CN1141328C - Use of nanometer grade antimony trioxide as polyester polycondensation catalyst - Google Patents
Use of nanometer grade antimony trioxide as polyester polycondensation catalyst Download PDFInfo
- Publication number
- CN1141328C CN1141328C CNB011094753A CN01109475A CN1141328C CN 1141328 C CN1141328 C CN 1141328C CN B011094753 A CNB011094753 A CN B011094753A CN 01109475 A CN01109475 A CN 01109475A CN 1141328 C CN1141328 C CN 1141328C
- Authority
- CN
- China
- Prior art keywords
- antimony trioxide
- polyester
- nanometer grade
- catalyst
- polycondensation reaction
- 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000006068 polycondensation reaction Methods 0.000 title claims abstract description 20
- 229920000728 polyester Polymers 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 title abstract description 13
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims abstract description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005886 esterification reaction Methods 0.000 claims abstract description 13
- 230000032050 esterification Effects 0.000 claims description 12
- 238000005809 transesterification reaction Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 150000002148 esters Chemical group 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FHUCUPVQDUPROK-UHFFFAOYSA-N acetic acid;antimony Chemical compound [Sb].CC(O)=O FHUCUPVQDUPROK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to an application of nanometer-level antimony trioxide used as a catalyst in a polycondensation reaction of polyester. The polycondensation reaction of polyester is a molecular polycondensation reaction after an esterification reaction of terephthalic acid or an ester exchange reaction of dimethyl terephthalate. The catalyst of the nanometer-level antimony trioxide has the characteristics of small average grain size, uniform dispersion in the polycondensation reaction of polyester, good solubility, high catalytic activity, low cost, etc.
Description
The present invention relates to nanometer grade antimony trioxide (Sb
2O
3) as the purposes of polyester polycondensation catalyst.
Annual ten thousand tons of the about 400-450 of polyester slice (ethylene glycol terephthalate) that produce of China, wherein about 80% uses antimony acetate (Sb (Ac)
3) as catalyzer, and these catalyzer 80% is external import.Therefore use the catalyzer of antimony acetate, not only cost an arm and a leg, and used up national a large amount of foreign exchange as polycondensation of polyester.
Nanotechnology is as one of the most popular technology of current research, and its range of application spreads all over a plurality of subjects.Nano level Sb
2O
3As type material, has purposes widely, as being used as polyester polycondensation catalyst, the fire retardant in chemical fibre, engineering plastics, the rubber industry etc.
Theme of the present invention is the purposes of nanometer grade antimony trioxide as polyester polycondensation catalyst.Compare with catalyst acetic acid antimony, used nanometer grade antimony trioxide has that cost is low, and median size is little, is uniformly dispersed in polyester polycondensation reaction, and solvability is good, characteristics such as catalytic activity height.
As everyone knows, the raw material of production PET mainly is terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG).Its production technique also is that those skilled in the art are known.Used catalyzer generally is Sb (Ac)
3
The present invention is by using nano level Sb
2O
3Replace Sb (Ac)
3As the catalyzer of the molecule polycondensation after the transesterification reaction of the esterification of terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT), obtained beyond thought effect.Its consumption is only less than Sb (Ac)
3Half of consumption but reached with Sb (Ac)
3Identical catalytic effect, even on some index, exceeded use Sb (Ac)
3Therefore resulting index has saved spending greatly, has improved catalytic effect simultaneously.
Catalyst nano level Sb of the present invention
2O
3With the weight ratio of employed PTA be in the scope of 100-450ppm.
Used nano level Sb
2O
3Can trade mark or strain state, the Hunan three profit nanometer novel material companies with mountains and rivers associating board buy from the Beijing Shanchuan Joint Nanometer Science and Technology Co., Ltd, its size range is 10-100nm.
Below in conjunction with example the present invention is described.
