CN102477147A - Polyester and application thereof - Google Patents
Polyester and application thereof Download PDFInfo
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- CN102477147A CN102477147A CN2010105576917A CN201010557691A CN102477147A CN 102477147 A CN102477147 A CN 102477147A CN 2010105576917 A CN2010105576917 A CN 2010105576917A CN 201010557691 A CN201010557691 A CN 201010557691A CN 102477147 A CN102477147 A CN 102477147A
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Abstract
The invention relates to polyester and an application thereof, and in the polyester synthetic process, a titanium catalyst, a magnesium compound, and a phosphorous compound stabilizer are added; the titanium catalyst comprises a titanium compound, an aliphatic diol, and a quarternary ammonium compound, and the adding amount of the titanium element in the titanium catalyst is 1-30 ppm with respect to the total amount of the polyester; the adding amount of the magnesium element in the magnesium compound is 10-80 ppm with respect to the total amount of the polyester; the adding amount of the phosphorus element in the phosphorous compound stabilizer is 5-60 ppm with respect to the total amount of the polyester; the polyester has an intrinsic viscosity of 0.50-0.80, a terminal carboxyl content of below 30 eq/ton, a polyethylene glycol content of below 1.2 wt%, and a tone b value of below 6. The polyester polymer obtained in the invention has an excellent tone, good heat stability, is environment friendly, and has good spinning performance.
Description
Technical field
The present invention relates to a kind of polyester and uses thereof, specifically is that this polyester uses a kind of titanium catalyst, magnesium compound and phosphonium stabilizer is arranged, the polyester tone excellence that makes, Heat stability is good, environmentally friendly, spinning properties good.
Background technology
Polyester, particularly polyethylene terephthalate have outstanding performance, are widely used in fields such as fiber, film, extremely people's favor.
Industrial production application at present and research mainly are the compounds of Sb, Ge, three series of Ti than multi-catalyst.That uses antimony catalyst production at present accounts for 90%.Though the catalytic effect of antimony-based catalyst is fine, when antimony compounds is used as polymerizing catalyst, when the gained polyester is implemented melt-spun continuously in the long time; The gained polyester has defective, and tramp material adheres to and is accumulated in the melt-spun mouth of pipe, if untimely removing; Residue forms easily bigger granular, becomes foreign matter, thereby filter presses liter when causing forming process; Phenomenon such as fracture of wire during spinning, spinning property is poor; And antimony can be leached out in the coloration of textile materials operation, and environment is very easily polluted, and runs counter to environmental requirement.Had research to point out that antimony metal can be detrimental to health in recent years successively, European recent regulations also begins to limit the antimony content in the textiles.Though and the germanium series catalysts has good performance, the tone of gained PET is also better, because price is too high, can't realize production.
In the face of this problem, actively carried out using the research of titanium compound as polymerizing catalyst.Titanium compound is compared with antimony compounds, and catalytic activity is high, and a small amount of interpolation can obtain desired catalytic activity, so can suppress the generation of foreign particle.But, when using titanium compound, owing to problems such as it are active high, and side reaction has been promoted that also it is bad that the result has produced the resulting polymers thermostability, or the polymkeric substance flavescence, and is painted as catalyzer.So titanium compound is as polycondensation catalyst, polymerization activity does not reduce, and the problem that suppresses side reaction is necessary to solve.
Therefore, the friendly type of environment for use, the catalyzer that do not contain antimony and heavy metal have become the inexorable trend of polyester industrial future development.Titanium compound is compared with antimony compounds, and catalytic activity is high, does not contain heavy metal, and spinning process does not have problems such as accumulation and the spinning jet pollution of impurity.
Set forth a kind of polyester manufacturing among the Chinese patent CN200480017234.1 and used titanium-containing catalyst solution, had only titanium and alcohol in this catalyzer.Set forth a kind of titanium compound that is suitable for esterification among the Chinese patent CN200480029424.5.Set forth a kind of polyester that uses titanium compound as catalyzer among the Chinese patent CN200480039813.6, and the acetaldehyde of this polyester has been carried out relevant regulations.
Polyester among the present invention comprises a kind of titanium catalyst, magnesium compound and phosphonium stabilizer is arranged, resulting polyester tone excellence, Heat stability is good, environmentally friendly, spinning properties good.
Summary of the invention
The object of the present invention is to provide a kind of tone excellence, good heat resistance, environmentally friendly, polyester that spinning properties is good.
