reaction generation.
The above-mentioned ethylene glycol and the weight ratio of antimonous oxide are 100: 4～20.
Reaction principle of the present invention is:
Preparation method of the present invention is simple, and the glycol antimony as polyester catalyst catalytic activity height that adopts preparation method of the present invention to produce can improve the quality of gathering terephthaldehyde's ester second diester PET.
3000 tons of batchwise polymerizations of Jinan research institute of chemical fibre main office are installed on 99 on July 21, to 23 days, and the glycol antimony as polyester catalyst that adopts the inventive method to produce to Kaifei High Energy Chem. Inductry Co., Ltd., Chengdu City's (be called for short Chengdu and open the company of flying) has carried out pilot plant test.
On the lab scale experiment basis, 3000 tons of device tissues of research institute are opened Chengdu and are flown company's new polyester catalyst glycol antimony and experimentize, and compare with import catalyst glycol antimony S-24, experiment is carried out ten batches altogether, and this report only summarizes to five batches of having with the equal working conditions of import antimony glycol S-24.Now relevant experimental data is summarized as follows:
One, the physical and chemical index of catalyzer and modulation case thereof (, seeing Table 1) with import antimony glycol S-24 contrast:
Table 1:
Its setter proportioning is: ethylene glycol: 260L antimony glycol: 12.0KG (Chengdu is opened and flown) two: the polymerization situation is (with use Sb
2O
3And import S-24 is relatively) 1, polycondensation control process parameters: (a): rough vacuum time: 40 minutes (b): high vacuum time: 180-200 minute (c): vacuum tightness during high vacuum :～25Pa (d): polycondensation cooling point: 273 ℃
| Project/sample | Chengdu is opened and is flown company's antimony glycol | Import antimony glycol S-24 |
| Antimony content (Wt%) | 54.98 | 57.40 |
| Compound concentration (Wt%) | 4.0 | 4.0 |
| Fe content (PPm) | 1.0 | ≤10.0 |
| Weight loss on drying (Wt%) | / | 1.1 |
| Preparation liquid color | Water white transparency | Water white transparency |
| Preparation liquid outward appearance | Clear does not have insolubles | Clear does not have insolubles |
| Preparation liquid normal temperature is placed | Substantially not having crystal grain separates out | Slight crystal grain is separated out |
| The catalyzer outward appearance | White particle | White particle |
| The preparation temperature | 120℃ | 120℃ |
Polycondensation shift points: 283 ℃ (e): section kind: light section (film level) is arranged (f) greatly: the intrinsic viscosity central value: 0.660 ± 0.012 (world) 2, relevant parameter comparison of polycondensation and product such as following table 2: table 2:
| Project/sample | Chengdu is opened and is flown company's antimony glycol | Import antimony glycol S-24 | Use homemade Sb 2O 3 |
| The catalyzer working concentration | 450ppm | 450ppm | 276ppm |
| Polymerization cycle (on average) | 3hr43min | 3hr35min | 3hr52min |
| Polycondensation is temperature eventually | 286℃ | 285℃ | 287℃ |
| Intrinsic viscosity | 0.662 | 0.650 | 0.680 |
| Form and aspect L value | 52.1 | 52.8 | 52.0 |
| The b value | 2.4 | 2.7 | 2.3 |
| The section fusing point (℃) | 261-263℃ | 260-262℃ | 260-262℃ |
| Remarks | Amount to five batches | Amount to five batches | Amount to eight batches (mean value) |
Three, conclusion (of pressure testing):
This uses Chengdu to open the company that flies and produces glycol antimony catalyst, produces ten batches of products altogether, is acceptable end product, experimental session, and the appliance arrangement operation is normal, and vacuum state is good, and the experimental result that obtains is reliable, and through Testing Team's research, it is as follows now to intend conclusion:
1, Chengdu is opened and is flown company's glycol antimony as polyester catalyst, except that antimony content is lower than import antimony glycol S-24 slightly, and other index and import antimony glycol S-24 no significant difference, solubility property is good in ethylene glycol.Its 120 ℃ of modulating liquids dissolving is (4%) fully, water white transparency, and it is non-crystallizable to place the long period.
2, be 450ppm at working concentration, produce film when the light section is arranged greatly, condensation polymerization speed is than use Sb
2O
3Want fast, use import antimony glycol S-24, have the certain reaction speed advantage but be slightly poorer than.
3, qualitatively, the company that flies that uses Chengdu to open produces its quality product of antimony glycol and all reaches the first grade standard, (enterprise's control standard: L value 〉=48.0b value≤4.0) basic approaching use import antimony glycol S-24 quality product at product (section).
Adopt the inventive method energy production catalytic activity height, can improve the glycol antimony as polyester catalyst of polyethylene terephthalate quality.
Introduce embodiments of the invention below:
Embodiment 1:
In the 3000L enamel reaction still, add ethylene glycol solution 3000L, slowly add Sb under stirring
2O
3400kg is warming up to 150-160 ℃, keeps 5-6hr, continues to be warming up to 190 ℃, keeps about 10-30hr, the separation solid substance, and clear liquid is cooled to below 30 ℃, centrifugation, the antimony glycol crystal that obtains is at 50-90 ℃, dry 3-10hr under the vacuum tightness 5-20mmHg.
Embodiment 2:
In the 3000L stainless steel cauldron, add ethylene glycol solution 3000L, slowly add Sb under stirring
2O
3200kg is warming up to 190 ℃, keeps about 15-40hr, separates solid substance, and clear liquid is cooled to below 20 ℃, centrifugation, the antimony glycol crystal, this crystal is at 50-90 ℃, dry 3-10hr under the vacuum tightness 6-20mmHg.
