CN106221148A - A kind of method of aluminum-based catalyst catalyzing and synthetizing modified copolyester section - Google Patents
A kind of method of aluminum-based catalyst catalyzing and synthetizing modified copolyester section Download PDFInfo
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- CN106221148A CN106221148A CN201610703911.XA CN201610703911A CN106221148A CN 106221148 A CN106221148 A CN 106221148A CN 201610703911 A CN201610703911 A CN 201610703911A CN 106221148 A CN106221148 A CN 106221148A
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- aluminum
- modified copolyester
- based catalyst
- esterification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
A kind of method that the invention discloses aluminum-based catalyst catalyzing and synthetizing modified copolyester section, the p-phthalic acid that mol ratio is 1:1.2 ~ 2.0 is esterified with dihydroxylic alcohols, aluminum-based catalyst, cobalt compound, after esterification products and blue dyes, orchil, the organic compound stabilizer of phosphorus and a small amount of ethylene glycol polycondensation, nitrogen is utilized to be extruded by melt, through Cast Strip pelletizing, obtaining modified copolyester section, slicing characteristics viscosity 0.77 ~ 0.83dl/g, b value is between 3 ~ 1.5.Modified copolyester product neutralc tint, intrinsic viscosity that the present invention obtains are high, the transparency is good, can be widely applied to the markets such as sheet material, sheet material, high-performance heat shrink films, bottle use.
Description
Technical field
The invention belongs to modified copolyester preparing technical field, particularly to a kind of aluminum-based catalyst catalyzing and synthetizing modified altogether
The method of polyester slice.
Background technology
Modified copolyester refers to use Third monomer that polyethylene terephthalate (PET) is carried out modification by copolymerization, makes
The regularity of PET macromole, by broken ring, prepares the noncrystalline or copolyesters of low-crystallinity.Modified copolyester is mainly used in
The markets such as sheet material, sheet material, high-performance heat shrink films, bottle use.Copolyesters heat shrink films has shrinkage and the printing of excellence
Can, may replace conventional thermal shrink film material pvc (PVC), along with growing to even greater heights of domestic and international environmental protection tide, copolyesters heat
The demand of shrink film will be skyrocketed through undoubtedly.
Most commonly used in polyester synthesis is antimony (Sb) series catalysts, and its price is relatively cheap, but its processing and should
With being unfavorable for environmental protection, and the hue of PET chip produced is partially dark, and therefore its range is greatly limited.Germanium (Ge)
Series catalysts, catalysis activity is moderate, and hue of PET chip is preferable, but its price is relatively costly, is unfavorable for large-scale production.Titanium
(Ti) series catalysts is nontoxic, the feature of environmental protection good, catalyst activity is high, and polyester can be made to have more high brightness and the transparency, but it is raw
It is the most yellow generally to there are form and aspect in the polyester slice of output, limits its development.Aluminum (Al) series catalysts, asepsis environment-protecting, will not bring
Problem of environmental pollution, price is the most relatively cheap, and catalysis activity is high, can shorten the polycondensation time, improves unit production capacity.It is produced
Copolyester section form and aspect are preferable, and transparency and brightness are preferable, have the most wide application prospect.
CN102234370A discloses the method for a kind of aluminum-based catalyst synthesizing polyester section, but its catalyst is only limitted to second
Two aluminium alcoholates.CN101962437A discloses the method for aluminum-based catalyst synthesis PET, but it does not synthesize modified copolyester and cuts
Sheet.
Summary of the invention
A kind of method that it is an object of the invention to provide aluminum-based catalyst catalyzing and synthetizing modified copolyester section, makes polymerization anti-
Answering speed to accelerate, technique is simple, it is simple to industrialization, and prepared copolyester section possesses neutralc tint.
