CN115181256B - Cage-shaped polysilsesquioxane titanium catalyst, liquid catalyst, preparation method and application thereof - Google Patents
Cage-shaped polysilsesquioxane titanium catalyst, liquid catalyst, preparation method and application thereof Download PDFInfo
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- 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
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- 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
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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Abstract
The application relates to a cage-shaped polysilsesquioxane titanium catalyst, a liquid catalyst, a preparation method and application thereof, wherein the structural formula of the cage-shaped polysilsesquioxane titanium catalyst is as follows
Description
Technical Field
The application belongs to the technical field of catalysts, and relates to a cage-shaped polysilsesquioxane titanium catalyst, a liquid catalyst, a preparation method and application thereof.
Background
The antimony catalyst used in the polyester has certain carcinogenicity, and under the high-temperature condition, antimony can migrate out of polyester clothes, beverage bottles and packaging films which are used by people in daily life, thereby threatening the health and ecological environment of human beings. Thus, GBT18885 specifies: the leaching amount of antimony in each kilogram of fabric cannot exceed 30 milligrams. In recent years, along with popularization of related policies, manufacturers and industry association pay more attention to green ecology and environmental protection, and each party gradually forms a consensus of 'antimony for changing titanium', but many titanium-based polyester catalysts can make final finished products look yellow and form more carboxyl end compounds, and have certain influence on product quality and influence on production line application, especially on a high-capacity melt direct spinning polyester production line with capacity of over hundred thousand tons due to thermal degradation rate of the titanium-based polyester catalysts in polymerization reaction being about 2 times of that of antimony.
The prior art often avoids the generation of more side reaction products by reducing the active center point of the titanium atom of the titanium-based polyester catalyst, and the ways of reducing the active center point of the titanium atom often include:
(1) Forming a complex by titanium with a reactive oxygen-containing group compound, such as titanium acetylacetonate with acetylacetonate;
(2) The active site of titanium formation is reduced by loading or combining the titanium compound with an inorganic compound, such as a titanium silicon compound that reacts with a silicon compound to form an oxidized or hydrogen oxidized titanium silicon compound.
However, the content of side reaction products still remains to be further reduced by using the titanium-based polyester catalyst of the prior art.
Disclosure of Invention
The application aims to solve the problems in the prior art and provides a cage-shaped polysilsesquioxane titanium catalyst, a liquid catalyst, a preparation method and application thereof.
In order to achieve the above purpose, the application adopts the following technical scheme:
the cage-shaped polysilsesquioxane titanium catalyst has the following structural formula:
wherein R is a functional group with amino, hydroxyl and carboxyl, wherein the amino, hydroxyl or carboxyl has better reactivity with the titanium compound, and the functional group as a connecting functional group of titanium atom has chelation stability, which is beneficial to the hydrolysis resistance of the titanium catalyst.
The cage-shaped polysilsesquioxane titanium catalyst is a titanium polyester catalyst generated by the reaction of cage-shaped polysilsesquioxane and a titanium compound. The cage polysilsesquioxane is a polyhedral nano-structure hybridization system formed by silicon atoms, and the titanium polyester catalyst generated by the reaction of the titanium compound and the cage polysilsesquioxane has excellent catalytic effects on esterification and polymerization of polyester synthesis. Compared with the titanium polyester catalyst in the prior art, the cage-shaped polysilsesquioxane titanium catalyst has the advantages of moderate steric hindrance, outstanding electron donating ability and excellent dispersion performance, and can avoid more side reaction products.