Example
Raw material
The PTA fibre-grade is raised sub-petro-chemical corporation
The EG fibre-grade is raised sub-petro-chemical corporation
Sb
2O
3Nano level (10-100nm) Beijing Shanchuan Joint Nanometer Science and Technology Co., Ltd
Sb (Ac)
3Catalyzer Yizheng Kang Run company
In whole embodiment, every still drops into PTA350g, EG222g.Nano level Sb
2O
3Addition is 0.0732g (Sb
3+With the mol ratio of PTA be 2.349 * 10
-4, Sb
2O
3With the weight ratio of PTA be 206.6ppm); Sb (Ac)
3Add-on is 0.1481g (Sb
3+With the mol ratio of PTA be 2.349 * 10
-4, Sb (Ac)
3With the weight ratio of PTA be 423.1ppm).Do not add anti-etherifying agent in the reaction.Table 1 has provided the processing parameter of each example.
Reaction process as shown in Figure 1.
Example 1
The chuck oil temperature of chuck heating agent circulation electric heater unit is arranged on 260 ℃, 2 groups of well heaters heat up at full speed, when treating that jacket temperature rises to 200 ℃, the slurry that the EG of PTA, the 222g of input 350g forms in stainless steel cauldron, and drop into 0.0732g catalyst nano level Sb simultaneously
2O
3Use 0.1MPa N
2After replacing 3 times, use N
2Be pressurized to 0.1MPa.Carrying out esterification under the 100rpm rotating speed stirs heats up.Utilize fractional column top valve regulated still internal pressure to be 0.25Mpa, calculate esterification time from beginning to react water outlet, esterification was carried out under 230 ± 5 ℃ temperature 107 minutes.The question response aquifer yield reaches and carries out pressure release behind the 71ml and finish esterification.The step-down that heats up subsequently constantly rose to 280 ℃ with temperature in the kettle in 45 minutes, simultaneously mixing speed is reduced to 40rpm, regulated that vacuum is 80Pa (manual regulation has certain variation range) in the still.Polymerization with this understanding, treat that polymerization is carried out 82 minutes after, power of agitator is changed to certain value, stops to stir and vacuum condition, finishes polyreaction, uses N
2Eliminate vacuum, nitrogen extrudes material, obtains the PET section.The section performance is referring to table 2.
Example 2
With example 1, just the time of esterification is 90 minutes, and aquifer yield is 66ml.The PET section performance that obtains is referring to table 2.
Example 3
With example 1, just the time of esterification is 92 minutes, and aquifer yield is 68ml, and the polycondensation time is 85 minutes.The PET section performance that obtains is referring to table 2.
Comparison example 1
Similar to example 1, only be to use 0.1481g Sb (Ac)
3Replacement 0.0732g catalyst nano level Sb
2O
3, esterification time is 93 minutes, and aquifer yield is 66ml, and the polycondensation time is 85 minutes.The section performance is referring to table 2.
Comparison example 2
Identical with comparison example 1, just esterification time is 90 minutes, and aquifer yield is 68ml, and the polycondensation time is 83 minutes.The section performance is referring to table 2.
Comparison example 3
Identical with comparison example 1, just esterification time is 90 minutes, and aquifer yield is 65ml, and the polycondensation time is 86 minutes.The section performance is referring to table 2.