For reaching above-mentioned purpose, this invention takes following technical scheme:
A kind of method of aluminum-based catalyst catalyzing and synthetizing modified copolyester section, comprises the steps:
1) esterification
By p-phthalic acid that mol ratio is 1:1.2 ~ 2.0 and dihydroxylic alcohols, in modified copolyester gross mass content be 100 ~
The aluminum-based catalyst of 800ppm, in modified copolyester gross mass content be 50 ~ 300ppm cobalt compound put into making beating still in,
Break into after slurry in delivery pump adds reactor, under 0.15 ~ 0.4MPa nitrogen pressure, carry out esterification at 235 ~ 260 DEG C anti-
Should, esterification stir speed (S.S.) is 30rpm, and esterification time is 140 min ~ 180 min, and the ethylene glycol formed in esterification reaction process steams
Vapour separates via distillation column with water vapour, flows into esterification water and receive tank after overhead vapor stream is condensed, and the ethylene glycol at the bottom of tower returns again
Flowing in esterifying kettle, when overhead temperature declines, esterification terminates, and prepares esterification reaction product；
2) polycondensation reaction
Utilize 0.3MPa nitrogen pressure, by the esterification reaction product that step 1) prepares with content in modified copolyester gross mass be
The blue dyes of 0.5 ~ 5ppm, in modified copolyester gross mass content be the orchil of 0.5 ~ 4ppm, at modified copolyester
During in gross mass, content is the organic compound stabilizer of the phosphorus of 100-600ppm and 100g ethylene glycol press-in reactor, 260 ~
270 DEG C, under 40rpm stirring, by continuous for reactor evacuation while stirring, in 30 ~ 40min, by Stress control in still 200
~ 600Pa, constantly has dihydroxylic alcohols to deviate from during this, then in 30 ~ 50min, by Stress control in still in below 60Pa, control
Reaction temperature processed is at 270 ~ 280 DEG C, after stirring motor current value arrives 5.2 ~ 7.2A, terminates stirring, utilizes nitrogen by melt
Extrude, through Cast Strip pelletizing, obtain modified copolyester section.
Wherein, during the aluminum-based catalyst in step 1) is aluminum acetate, eston, ethylene glycol aluminum, aluminum isopropylate.
Kind.
Dihydroxylic alcohols in step 1) be neopentyl glycol, 1,4-CHDM, isosorbide, 2,2,4,4-tetramethyls-
One or more in 1,3-cyclobutanediol.
One during cobalt compound is cobaltous acetate tetrahydrate, cobalt nitrate, C.I. Pigment Violet 14 in step 1).
Step 2) in the organic compound of phosphorus be the one in trimethyl phosphate, triethyl phosphate, triphenyl phosphate.
Step 2) in blue dyes be Anthraquinones organic compound, following structure:
Wherein R and R1 be carbon atom number be the alkyl of 1 ~ 3
Step 2) in orchil be Anthraquinones organic compound, following structure:
One during wherein R is methyl, ethyl or methoxyl group
Beneficial effects of the present invention: the modified copolyester product obtained by the present invention carries out performance survey by GB/T 14190-2008
Examination, obtained result is as follows: intrinsic viscosity 0.77 ~ 0.83dl/g, b value is between-3 ~ 1.5, and the modification that the present invention obtains is altogether
Polyester product neutralc tint, intrinsic viscosity is high, the transparency is good, can be widely applied to sheet material, sheet material, high-performance heat shrink films,
The markets such as bottle use.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but the present invention is not only limited to these embodiments.
Except as otherwise noted, in embodiment, all of parts and percentages is all on the basis of the quality of modified copolyester.
Example formulations table
Embodiment 1
By list of ingredients, p-phthalic acid, ethylene glycol, neopentyl glycol, aluminum acetate and cobaltous acetate four hydrate are added still of pulling an oar
In, break into after slurry in delivery pump imports reactor, under 0.2MPa nitrogen pressure, at 255 DEG C, carry out esterification, esterification
Stir speed (S.S.) is 30rpm.After reacting 150 min, collecting esterification water 4.2 kg, esterification terminates.