As a preferable technical scheme:
the cage-shaped polysilsesquioxane titanium catalyst has uniform particle size, is caused by the structure of the catalyst, is an inorganic core composed of silicon frameworks alternately connected by Si-O, has the shape like a cage, and is named as cage-shaped polysilsesquioxane, the three-dimensional size of the cage-shaped polysilsesquioxane is between 1 and 3nm, the distance between Si atoms is 0.5nm, the distance between R groups is 1.5nm, and the cage-shaped polysilsesquioxane titanium catalyst belongs to nano compounds; because POSS is an organic-inorganic hybrid material, the outside of an inorganic inner core is covered by organic groups, the POSS is easy to disperse, and the POSS organic groups in the catalyst are in a dissolved state and simultaneously keep an inorganic nano inorganic skeleton structure, so that the POSS is nano particles in the catalyst;
the system of the cage-shaped polysilsesquioxane titanium catalyst is strong in compatibility, and the POSS consists of an inorganic core and an organic shell, and the organic shell and a high polymer material are close in polarity, so that the POSS has good compatibility;
the cage-shaped polysilsesquioxane titanium catalyst has good hydrolysis resistance and storage stability, because each Ti atom is connected with organic groups of four POSS functional groups (with certain water repellency) and forms a stable annular structure with an inorganic core, the bond energy is larger, and the catalyst is difficult to be solvated by water molecules; the hydrolysis rate of titanium is lower than 0.5% after the cage polysilsesquioxane titanium catalyst is hydrolyzed for 100 hours at 90 ℃.
The application also provides a liquid catalyst, which comprises dihydric alcohol and a cage-shaped polysilsesquioxane titanium catalyst, wherein the dihydric alcohol is dihydric alcohol used for synthesizing polyester (for example, 1, 3-glycol used for synthesizing PET, 1, 4-butanediol used for synthesizing PBT, PBAT or PBS, and the dihydric alcohol is used as a solution carrier of the cage-shaped polysilsesquioxane titanium catalyst, so that the later use of the cage-shaped polysilsesquioxane titanium catalyst is facilitated, and the structural formula of the cage-shaped polysilsesquioxane titanium catalyst is as follows:
wherein R is a functional group with amino, hydroxyl and carboxyl.
As a preferable technical scheme:
as for the liquid catalyst, the titanium content of the liquid catalyst is 0.1-10wt%, and the titanium content of the liquid catalyst is not too low, otherwise, the adding amount of the liquid catalyst is too high in use, so that waste is caused.
The liquid catalyst also comprises a phosphorus compound, wherein the content of the phosphorus compound in the liquid catalyst is 3-10wt%, the phosphorus compound can inhibit the color development of polyester when the subsequent liquid catalyst is applied to a polyester synthesis system, and the content of the phosphorus compound in the liquid catalyst is controlled within the range, so that the influence on the reaction activity of the catalyst caused by the excessively high content can be avoided, and the poor effect of inhibiting the yellowing of polyester caused by the excessively low content can be avoided.
The liquid catalyst is a liquid catalyst, and the phosphorus compound is trimethyl phosphate, triethyl phosphate, triphenyl phosphite or phosphoric acid.
The liquid catalyst also comprises an acid regulator, the pH value of the liquid catalyst is 4-6.8, and the acid regulator can enable the liquid catalyst to be acidic, so that the hydrolysis resistance of the caged polysilsesquioxane titanium catalyst is improved.
The liquid catalyst as described above, the acid regulator is citric acid, malic acid, tartaric acid, lactic acid, acetic acid, propionic acid or trimellitic acid.
