CN101328263B - Catalyst for producing polyester - Google Patents
Catalyst for producing polyester Download PDFInfo
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- CN101328263B CN101328263B CN2007100238611A CN200710023861A CN101328263B CN 101328263 B CN101328263 B CN 101328263B CN 2007100238611 A CN2007100238611 A CN 2007100238611A CN 200710023861 A CN200710023861 A CN 200710023861A CN 101328263 B CN101328263 B CN 101328263B
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Abstract
The invention discloses a catalyst for producing polyester, which comprises a titanium compound, a magnesium compound and a trivalent phosphorus compound solution. The catalyst is characterized in that: a trivalent phosphorus compound solution also contains 0.2 to 5 weight percent of phenol and 0 to 30 weight percent of quinquevalent phosphorus compound. The catalyst has apparent advantages, and a polymer produced by the catalyst has good color and luster and good heat resistance.
Description
Technical field:
The present invention relates to produce the catalyzer of polyester.
Background technology:
Polyester; Particularly polyethyleneterephthalate, polytrimethylene terephthalate and polybutylene terephthalate; Because its machinery, physics, chemical property excellence; Characteristics such as, chemical-resistant reagent good, heat-resisting like physical strength, the transparency are good have been widely used in many aspects at present, like spinning short fiber, long filament, as wrapping material, electrically insulating material, sake and other layered products etc.
As the preparation method of polyethyleneterephthalate, under polymerizing catalyst existence, decompression, make this reaction product generation polycondensation obtain the method for the predetermined polymerization degree.Polytrimethylene terephthalate and polybutylene terephthalate are also according to above-mentioned same method preparation.
Well-knownly be: the quality of the speed of reaction of polyreaction and product polyester receives the influence of type of the catalyzer in the polymerization procedure very big.As the polymerizing catalyst of polyethyleneterephthalate, antimony compounds is extensively adopted, because they have excellent catalytic property to polymerization, and tool gained polyester has good color tone.In general, polyester film is with polymerization polymkeric substance once fusion system film once more during film in system.Yet when making catalyzer with antimony compounds; Antimony is precipitated out in polycondensation process, when fusion is carried out once more with polymkeric substance, produces the residence time, forms to adhere to and accumulation; Cause filter screen to stop up and bring out filter and press and rise or the film article defective, thereby become problem.And, 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; Tramp material adheres to and is accumulated in the melt-spun mouth of pipe, and causes that the polymer melt of extruding through the mouth of pipe bends, in melt-spun and drawing process; Buckling phenomenon causes the formation of fine hair and the breakage of melt-spun silk, contaminate environment.
As the polyalcohol catalyst of non-antimony compounds, titanium compound is adopted in suggestion, when having adopted titanium compound, can solve the accumulation problem of mouth of pipe tramp material.Yet this catalyzer produces a new defective: gained polyester self tone flavescence also has relatively poor hot melt stability.In order to improve the color harmony heat-resistant stability, generally all can add phosphate compounds.
But the problem points of phosphorus compound is; The thermal stability result of different prices and different types of phosphorus compound is different, and residual dissimilar phosphorus compound contains thing with other in the preparation process of phosphorus compound all can have different influences to thermostability, the prolongation of shelf time; Hydrolysis possibly take place in compound; Bring influence, therefore the thing that contains of phosphorus compound is stipulated, make it in the scope of regulation.
Summary of the invention:
The polyester tone that the purpose of this invention is to provide a kind of production is good, and the production polyester of good heat resistance is used catalyzer.
Technical solution of the present invention is:
A kind of production polyester is used catalyzer, and used catalyzer comprises titanium compound, magnesium compound, trivalent phosphorous compound solution, it is characterized in that: also contain the phenol of 0.2%～5% weight, the pentavalent phosphorous compound of 0%～30% weight in the trivalent phosphorous compound solution.
The sterically hindered phenol Wheat Protein that contains thing phenol a spot ofly contains the effect of playing a kind of composite catalyst, strengthens its oxidation-resistance, but when the phenol amount acquires a certain degree, has changed its composite effect, influences oxidation-resistance on the contrary.Tervalent phosphorus compound decomposes in the phosphorus compound, thereby forms the phosphorus compound of pentavalent, has changed the oxidation-resistance of trivalent phosphorous compound.