Utilize 0.3MPa nitrogen pressure, by above-mentioned esterification reaction product press-in polycondensation vessel.By list of ingredients by ethylene glycol, (R
=1, R1=1) blue dyes, R are that the orchil of methyl, trimethyl phosphate are made solution and joined in polycondensation vessel, 265
DEG C, under 40rpm stirring, by continuous for polycondensation vessel evacuation, in 40 min, it is 200 Pa by Stress control in still, then 30
In min, by Stress control in still at 50 Pa, control reaction temperature is at 275 DEG C, when stirring motor current value arrives 5.2 A, eventually
Only stirring, utilizes nitrogen to be extruded by melt, through Cast Strip pelletizing, obtains modified copolyester section.The intrinsic viscosity of section is
0.83dl/g, b value is-1.5.
Embodiment 2
By list of ingredients, p-phthalic acid, ethylene glycol, 1,4 cyclohexane dimethanol, eston, cobalt nitrate are put into making beating still
In, break into after slurry in delivery pump adds reactor still, under 0.3MPa nitrogen pressure, at 235 DEG C, carry out esterification, ester
Change stir speed (S.S.) is 30rpm, after 40 min, collects esterification water 3.9 kg, and esterification terminates.
Utilize 0.3MPa nitrogen pressure, by above-mentioned esterification reaction product press-in polycondensation vessel.By list of ingredients by ethylene glycol, (R
=2, R1=3) blue dyes, R are that the orchil of ethyl, triphenyl phosphate are made solution and joined in polycondensation vessel, 260
DEG C, under 40rpm stirring, by continuous for polycondensation vessel evacuation, in 30 min, it is 500 Pa by Stress control in still, then 40
In min, by Stress control in still at 30 Pa, control reaction temperature is at 270 DEG C, when stirring motor current value arrives 5.7 A, eventually
Only stirring, utilizes nitrogen to be extruded by melt, through Cast Strip pelletizing, obtains modified copolyester section.The intrinsic viscosity of section is
0.77dl/g, b value is-0.5.
Embodiment 3
By list of ingredients, p-phthalic acid, ethylene glycol, isosorbide, ethylene glycol aluminum, cobaltous acetate tetrahydrate are put in making beating still,
Breaking into after slurry in delivery pump adds reactor, under 0.15MPa nitrogen pressure, carry out esterification at 258 DEG C, esterification is stirred
Mixing speed is 30rpm.After reacting 180 min, collecting on esterification water 4.2 kg, esterification terminates.
Utilize 0.3MPa nitrogen pressure, by above-mentioned esterification reaction product press-in polycondensation vessel.By list of ingredients by ethylene glycol, (R
=3, R1=1) blue dyes, R are that the orchil of methoxyl group, triethyl phosphate are made solution and joined in polycondensation vessel, 265
DEG C, under 40rpm stirring, by continuous for polycondensation vessel evacuation, in 30 min, it is 400 Pa by Stress control in still, then 40
In min, by Stress control in still at 60 Pa, control reaction temperature is at 280 DEG C, when stirring motor current value arrives 7.2 A, eventually
Only stirring, utilizes nitrogen to be extruded by melt, through Cast Strip pelletizing, obtains modified copolyester section.The intrinsic viscosity of section is
0.81dl/g, b value is 1.5.
Embodiment 4
By list of ingredients by p-phthalic acid, ethylene glycol, 1,4 cyclohexane dimethanol (CHDM), isosorbide, aluminum isopropylate., phosphoric acid
Cobalt puts in making beating still, breaks into after slurry in delivery pump adds reactor, under 0.4 MPa nitrogen pressure, carries out at 260 DEG C
Esterification, esterification stir speed (S.S.) is 30rpm.After reacting 180 min, collecting esterification water 4.0 kg, esterification terminates.
Utilize 0.3MPa nitrogen pressure, by above-mentioned esterification reaction product press-in polycondensation vessel.By list of ingredients by ethylene glycol, (R
=2, R1=2) blue dyes, R are that the orchil of methoxyl group, triphenyl phosphate are made solution and joined in polycondensation vessel, 270
DEG C, under 40rpm stirring, by continuous for polycondensation vessel evacuation, in 40 min, it is 600 Pa by Stress control in still, then 50
In min, by Stress control in still at 30 Pa, control reaction temperature is at 280 DEG C, when stirring motor current value arrives 7.0 A, eventually
Only stirring, utilizes nitrogen to be extruded by melt, through Cast Strip pelletizing, obtains modified copolyester section.The intrinsic viscosity of section is
0.82dl/g, b value is-3.0.