The application also provides a method for preparing the liquid catalyst, which comprises the steps of mixing dihydric alcohol, cage polysilsesquioxane, titanium compound and ethanol, reacting at 70-90 ℃ for 1-4 h, distilling to remove small molecules, adding an acid regulator and a phosphorus compound into a reaction system, reacting at 80-110 ℃ for 2-8 h, distilling to remove small molecules, and obtaining the liquid catalyst;
six raw materials are used in the preparation process, wherein: the cage-shaped polysilsesquioxane and the titanium compound are used as a main framework for synthesizing the cage-shaped polysilsesquioxane titanium catalyst; the ethanol has the functions of reducing the viscosity of the system and promoting the reaction synthesis, is used as a diluting solvent, and is used for ending the reaction, so that most of ethanol is distilled out finally; the dihydric alcohol is used as a solution carrier of the cage-shaped polysilsesquioxane titanium catalyst, which is beneficial to the later use of the cage-shaped polysilsesquioxane titanium catalyst; the phosphorus compound can inhibit the color development of polyester when the subsequent liquid catalyst is applied to a polyester synthesis system; the acid regulator can make the liquid catalyst acidic, so as to improve the hydrolysis resistance of the cage-shaped polysilsesquioxane titanium catalyst;
wherein the cage polysilsesquioxane is octahydroxyalkyl cage polysilsesquioxane, octaaminoalkyl cage polysilsesquioxane or octacarboxyalkyl cage polysilsesquioxane;
the titanium compound is titanium tetrachloride, n-butyl titanate or tetraisopropyl titanate.
As a preferable technical scheme:
as described above, the alkyl group in the octahydroxyalkyl cage polysilsesquioxane, octaaminoalkyl cage polysilsesquioxane or octacarboxyalkyl cage polysilsesquioxane is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or phenyl.
The application also provides an application of the liquid catalyst, wherein PTA, EG and the liquid catalyst are mixed and then sequentially subjected to esterification, pre-polycondensation and final polycondensation to prepare polyester; the L value of the polyester is 70-85%, the b value is 1.2-4, and the carboxyl end group content is 5-25 mol/t.
As a preferable technical scheme:
in the application, the molar ratio of PTA to EG is 1:1.1-1.6; the mass of titanium element in the liquid catalyst is 5-200 ppm of the theoretical yield of polyester.
By the application, the temperature of the esterification reaction is 230-245 ℃, the pressure is 130-180 KPa, and the time is 120-150 min; the temperature of the pre-polycondensation reaction is 250-260 ℃, the pressure is 1000-2000 Pa, and the time is 80-100 min; the final polycondensation reaction temperature is 280-285 deg.c, pressure is 50-80 Pa and time is 140-160 min.
The beneficial effects are that:
(1) The cage-shaped polysilsesquioxane titanium catalyst is not easy to hydrolyze;
(2) The liquid catalyst has excellent dispersion performance;
(3) The liquid catalyst has high catalytic activity;
(4) The liquid catalyst of the application is used for synthesizing polyester with larger L value and fewer side reaction products.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The application will now be described in more detail with the aid of the following examples.
Analysis of the quality of the polyester was carried out with reference to the GB/T14190-1993 method for analysis of fiber-grade polyester chips.
The intrinsic viscosity of the polyester was measured in a phenol-tetrachloroethane mixture (mass ratio 1:1) at 25 ℃.
The hue of the polyester is used as an evaluation standard by using an L, a and b color system, wherein L is a brightness factor, a and b are color measurement numbers, and b value represents yellow-blue balance, has very important significance on the color of the polyester, and the lower the b value is, the better the hue of the polyester is, especially for a fiber-forming polyester chip.
The main components of the liquid catalysts prepared in examples 1 to 9 below were ethylene glycol and a cage-like polysilsesquioxane titanium catalyst, wherein the structural formula of the cage-like polysilsesquioxane titanium catalyst is as follows:
wherein R is a functional group with amino, hydroxyl and carboxyl.
Example 1
A method for preparing a liquid catalyst comprises the steps of mixing 127.5g of ethylene glycol, 10.02g of octahydroxybutyl polyhedral oligomeric silsesquioxane, 6.8g of n-butyl titanate and 50g of ethanol, reacting for 3 hours at 90 ℃, distilling to remove small molecules, adding 3.189g of citric acid and 28.1g of triethyl phosphate into a reaction system, reacting for 2.5 hours at 80 ℃, and distilling to remove the small molecules, thus obtaining the liquid catalyst with the titanium content of 0.726 wt%.