Technical solution of the present invention is following:
A kind of polyester adds titanium catalyst, magnesium compound, phosphonium stabilizer is arranged in the polyester building-up process; Contain titanium compound, aliphatic dihydroxy alcohol, quaternary ammonium compound in the titanium catalyst, and the addition of titanium elements is 1～30ppm with respect to the polyester total amount in this titanium catalyst; The addition of magnesium elements is 10～80ppm with respect to the polyester total amount in the magnesium compound; There is the addition of phosphoric in the phosphonium stabilizer to be 5～60ppm with respect to the polyester total amount; The intrinsic viscosity of said polyester is 0.50～0.80, and terminal carboxyl(group) content is below the 30eq/ton, and polyethyleneglycol content is below the 1.2wt%, and tone b value is below 6.
Titanium catalyst, magnesium compound, there is phosphonium stabilizer proportionally to add reaction system after the uniform mixing to.
The chemical formula of the titanium compound in the said titanium catalyst is as follows,
R
1O-[Ti(OR
2)(OR
3)-O-]
n-R
4
R wherein
1, R
2, R
3And R
4Be respectively the alkyl or phenyl of carbonatoms 2～10, can be the same or different, n is 1～6 integer.
Aliphatic dihydroxy alcohol is a 1,1 in the said titanium catalyst, 2-Ucar 35,1, ammediol, 1,4-butyleneglycol or polyoxyethylene glycol.Quaternary ammonium compound is tetraethyl ammonium hydroxide or TMAH in the said titanium catalyst.
Said magnesium compound is magnesium oxalate, propionic acid magnesium, vinylformic acid magnesium, magnesium acetate, Magnesium Stearate, Marinco H, sal epsom or magnesium chloride.
Said organo phosphorous compounds stablizer is phosphoric acid, tricresyl phosphate methyl, tricresyl phosphate ethyl, tricresyl phosphate phenolic aldehyde, phosphorous acid, tricresyl phosphite methyl, methyl-phosphorous acid, phenolic aldehyde phosphonic acids, phenylbenzene phosphonic acids, methyl methylphosphonic acid, phenolic aldehyde phosphinic acid ethyl ester, phenylbenzene phosphonic acids phenolic aldehyde ester or phosphoryl ETHYLE ACETATE.
The addition of titanium elements is preferred 3～10ppm with respect to the polyester total amount in the titanium catalyst.If the addition of titanium elements is greater than 30ppm, because titanium catalyst is active high, side reaction is promoted easily that also resulting polymers stability is bad, its colour changed into yellow; The addition of preferred titanium elements is 3～8ppm, and this moment, thermostability, the tone of polymkeric substance became.
The addition of phosphoric is preferred 10～50ppm with respect to the polyester total amount in the organo phosphorous compounds stablizer.If phosphoric adds to more than the 60ppm, then can excessively suppress the activity of titanium compound, make polymerization reaction time prolong, cause the deterioration of polymkeric substance tone.
Polyester of the present invention can pass through the direct polymerization method, and the DMT manufactured can also be passed through batchwise polymerization method, successive polymerization manufactured.In addition, copolyesters of the present invention can be processed fiber and then form fabric through known method.
The prepared polyester product of the present invention has excellent tone and good thermotolerance; And polymerization process is used titanium catalyst, and little to environmental influence, the pollution that in spinning process, spinning plate surface is caused is little, and the filter pressure is difficult for rising, fracture of wire is few, helps carrying out smoothly of spinning like this.
Embodiment
Below in conjunction with specific embodiment the present invention is described further.In addition, the measuring method of each index of embodiment and comparative example is following:
(1) limiting viscosity [η]
Under 25 ℃, test as solvent with ortho chloro phenol
(2) (the equivalent/ton) of the terminal group carboxy CO OH in the polymkeric substance
, measure on automatic titration device (COM-550 of flat natural pond industry manufactured) with the NaOH aqueous solution of concentration 0.02mol/L down as solvent with Ortho Cresol at 25 ℃.
(3) tone L/b value
Measure by GB GB/T 14190-1993
(4)％BB
*
Backbone breaking rate (numerical value is high more, and thermotolerance is poor more)
In the nitrogen, 300 ℃, heat treated 6hr carries out the η pH-value determination pH.
(5) observation of spinning jet place stores
290 ℃ of following fusions, the spinning orifice of 12 of 0.35mm Φ, hole count spues from the aperture with polyester.Use long focusing microscope to observe to spinning the orifice of fiber after 72 hours stores amount on every side.With condition judgement that almost can't see stores is A, although will can see stores but still exercisable condition judgement is B, can the condition judgement of seeing stores and fracture of wire frequently taking place is C.