Trivalent phosphorous compound is the phosphorous acid esters of following general formula:
R wherein
1, R
2, R
3, R
4Be that carbon is 4～25 alkyl, naphthenic base, arylalkyl or alkylaryl.Example R
1, R
2, R
3, R
4Can be 3-methyl-5-ethyl octane, 2,5-dimethyl--3,4-diethylammonium hexane, lauryl, hard ester group, 2,3,7-trimethylammonium-5-ethyl octane, 2,4-dibutyl phenyl, octyl phenyl, phenyl nonyl, phenyl dihydroxyphenyl propane, phenyl isodecyl etc.
Pentavalent phosphorous compound is the compound of following structural formula:
Wherein R is that carbon is 4～25 alkyl, naphthenic base, arylalkyl or alkylaryl.
Said titanium compound is a kind of metallic compound, and titanium and part form the chelating type structure, and its part is 1～30 ketone group, aldehyde radical, carboxyl or ester group.The example part can be Succinic Acid, hexanodioic acid, adjacent benzene dicarboxylic acid, terephthalic acid, vinyl-acetic ester, methyl-formiate, methyl-malonate, pentyl acetate, methyl phenyl ketone, 2-phenylpropionaldehyde, salicylaldhyde, crotonic aldehyde, 3-phenylacrolein etc.
Magnesium compound is organic acid magnesium or mineral acid magnesium.Organic acid magnesium is magnesium oxalate, propionic acid magnesium, vinylformic acid magnesium, magnesium acetate or Magnesium Stearate; Mineral acid magnesium is Marinco H, sal epsom or magnesium chloride.
The consumption of each component is respectively: the mol ratio of magnesium and phosphorus is 0.1 < Mg/>P < 17 in the catalyzer, with respect to the titanium elements addition of weight polyester be 3ppm Ti 8ppm, the mol ratio of titanium, magnesium sum and phosphorus be 0.3 (Ti+Mg)/>P < 18.
Advantage of the present invention is very tangible, with the polymkeric substance color and luster that this Catalyst Production makes, good heat resistance.
Below in conjunction with embodiment the present invention is described further.
Embodiment:
Embodiment 1:
A kind of catalyzer of producing polyester, catalyzer comprise titanium compound, magnesium compound, trivalent phosphorous compound solution.Titanium compound is the chelating type titanium compound of lactic acid, and in the trivalent phosphorous compound solution, the content that contains thing phenol is 2.0%, and the content that contains the thing pentavalent phosphorous compound is 15%, contains two kinds of compounds that the thing pentavalent phosphorous compound is respectively following structure:
and
Wherein P contained compound is the compound (I) of following general formula
Magnesium compound is magnesium oxalate (or propionic acid magnesium, vinylformic acid magnesium, magnesium acetate, Magnesium Stearate, Marinco H, sal epsom, magnesium chloride).
Concrete reaction process is following:
Under 250 ℃ temperature; Make 166 parts of (weight) terephthalic acids and 75 parts of (weight) terepthaloyl moietie carry out the direct esterification reaction, the gained reaction product is placed the polymerization flask of being furnished with rectifying tower, and titanium compound 5ppm, magnesium compound 40ppm and the above-mentioned trivalent phosphorous compound solution 13ppm (wherein addition is titanium, magnesium, the phosphoric amount addition with respect to weight polyester) that add polymerizing catalyst mix; Under atmospheric pressure be decompressed to about 300Pa through one hour; Temperature was warming up to 290 ℃ through one and a half hours, and when said reaction was accomplished, the temperature in the flask was 290 ℃; Resulting pressure is about 200Pa, and the viscosity of gained polyester is 0.65.
Embodiment 2:
In the trivalent phosphorous compound solution, the content that contains thing phenol is 1.0%, and the content that contains the thing pentavalent phosphorous compound is 15%, and remaining condition is with embodiment 1.
Embodiment 3:
In the trivalent phosphorous compound solution, the content that contains thing phenol is 2.0%, and the content that contains the thing pentavalent phosphorous compound is 4%, and remaining condition is with embodiment 1.
Embodiment 4:
In the trivalent phosphorous compound solution, the content that contains thing phenol is 0.2%, and the content that contains the thing pentavalent phosphorous compound is 15%.