Embodiment 3:
In the 2000L stainless steel cauldron, add ethylene glycol solution 2000L, add Sb under stirring
2O
380kg is warming up to 150 ℃, keeps temperature, continues stir about 20hr, removes solid substance in the solution, and clear liquid was cooled to below 30 ℃ with 20 hours, isolated the antimony glycol crystal, and this crystal kept vacuum tightness 2-5mmHg dry 15 hours under 50 ℃.
Embodiment 4:
In the 2000L stainless steel cauldron, add ethylene glycol solution 2000L, add Sb under stirring
2O
3400kg, be warming up to 195 ℃, keep temperature, continue stir about 50hr, remove solid substance in the solution, the clear liquid holding temperature is more than 155 ℃, with 70hr temperature is reduced to below 30 ℃ then, isolate the antimony glycol crystal, this crystal keeps vacuum tightness under the 15-20mmHg condition dry 34 hours under 90 ℃ of temperature.
In the various embodiments described above, ethylene glycol solution is the seconds that meets GB4649-84, antimonous oxide (Sb
2O
3) in Sb
2O
3Content is greater than 99.0%, Fe＜0.005%, SO
2- 4＜0.02%, H
2O＜0.1%.
Claims (2)
1, the preparation method of glycol antimony as polyester catalyst, it is characterized in that described method is to add antimonous oxide in ethylene glycol solution, stirring is warming up to 150-197 ℃, kept 10～50 hours, remove the solid substance in the solution, clear liquid maintains more than 100 ℃, in 10～80 hours, cool the temperature to below 30 ℃ then, centrifugation goes out the antimony glycol crystal, slough free ethylene glycol, under 50～90 ℃, vacuum tightness 2～20mmHg condition, promptly got glycol antimony as polyester catalyst in dry 3～40 hours.
2, the preparation method of glycol antimony as polyester catalyst according to claim 1, the weight ratio that it is characterized in that ethylene glycol solution and antimonous oxide is 100: 4～20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99117315A CN1088452C (en) | 1999-10-19 | 1999-10-19 | Process for preparing glycol antimony as polyester catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99117315A CN1088452C (en) | 1999-10-19 | 1999-10-19 | Process for preparing glycol antimony as polyester catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1255478A CN1255478A (en) | 2000-06-07 |
| CN1088452C true CN1088452C (en) | 2002-07-31 |
Family
ID=5279949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99117315A Expired - Fee Related CN1088452C (en) | 1999-10-19 | 1999-10-19 | Process for preparing glycol antimony as polyester catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1088452C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075510C (en) * | 1999-10-26 | 2001-11-28 | 郑立梅 | Glycol antimony catalyst and preparation process thereof |
| CN101735013A (en) * | 2008-11-19 | 2010-06-16 | 辽阳市宏伟区合成催化剂厂 | Process for preparing ethylene glycol antimony serving as polyester polycondensation catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB805543A (en) * | 1954-11-10 | 1958-12-10 | Snecma | Improvements in heating apparatus operated by means of a pulsatory combustion chamber |
-
1999
- 1999-10-19 CN CN99117315A patent/CN1088452C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB805543A (en) * | 1954-11-10 | 1958-12-10 | Snecma | Improvements in heating apparatus operated by means of a pulsatory combustion chamber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1255478A (en) | 2000-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1110988B1 (en) | Catalyst for polyester production and process for producing polyester with the same | |
| JP3897756B2 (en) | Catalyst for producing polyester and method for producing polyester using the same | |
| CA2459580C (en) | Process for producing poly(ethylene aromatic carboxylate ester) resin and resin product | |
| CN107266664A (en) | A kind of Reclaim of PET Scrap technique | |
| LV13428B (en) | Polymerization catalyst for preparing polyesters, preparation of polyethylene terephthalate and use of polymerization catalyst | |
| US6153679A (en) | Titanium oxide and resin composition | |
| CN113881027A (en) | Titanium polyester catalyst and preparation method and application thereof | |
| JP2001055434A (en) | Catalyst for producing polyester, production of polyester using the same catalyst and polyethylene terephthalate produced by the same catalyst | |
| CA2113639A1 (en) | Copolyesters for high modulus fibers | |
| US7262263B2 (en) | Method and apparatus for producing solid-state polycondensed polyesters | |
| DE10121542A1 (en) | Composition and process for the production of polyester | |
| CN1088452C (en) | Process for preparing glycol antimony as polyester catalyst | |
| WO2001081447A2 (en) | Optimum dipropylene glycol content polytrimethylene terephthalate compositions | |
| KR20000069134A (en) | Modified 1,3-propanediol-based polyesters | |
| KR20030094236A (en) | Polymerization catalyst for polyester, polyester, and process for producing the same | |
| JP2002013024A (en) | High-strength polyester fiber and method for producing the same | |
| KR20090053900A (en) | Process for producing polyester with metal phosphonic acid complex catalysts | |
| EP2491012A2 (en) | Use of an acetic acid/water solvent mixture for the preparation of low-sulfate 5-sulfoisophthalic acid, mono-lithium salt from 5-sulfoisophthalic acid | |
| DE69823632T2 (en) | Method of reducing gel formation in PET resin | |
| CN1156511C (en) | Process for preparing polyethylene terephthalate | |
| EP1584712B1 (en) | Knitted/woven fabric of polyethylene terephthalate fiber | |
| JP3888884B2 (en) | Polyester production method | |
| EP1919978A2 (en) | Inherently coloured polyester polymers, fibers or filaments and process for producing them | |
| EP1426395B1 (en) | Polytrimethylene terephthalate polyester | |
| JPH03215522A (en) | Production of polyester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20020731 Termination date: 20101019 |