Embodiment 5
By list of ingredients by p-phthalic acid, ethylene glycol, TMCBD, 1,4-CHDM
(CHDM), eston, cobaltous acetate four hydrate put in making beating still, break into and add reactor through delivery pump after slurry
In, under 0.35MPa nitrogen pressure, at 255 DEG C, carrying out esterification, esterification stir speed (S.S.) is 30rpm.After reacting 180 min,
Collecting esterification water 4.1 kg, esterification terminates.
Utilize 0.3MPa nitrogen pressure, by above-mentioned esterification reaction product press-in polycondensation vessel.By list of ingredients by ethylene glycol, (R
=2, R1=2) blue dyes, R are that the orchil of methoxyl group, triphenyl phosphate are made solution and joined in polycondensation vessel, 270
DEG C, under 40rpm stirring, by continuous for polycondensation vessel evacuation, in 40 min, it is 600 Pa by Stress control in still, then 50
In min, by Stress control in still at 30 Pa, control reaction temperature is at 277 DEG C, when stirring motor current value arrives 7.2 A, eventually
Only stirring, utilizes nitrogen to be extruded by melt, through Cast Strip pelletizing, obtains modified copolyester section.The intrinsic viscosity of section is
0.82dl/g, b value is-1.0.
Can be drawn by embodiment 1～5, modified copolyester product neutralc tint, intrinsic viscosity that the present invention obtains are high, thoroughly
Bright property is good, can be widely applied to the markets such as sheet material, sheet material, high-performance heat shrink films, bottle use.
Claims (7)
1. the method for an aluminum-based catalyst catalyzing and synthetizing modified copolyester section, it is characterised in that described dicing method includes
Following steps:
1) esterification
By p-phthalic acid that mol ratio is 1:1.2 ~ 2.0 and dihydroxylic alcohols, in modified copolyester gross mass content be 100 ~
The aluminum-based catalyst of 800ppm, in modified copolyester gross mass content be 50 ~ 300ppm cobalt compound put into making beating still in,
Break into after slurry in delivery pump adds reactor, under 0.15 ~ 0.4MPa nitrogen pressure, carry out esterification at 235 ~ 260 DEG C anti-
Should, esterification stir speed (S.S.) is 30rpm, and esterification time is 140 min ~ 180 min, and the ethylene glycol formed in esterification reaction process steams
Vapour separates via distillation column with water vapour, flows into esterification water and receive tank after overhead vapor stream is condensed, and the ethylene glycol at the bottom of tower returns again
Flowing in esterifying kettle, when overhead temperature declines, esterification terminates, and prepares esterification reaction product；
2) polycondensation reaction
Utilize 0.3MPa nitrogen pressure, by the esterification reaction product that step 1) prepares with content in modified copolyester gross mass be
The blue dyes of 0.5 ~ 5ppm, in modified copolyester gross mass content be the orchil of 0.5 ~ 4ppm, at modified copolyester
During in gross mass, content is the organic compound stabilizer of the phosphorus of 100-600ppm and 100g ethylene glycol press-in reactor, 260 ~
270 DEG C, under 40rpm stirring, by continuous for reactor evacuation while stirring, in 30 ~ 40min, by Stress control in still 200
~ 600Pa, constantly has dihydroxylic alcohols to deviate from during this, then in 30 ~ 50min, by Stress control in still in below 60Pa, control
Reaction temperature processed is at 270 ~ 280 DEG C, after stirring motor current value arrives 5.2 ~ 7.2A, terminates stirring, utilizes nitrogen by melt
Extrude, through Cast Strip pelletizing, obtain modified copolyester section.
A kind of method of aluminum-based catalyst catalyzing and synthetizing modified copolyester section, it is characterised in that:
One during aluminum-based catalyst is aluminum acetate, ethylene glycol aluminum, aluminum isopropylate., eston in described step 1).