In the concrete reaction process, catalyst consumption is:
Addition with respect to weight polyester is: the addition of titanium elements is 5ppm in the titanium compound
The addition of phosphoric is 13ppm in the phosphorus compound
The addition of magnesium elements is 10ppm in the magnesium compound
All the other are with embodiment 1.
Embodiment 5:
In the trivalent phosphorous compound solution, the content that contains thing phenol is 2.0%, and the content that contains the thing pentavalent phosphorous compound is 12%.
In the concrete reaction process, catalyst consumption is:
Addition with respect to weight polyester is: the addition of titanium elements is 5ppm in the titanium compound
The addition of phosphoric is 13ppm in the phosphorus compound
The addition of magnesium elements is 20ppm in the magnesium compound
All the other are with embodiment 1.
Embodiment 6:
In the trivalent phosphorous compound solution, the content that contains thing phenol is 2.0%, and the content that contains the thing pentavalent phosphorous compound is 15%.
In the concrete reaction process, catalyst consumption is:
Addition with respect to weight polyester is: the addition of titanium elements is 4ppm in the titanium compound
The addition of phosphoric is 13ppm in the phosphorus compound
The addition of magnesium elements is 10ppm in the magnesium compound
Remaining condition is with embodiment 1.
Embodiment 7:
In the trivalent phosphorous compound solution, the content that contains thing phenol is 2.0%, and the content that contains the thing pentavalent phosphorous compound is 30%.
In the concrete reaction process, catalyst consumption is:
Addition with respect to weight polyester is: the addition of titanium elements is 7ppm in the titanium compound
The addition of phosphoric is 13ppm in the phosphorus compound
The addition of magnesium elements is 10ppm in the magnesium compound
Remaining condition is with embodiment 1.
The present invention can also have other suitable embodiment, and example wherein P contained compound is the phosphorous acid esters that the compound of following general formula (I) is represented:
R wherein
1, R
2, R
3, R
4Be that carbon is 4～25 alkyl, naphthenic base, arylalkyl or alkylaryl.R
1, R
2, R
3, R
4Can be 3-methyl-5-ethyl octane, 2,5-dimethyl--3,4-diethylammonium hexane, lauryl, hard ester group, 2,3,7-trimethylammonium-5-ethyl octane, 2,4-dibutyl phenyl, octyl phenyl, phenyl nonyl, phenyl dihydroxyphenyl propane, phenyl isodecyl etc.
Contain two kinds of compounds that the thing pentavalent phosphorous compound is respectively following structure
Wherein R is that carbon is 4～25 alkyl, naphthenic base, arylalkyl or alkylaryl.R can be 3-methyl-5-ethyl octane, 2,5-dimethyl--3,4-diethylammonium hexane, lauryl, hard ester group etc.
Magnesium compound is an organic acid magnesium.Organic acid magnesium is magnesium oxalate, propionic acid magnesium, vinylformic acid magnesium, magnesium acetate or Magnesium Stearate; Mineral acid magnesium is Marinco H, sal epsom or magnesium chloride.
Titanium compound is a kind of metallic compound; Wherein metal is basic metal potassium, sodium, lithium etc.; Titanium and part form the chelating type structure; Its part is 1～30 ketone group, aldehyde radical, carboxyl or ester group, and routine part can be Succinic Acid, hexanodioic acid, adjacent benzene dicarboxylic acid, terephthalic acid, vinyl-acetic ester, methyl-formiate, methyl-malonate, pentyl acetate, methyl phenyl ketone, 2-phenylpropionaldehyde, salicylaldhyde, crotonic aldehyde, 3-phenylacrolein etc.
[comparative example 1]
In the trivalent phosphorous compound solution, the content that contains thing phenol is 0.1%, and the content that contains the thing pentavalent phosphorous compound is 15%, and remaining condition is with embodiment 1.
[comparative example 2]
In the trivalent phosphorous compound solution, the content that contains thing phenol is 2.0%, contains the thing pentavalent phosphorous compound
Content is 35%, and remaining condition is with embodiment 1.
[comparative example 3]
In the trivalent phosphorous compound solution, the content that contains thing phenol is 0%, and the content that contains the thing pentavalent phosphorous compound is 40%, and remaining condition is with embodiment 1.