The concrete numerical value of each embodiment and comparative example is seen table 1.
Embodiment 1
Bishydroxyethyl terephthalate is added the esterification groove, keep 250 ℃ of temperature, pressure 1.2 * 10
5Pa joined the esterification layer gradually with the high purity terephthalic acid of 8.25kg and the terepthaloyl moietie slurry of 3.54kg in 4 hours, carry out 1 hour esterification again.From the reactant of esterification that obtains, get 10.2kg at last and join the polycondensation layer.
Esterification reaction product is remained under 250 ℃, normal pressure; Add titanium-containing catalyst, the magnesium compound mix and the mixed solution that phosphonium stabilizer is arranged (mixed solution compound method: a certain amount of titanium catalyst of weighing, magnesium compound and the phosphorus stabilizer immunomodulator compounds is arranged; Add certain amount of solvent terepthaloyl moietie; Mix and stirred 1 hour, to reach mixed uniformly purpose), begin decompression after 5 minutes, heat up.Temperature rises to 290 ℃, pressure by 250 ℃ and reduces to 40Pa.Reach outlet temperature, resulting pressure after 90 minutes.After arriving certain stirring extent, in reaction system, import nitrogen and be back to normal pressure, stop polycondensation.Polymkeric substance is strip and spues, cooling back section in tank.
Make its moisture rate remain on 50ppm the chip drying that obtains, melt-spinning under 290 ℃ spinning temperature then, portion spues from filament spinning component, batches with the pulling speed of 3000m.In the operation of melt-spinning, stores and filter around the orifice when almost not finding spinning press liter.
The amount of catalyzer, polymer performance and spinning properties are seen table 1 in the resulting polymers.
Embodiment 2～embodiment 6
Prepare polyester with embodiment 1 method, the amount of catalyzer and additive in the change polyester.Make its moisture rate remain on 50ppm the chip drying that obtains, melt-spinning under 290 ℃ spinning temperature then, portion spues from filament spinning component, batches with the pulling speed of 3000m.Observe spinning nozzle stores and filter on every side and press liter.The addition and the result of concrete catalyzer and additive see table 1.
Comparative example 1
Prepare polyester with embodiment 1 method, just addition and the addition manner with catalyzer among the embodiment and additive changes to 5 minutes pitch times by mixing to add, and is added with phosphonium stabilizer, magnesium compound and titanium compound successively.Make its moisture rate remain on 50ppm the chip drying that obtains, melt-spinning under 290 ℃ spinning temperature then, portion spues from filament spinning component, batches with the pulling speed of 3000m.Observe spinning nozzle stores and filter on every side and press liter.Concrete addition transitivity result sees table 1.
Comparative example 2
Prepare polyester with embodiment 1 method, be added with phosphonium stabilizer, magnesium compound and antimony compounds successively, 5 minutes pitch times.Make its moisture rate remain on 50ppm the chip drying that obtains, melt-spinning under 290 ℃ spinning temperature then, portion spues from filament spinning component, batches with the pulling speed of 3000m.Observe spinning nozzle stores and filter on every side and press liter.Concrete addition and result see table 1.
Claims (10)
1. a polyester is characterized in that: add titanium catalyst, magnesium compound, organo phosphorous compounds stablizer in the polyester building-up process; Contain titanium compound, aliphatic dihydroxy alcohol, quaternary ammonium compound in the titanium catalyst, and the addition of titanium elements is 1～30ppm with respect to the polyester total amount in this titanium catalyst; The addition of magnesium elements is 10～80ppm with respect to the polyester total amount in the magnesium compound; The addition of phosphoric is 5～60ppm with respect to the polyester total amount in the organo phosphorous compounds stablizer; The intrinsic viscosity of said polyester is 0.50～0.80, and terminal carboxyl(group) content is below the 30eq/ton, and polyethyleneglycol content is below the 1.2wt%, and tone b value is below 6.
2. polyester according to claim 1 is characterized in that: titanium catalyst, magnesium compound, organo phosphorous compounds stablizer proportionally add reaction system to after the uniform mixing.
3. polyester according to claim 1 and 2 is characterized in that: the chemical formula of the titanium compound in the titanium catalyst is as follows:
R
1O-[Ti(OR
2)(OR
3)-O-]
n-R
4
R wherein
1, R
2, R
3And R
4Be respectively the alkyl or phenyl of carbonatoms 2～10, can be the same or different, n is 1～6 integer.
4. polyester according to claim 1 and 2 is characterized in that: aliphatic dihydroxy alcohol is a 1,1 in the titanium catalyst, 2-Ucar 35,1, ammediol, 1,4-butyleneglycol or polyoxyethylene glycol.