The processing parameter of each example of table 1
| Catalyzer | Esterification time (min) | Aquifer yield (ml) | The intensification step-down time (min) | The polycondensation time (min) | The AW variable power | |
| Example 1 example 2 examples 3 mean values | Nano level Sb 2O 3 | 107 90 92 96.3 | 71 66 68 68.3 | 45 45 45 45 | 82 82 85 83 | 5.0 5.0 5.0 5.0 |
| Comparison example 1 comparison example 2 comparison example 3 mean values | Sb(Ac) 3 | 93 90 90 91 | 66 68 65 66.3 | 45 45 45 45 | 85 83 86 84.7 | 5.0 5.0 5.0 5.0 |
Table 2 section The performance test results
| Catalyzer | [IV] (dL/g) | COOH (mol/t) | DEG (％) | MP(℃) | L | b | YI | |
| Example 1 | Nano level Sb 2O 3 | 0.644 | 9.30 | 4.58 | 248.7 | 85.83 | 2.78 | 5.34 |
| Example 2 | 0.656 | 9.55 | 4.62 | 248.5 | 86.34 | 3.07 | 5.93 | |
| Example 3 | 0.676 | 9.92 | 4.39 | 248.3 | 86.70 | 3.05 | 5.93 | |
| Mean value | 0.659 | 9.59 | 4.53 | 248.5 | 86.29 | 2.97 | 5.73 | |
| Comparison example 1 | Sb(Ac) 3 | 0.666 | 14.38 | 4.63 | 248.0 | 86.83 | 3.05 | 5.83 |
| Comparison example 2 | 0.661 | 10.17 | 4.50 | 248.5 | 85.15 | 2.69 | 5.32 | |
| Comparison example 3 | 0.663 | 14.62 | 4.33 | 248.9 | 86.44 | 2.74 | 5.21 | |
| Mean value | 0.663 | 13.06 | 4.49 | 248.5 | 86.14 | 2.83 | 5.45 | |
Interpretation of result
Test-results shows, under the essentially identical situation of catalytic effect:
1, nano level Sb
2O
3Amount ratio Sb (Ac)
3Few over half;
2, use nano level Sb
2O
3The polyester slice that comes out as Catalyst Production is better than on some index with Sb (Ac)
3As the polyester slice that Catalyst Production is come out, as carboxyl-content, the former is 9.59mol/t, and the latter is 13.06mol/t.
Claims (3)
1, nanometer grade antimony trioxide is as the purposes of the catalyzer in the polyester polycondensation reaction, described polyester polycondensation reaction be the p phthalic acid esterification react or the transesterification reaction of dimethyl terephthalate (DMT) after the molecule polycondensation, the size range of described nanometer grade antimony trioxide is 10-100nm.
2, according to the purposes of claim 1, the consumption of wherein said nanometer grade antimony trioxide is the 0.01-0.045wt% of terephthalic acid or dimethyl terephthalate (DMT).
3, according to the purposes of claim 1, the consumption of wherein said nanometer grade antimony trioxide is the 0.02066wt% of terephthalic acid or dimethyl terephthalate (DMT).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011094753A CN1141328C (en) | 2001-03-15 | 2001-03-15 | Use of nanometer grade antimony trioxide as polyester polycondensation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011094753A CN1141328C (en) | 2001-03-15 | 2001-03-15 | Use of nanometer grade antimony trioxide as polyester polycondensation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1319620A CN1319620A (en) | 2001-10-31 |
| CN1141328C true CN1141328C (en) | 2004-03-10 |
Family
ID=4657952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011094753A Expired - Fee Related CN1141328C (en) | 2001-03-15 | 2001-03-15 | Use of nanometer grade antimony trioxide as polyester polycondensation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1141328C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302042C (en) * | 2003-03-31 | 2007-02-28 | 世韩工业株式会社 | Saturated polyester possessing excellent crystallization property |
| DE602004015638D1 (en) * | 2003-12-04 | 2008-09-18 | Teijin Fibers Ltd | POLYESTER, MANUFACTURING METHOD, FIBER AND |
| CN104355332B (en) * | 2014-10-20 | 2017-01-11 | 郑香萍 | Preparation device of antimony trioxide for polyester |
-
2001
- 2001-03-15 CN CNB011094753A patent/CN1141328C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1319620A (en) | 2001-10-31 |
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| C06 | Publication | ||
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| ASS | Succession or assignment of patent right |
Owner name: SUN QIMING Free format text: FORMER OWNER: BEIJING SHANCHUAN JOINT NANOMETER SCIENCE AND TECHNOLOGY CO., LTD. Effective date: 20030927 |
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Effective date of registration: 20030927 Address after: 100038, Fuxing Road, Beijing, Haidian District, No. 15, building 6, 101 Applicant after: Sun Qiming Address before: 100873, room 50411, Friendship Hotel, 1 South Avenue, Beijing, Haidian District, Zhongguancun Applicant before: Beijing Shanchuan Joint Nanometer Science and Technology Co., Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040310 Termination date: 20100315 |