The method of a kind of aluminum-based catalyst catalyzing and synthetizing modified copolyester section the most according to claim 1, its feature exists
In: the dihydroxylic alcohols in described step 1) is neopentyl glycol, 1,4-CHDM, isosorbide, 2,2,4,4-tetramethyl-1,
One or more in 3-cyclobutanediol.
The method of a kind of aluminum-based catalyst catalyzing and synthetizing modified copolyester section the most according to claim 1, its feature exists
In: the cobalt compound in described step 1) is the one in cobaltous acetate tetrahydrate, cobalt nitrate, C.I. Pigment Violet 14.
The method of a kind of aluminum-based catalyst catalyzing and synthetizing modified copolyester section the most according to claim 1, its feature exists
In described step 2) in the organic compound of phosphorus be the one in trimethyl phosphate, triethyl phosphate, triphenyl phosphate.
The method of a kind of aluminum-based catalyst catalyzing and synthetizing modified copolyester section the most according to claim 1, its feature exists
In described step 2) in blue dyes be Anthraquinones organic compound, following structure:
Wherein R and R1 be carbon atom number be the alkyl of 1 ~ 3.
The method of a kind of aluminum-based catalyst catalyzing and synthetizing modified copolyester section the most according to claim 1, its feature exists
In described step 2) in orchil be Anthraquinones organic compound, following structure:
One during wherein R is methyl, ethyl or methoxyl group.
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Citations (7)
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|---|---|---|---|---|
| CN1147824A (en) * | 1994-12-22 | 1997-04-16 | 伊斯曼化学公司 | Production of particular polyesters using a novel catalyst system |
| CN101210067A (en) * | 2006-12-29 | 2008-07-02 | 财团法人工业技术研究院 | Amorphous copolyester and application thereof |
| CN101263175A (en) * | 2005-09-14 | 2008-09-10 | 东洋纺织株式会社 | Polyester, process for production of polyester, and polyester molded article |
| CN101962437A (en) * | 2009-07-24 | 2011-02-02 | 常州化学研究所 | Novel aluminum catalyst for use in synthesis of PET by esterification condensation method |
| CN103772673A (en) * | 2013-06-13 | 2014-05-07 | 淄博晓光化工材料有限公司 | Method for synthesizing PET polyester chips by using titanium catalyst |
| CN104497290A (en) * | 2014-11-13 | 2015-04-08 | 哈尔滨工业大学无锡新材料研究院 | Optical fluorine-containing copolyester, optical film and production method thereof |
| CN105061738A (en) * | 2015-07-29 | 2015-11-18 | 无锡博强高分子材料科技有限公司 | Polyester type UV-cured acrylic acid monomer, preparation method and applications thereof |
-
2016
- 2016-08-23 CN CN201610703911.XA patent/CN106221148A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147824A (en) * | 1994-12-22 | 1997-04-16 | 伊斯曼化学公司 | Production of particular polyesters using a novel catalyst system |
| CN101263175A (en) * | 2005-09-14 | 2008-09-10 | 东洋纺织株式会社 | Polyester, process for production of polyester, and polyester molded article |
| CN101210067A (en) * | 2006-12-29 | 2008-07-02 | 财团法人工业技术研究院 | Amorphous copolyester and application thereof |
| CN101962437A (en) * | 2009-07-24 | 2011-02-02 | 常州化学研究所 | Novel aluminum catalyst for use in synthesis of PET by esterification condensation method |
| CN103772673A (en) * | 2013-06-13 | 2014-05-07 | 淄博晓光化工材料有限公司 | Method for synthesizing PET polyester chips by using titanium catalyst |
| CN104497290A (en) * | 2014-11-13 | 2015-04-08 | 哈尔滨工业大学无锡新材料研究院 | Optical fluorine-containing copolyester, optical film and production method thereof |
| CN105061738A (en) * | 2015-07-29 | 2015-11-18 | 无锡博强高分子材料科技有限公司 | Polyester type UV-cured acrylic acid monomer, preparation method and applications thereof |
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