The main components of the liquid catalyst are glycol and cage-shaped polysilsesquioxane titanium catalyst, and the hydrolysis rate of titanium of the cage-shaped polysilsesquioxane titanium catalyst is 0.16 percent after a hydrolysis resistance test at 90 ℃ for 100 hours.
Example 2
A method for preparing a liquid catalyst comprises the steps of mixing 127.5g of ethylene glycol, 9.977g of octaaminobutyl cage polysilsesquioxane, 5.76g of tetraisopropyl titanate and 50g of ethanol, reacting for 3 hours at 90 ℃ and distilling to remove small molecules, adding 3.189g of citric acid and 28.1g of triethyl phosphate into a reaction system, reacting for 2.5 hours at 80 ℃ and distilling to remove the small molecules, and obtaining the liquid catalyst with the titanium content of 0.985 wt%.
The main components of the liquid catalyst are glycol and cage-shaped polysilsesquioxane titanium catalyst, and the hydrolysis rate of titanium of the cage-shaped polysilsesquioxane titanium catalyst is 0.28 percent after a hydrolysis resistance test at 90 ℃ for 100 hours.
Example 3
A method for preparing a liquid catalyst comprises the steps of mixing 127.5g of ethylene glycol, 8.567g of octahydroxypropyl cage-type polysilsesquioxane, 6.8g of n-butyl titanate and 50g of ethanol, reacting for 3 hours at 90 ℃ and distilling to remove small molecules, adding 3.189g of citric acid and 28.1g of triethyl phosphate into a reaction system, reacting for 2.5 hours at 80 ℃ and distilling to remove the small molecules, and thus obtaining the liquid catalyst with the titanium content of 1.035 wt%.
The main components of the liquid catalyst are glycol and cage-shaped polysilsesquioxane titanium catalyst, and the hydrolysis rate of titanium of the cage-shaped polysilsesquioxane titanium catalyst is 0.16 percent after a hydrolysis resistance test at 90 ℃ for 100 hours.
Example 4
A method for preparing a liquid catalyst comprises the steps of mixing 127.5g of ethylene glycol, 8.567g of octahydroxypropyl cage-type polysilsesquioxane, 3.8g of titanium tetrachloride and 50g of ethanol, reacting at 90 ℃ for 3 hours, distilling to remove small molecules, adding 2.68g of malic acid and 21.6g of trimethyl phosphate into a reaction system, reacting at 80 ℃ for 2.5 hours, distilling to remove the small molecules, and obtaining the liquid catalyst with titanium content of 1.123 wt%.
The main components of the liquid catalyst are glycol and cage-shaped polysilsesquioxane titanium catalyst, and the hydrolysis rate of titanium of the cage-shaped polysilsesquioxane titanium catalyst is 0.16 percent after a hydrolysis resistance test at 90 ℃ for 100 hours.
Example 5
A method for preparing a liquid catalyst comprises the steps of mixing 127.5g of ethylene glycol, 9.977g of octaaminobutyl cage polysilsesquioxane, 6.8g of n-butyl titanate and 50g of ethanol, reacting for 3 hours at 90 ℃, distilling to remove small molecules, adding 2.49g of tartaric acid and 50.33g of triphenyl phosphate into a reaction system, reacting for 2.5 hours at 80 ℃, and distilling to remove the small molecules, thus obtaining the liquid catalyst with titanium content of 0.955 wt%.
The main components of the liquid catalyst are glycol and cage-shaped polysilsesquioxane titanium catalyst, and the hydrolysis rate of titanium of the cage-shaped polysilsesquioxane titanium catalyst is 0.28 percent after a hydrolysis resistance test at 90 ℃ for 100 hours.