[comparative example 4]
The catalyzer addition is in the concrete reaction process:
Wherein the addition with respect to weight polyester is:
The addition of antimony element is 110ppm in the Antimony Trioxide: 99.5Min compound
The addition of phosphoric is 16ppm in the phosphate cpd
The addition of magnesium elements is 55ppm in the magnesium acetate compound
The addition of potassium element is 4ppm in the Pottasium Hydroxide compound
Other condition is with the same among the embodiment 1
The measuring method of each index of the foregoing description 1～7, comparative example 1～4 is:
(1) limiting viscosity (IV) (dL/g)
1.6 gram polyester are dissolved in 20 milliliters of phenol, measure its limiting viscosity (IV) down at 25 ℃
(2) carboxyl-content (COOH):
Adopt the optics titration measuring.Polyester is dissolved in the mixed solution (weight ratio 70:30) of neighbour-cresols and chloroform, adds bromthymol blue indicator, neutralize with the ethanolic soln of the Pottasium Hydroxide of 0.05N then and carry out titration
(3) tone L/b value
Measure by GB GB/T14190-1993.
(4) judgement of foreign matter
The section weighing that will observe is good, and cover glass is placed in the well heater, and load weighted section is placed on the cover glass; Put another cover glass, press sample preparation with the cephalomenia of tweezers; After the sample cooling, observe under high power with powerful microscope (NIKON ME600), confirm foreign matter.
(5) contain the mensuration of thing phenol and pentavalent phosphorus content
(GC-14A, SHIMADZU) measure: measuring method is the internal standard method to adopt gc.
Condition determination:
Vaporizer temperature: 300 ℃
Analyzer temperature: 300 ℃
The intensification condition: 50 ℃ of starting temperatures, heat-up rate are 8 ℃/min, and outlet temperature is 300 ℃.
IR: 1ul.
Claims (3)
1. a production polyester is used catalyzer; Used catalyzer comprises titanium compound, magnesium compound, trivalent phosphorous compound solution; It is characterized in that: also contain the phenol of 0.2%～5% weight, the pentavalent phosphorous compound of 4%～30% weight in the trivalent phosphorous compound solution, below pentavalent phosphorous compound is
Wherein R is that carbon is 4～25 alkyl, naphthenic base, arylalkyl or alkylaryl;
Trivalent phosphorous compound is the phosphorous acid esters of following general formula:
R wherein
1, R
2, R
3, R
4Be that carbon is 4～25 alkyl, naphthenic base, arylalkyl or alkylaryl.
2. production polyester according to claim 1 is used catalyzer, it is characterized in that: magnesium compound is organic acid magnesium or mineral acid magnesium.
3. use catalyzer according to the described production polyester of claim 1; It is characterized in that: the consumption of each component is respectively: the mol ratio of magnesium and phosphorus is 0.1＜Mg/P＜17 in the catalyzer; Titanium elements addition with respect to weight polyester is 3ppm＜Ti＜8ppm, and the mol ratio of titanium, magnesium sum and phosphorus is 0.3＜(Ti+Mg)/P＜18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100238611A CN101328263B (en) | 2007-06-22 | 2007-06-22 | Catalyst for producing polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100238611A CN101328263B (en) | 2007-06-22 | 2007-06-22 | Catalyst for producing polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101328263A CN101328263A (en) | 2008-12-24 |
| CN101328263B true CN101328263B (en) | 2012-06-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100238611A Expired - Fee Related CN101328263B (en) | 2007-06-22 | 2007-06-22 | Catalyst for producing polyester |
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| Country | Link |
|---|---|
| CN (1) | CN101328263B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1576292A (en) * | 2003-06-26 | 2005-02-09 | 东丽株式会社 | Polyester production method, polyester composition, and polyester fiber |
| CN1675284A (en) * | 2002-08-05 | 2005-09-28 | 三菱化学株式会社 | Polyester resin and its production process |
-
2007
- 2007-06-22 CN CN2007100238611A patent/CN101328263B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675284A (en) * | 2002-08-05 | 2005-09-28 | 三菱化学株式会社 | Polyester resin and its production process |
| CN1576292A (en) * | 2003-06-26 | 2005-02-09 | 东丽株式会社 | Polyester production method, polyester composition, and polyester fiber |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平7-118381A 1995.05.09 |
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| CN101328263A (en) | 2008-12-24 |
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