5. polyester according to claim 1 and 2 is characterized in that: quaternary ammonium compound is tetraethyl ammonium hydroxide or TMAH in the titanium catalyst.
6. polyester according to claim 1 and 2 is characterized in that: magnesium compound is magnesium oxalate, propionic acid magnesium, vinylformic acid magnesium, magnesium acetate, Magnesium Stearate, Marinco H, sal epsom or magnesium chloride.
7. polyester according to claim 1 and 2 is characterized in that: the organo phosphorous compounds stablizer is phosphoric acid, tricresyl phosphate methyl, tricresyl phosphate ethyl, tricresyl phosphate phenolic aldehyde, phosphorous acid, tricresyl phosphite methyl, methyl-phosphorous acid, phenolic aldehyde phosphonic acids, phenylbenzene phosphonic acids, methyl methylphosphonic acid, phenolic aldehyde phosphinic acid ethyl ester, phenylbenzene phosphonic acids phenolic aldehyde ester or phosphoryl ETHYLE ACETATE.
8. polyester according to claim 1 and 2 is characterized in that: the addition of titanium elements is 3～10ppm with respect to the polyester total amount in the titanium catalyst.
9. polyester according to claim 1 and 2 is characterized in that: the addition of phosphoric is 10～50ppm with respect to the polyester total amount in the organo phosphorous compounds stablizer.
10. the application of the described polyester of claim 1 in the preparation fiber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105576917A CN102477147A (en) | 2010-11-25 | 2010-11-25 | Polyester and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105576917A CN102477147A (en) | 2010-11-25 | 2010-11-25 | Polyester and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102477147A true CN102477147A (en) | 2012-05-30 |
Family
ID=46089935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105576917A Pending CN102477147A (en) | 2010-11-25 | 2010-11-25 | Polyester and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058798A (en) * | 2014-06-10 | 2014-09-24 | 陕西喜嘉旺生物科技有限责任公司 | Organic magnesium fertilizer and preparation method thereof |
| CN108505201A (en) * | 2018-04-04 | 2018-09-07 | 湖南七纬科技有限公司 | A kind of easy dye hydrophilic polyesters fabric lining of durable antibiotic and preparation method thereof |
| CN109666136A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The preparation method of the polyester-injected parts of low acetaldehyde |
| CN109721964A (en) * | 2017-10-31 | 2019-05-07 | 丹阳市金长汽车部件有限公司 | A kind of safe and healthy vehicle window film |
| CN109867771A (en) * | 2019-03-27 | 2019-06-11 | 佛山杜邦鸿基薄膜有限公司 | It is a kind of it is low extraction, high-temperature insulation polyester film preparation method |
| CN110117356A (en) * | 2019-05-21 | 2019-08-13 | 中国石油化工股份有限公司 | A kind of preparation method and application of carboxy lower composition containing weight polyester and composition solution |
| WO2022217818A1 (en) * | 2021-04-16 | 2022-10-20 | 浙江桐昆新材料研究院有限公司 | Preparation method and application of titanium-phosphorus catalyst for polyester synthesis |
-
2010
- 2010-11-25 CN CN2010105576917A patent/CN102477147A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058798A (en) * | 2014-06-10 | 2014-09-24 | 陕西喜嘉旺生物科技有限责任公司 | Organic magnesium fertilizer and preparation method thereof |
| CN109666136A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The preparation method of the polyester-injected parts of low acetaldehyde |
| CN109721964A (en) * | 2017-10-31 | 2019-05-07 | 丹阳市金长汽车部件有限公司 | A kind of safe and healthy vehicle window film |
| CN108505201A (en) * | 2018-04-04 | 2018-09-07 | 湖南七纬科技有限公司 | A kind of easy dye hydrophilic polyesters fabric lining of durable antibiotic and preparation method thereof |
| CN109867771A (en) * | 2019-03-27 | 2019-06-11 | 佛山杜邦鸿基薄膜有限公司 | It is a kind of it is low extraction, high-temperature insulation polyester film preparation method |
| CN110117356A (en) * | 2019-05-21 | 2019-08-13 | 中国石油化工股份有限公司 | A kind of preparation method and application of carboxy lower composition containing weight polyester and composition solution |
| WO2022217818A1 (en) * | 2021-04-16 | 2022-10-20 | 浙江桐昆新材料研究院有限公司 | Preparation method and application of titanium-phosphorus catalyst for polyester synthesis |
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Application publication date: 20120530 |