Example 6
A method for preparing a liquid catalyst comprises the steps of mixing 127.5g of ethylene glycol, 8.567g of octahydroxypropyl cage-type polysilsesquioxane, 5.76g of tetraisopropyl titanate and 50g of ethanol, reacting for 3 hours at 90 ℃ and distilling to remove small molecules, adding 1.5g of lactic acid and 47.87g of triphenyl phosphite into a reaction system, reacting for 2.5 hours at 80 ℃ and distilling to remove the small molecules, and obtaining the liquid catalyst with the titanium content of 0.788 wt%.
The main components of the liquid catalyst are glycol and cage-shaped polysilsesquioxane titanium catalyst, and the hydrolysis rate of titanium of the cage-shaped polysilsesquioxane titanium catalyst is 0.16 percent after a hydrolysis resistance test at 90 ℃ for 100 hours.
Example 7
A method for preparing a liquid catalyst comprises the steps of mixing 127.5g of ethylene glycol, 9.977g of octaaminobutyl cage polysilsesquioxane, 3.8g of titanium tetrachloride and 50g of ethanol, reacting at 90 ℃ for 3 hours, distilling to remove small molecules, adding 1g of acetic acid and 15.11g of phosphoric acid into a reaction system, reacting at 80 ℃ for 2.5 hours, distilling to remove the small molecules, and obtaining the liquid catalyst with titanium content of 0.986 wt%.
The main components of the liquid catalyst are glycol and cage-shaped polysilsesquioxane titanium catalyst, and the hydrolysis rate of titanium of the cage-shaped polysilsesquioxane titanium catalyst is 0.28 percent after a hydrolysis resistance test at 90 ℃ for 100 hours.
Example 8
A method for preparing a liquid catalyst comprises the steps of mixing 127.5g of ethylene glycol, 8.567g of octahydroxypropyl cage-type polysilsesquioxane, 6.8g of n-butyl titanate and 50g of ethanol, reacting for 3 hours at 90 ℃ and distilling to remove small molecules, adding 1.23g of propionic acid and 47.87g of triphenyl phosphite into a reaction system, reacting for 2.5 hours at 80 ℃ and distilling to remove the small molecules, and thus obtaining the liquid catalyst with the titanium content of 0.791 wt%.
The main components of the liquid catalyst are glycol and cage-shaped polysilsesquioxane titanium catalyst, and the hydrolysis rate of titanium of the cage-shaped polysilsesquioxane titanium catalyst is 0.16 percent after a hydrolysis resistance test at 90 ℃ for 100 hours.
Example 9
A method for preparing a liquid catalyst comprises the steps of mixing 127.5g of ethylene glycol, 10.02g of octahydroxybutyl cage polysilsesquioxane, 5.76g of tetraisopropyl titanate and 50g of ethanol, reacting for 3 hours at 90 ℃, distilling to remove small molecules, adding 3.49g of trimellitic acid and 15.11g of phosphoric acid into a reaction system, reacting for 2.5 hours at 80 ℃, and distilling to remove the small molecules, thus obtaining the liquid catalyst with the titanium content of 0.954 wt%.
The main components of the liquid catalyst are glycol and cage-shaped polysilsesquioxane titanium catalyst, and the hydrolysis rate of titanium of the cage-shaped polysilsesquioxane titanium catalyst is 0.16 percent after a hydrolysis resistance test at 90 ℃ for 100 hours.
Example 10
A method for synthesizing polyester comprises the following specific processes: 1661g PTA, 807g EG and 2.38g liquid catalyst prepared in example 1 are mixed and then subjected to esterification, pre-polycondensation and final polycondensation in sequence to obtain polyester, wherein the temperature of the esterification is 238 ℃, the pressure is 145KPa and the time is 126min; the temperature of the pre-polycondensation reaction is 255 ℃, the pressure is 1500Pa, and the time is 85min; the final polycondensation reaction was carried out at a temperature of 285℃and a pressure of 55Pa for 146 minutes.
The intrinsic viscosity of the polyester was 0.682, the melting point was 255.8 ℃, the L value was 81.7, the b value was 2.3, the carboxyl end group content was 8.2mol/t, and the diethylene glycol content was 1.02%.
Comparative example 1
A method for synthesizing polyester is basically the same as in example 10, except that the catalyst is Sb 2 O 3 The catalyst was added in an amount of 0.74g.
The intrinsic viscosity of the polyester was 0.67, the melting point was 258 ℃, the L value was 78.8, the b value was 2.4, the carboxyl end group content was 18.5mol/t, and the diethylene glycol content was 0.99%.
The polyester of comparative example 1 has a higher carboxyl end group content than example 10 because the catalyst of comparative example 1 has no catalytic effect on the esterification reaction, whereas the synthetic catalyst of example 10 has a remarkable catalytic effect on the esterification reaction.
Comparative example 2
A polyester synthesis process was substantially the same as in example 10, except that the catalyst was tetrabutyl titanate and the catalyst was added in an amount of 0.1227g.
The intrinsic viscosity of the polyester was 0.67, the melting point was 258 ℃, the L value was 63.7, the b value was 11.4, the carboxyl end group content was 22.4mol/t, and the diethylene glycol content was 2%.
The polyester of comparative example 2 has a lower L value and a higher b value and a higher carboxyl end group content than those of example 10, and thus the catalyst used in example 10 is known to have better stability and side reaction inhibition.
Example 11
A method for synthesizing polyester comprises the following specific processes: 1661g PTA, 807g EG and 1.754g liquid catalyst prepared in example 2 are mixed and then subjected to esterification, pre-polycondensation and final polycondensation in sequence to obtain polyester, wherein the esterification is carried out at 235 ℃ under 150KPa for 122min; the temperature of the pre-polycondensation reaction is 255 ℃, the pressure is 1800Pa, and the time is 82min; the final polycondensation reaction was carried out at a temperature of 285℃and a pressure of 60Pa for 148 minutes.
The intrinsic viscosity of the polyester was 0.671, the melting point was 256.1 ℃, the L value was 82.3%, the b value was 2.3, the carboxyl end group content was 8.8mol/t, and the diethylene glycol content was 1.04%.
Example 12
A method for synthesizing polyester comprises the following specific processes: 1661g PTA, 807g EG and 1.67g liquid catalyst prepared in example 3 are mixed and then subjected to esterification, pre-polycondensation and final polycondensation in sequence to obtain polyester, wherein the temperature of the esterification is 239 ℃, the pressure is 155KPa and the time is 124min; the temperature of the pre-polycondensation reaction is 255 ℃, the pressure is 1200Pa, and the time is 81min; the final polycondensation reaction was carried out at 283℃and a pressure of 55Pa for 146min.
The intrinsic viscosity of the polyester was 0.676, the melting point was 256.6 ℃, the L value was 82.4%, the b value was 2.2, the carboxyl end group content was 7.9mol/t, and the diethylene glycol content was 0.98%.
Example 13
A method for synthesizing polyester comprises the following specific processes: 1661g PTA, 807g EG and 1.542g liquid catalyst prepared in example 4 are mixed and then subjected to esterification, pre-polycondensation and final polycondensation in sequence to obtain polyester, wherein the temperature of the esterification is 238 ℃, the pressure is 170KPa and the time is 133min; the temperature of the pre-polycondensation reaction is 250 ℃, the pressure is 2000Pa, and the time is 80min; the final polycondensation reaction was carried out at 282℃and a pressure of 65Pa for 155min.
The intrinsic viscosity of the polyester was 0.678, the melting point was 255.5 ℃, the L value was 83.2%, the b value was 1.8, the carboxyl end group content was 7.4mol/t, and the diethylene glycol content was 0.95%.
Example 14
A method for synthesizing polyester comprises the following specific processes: 1661g PTA, 807g EG and 1.814g liquid catalyst prepared in example 5 are mixed and then subjected to esterification, pre-polycondensation and final polycondensation in sequence to obtain polyester, wherein the temperature of the esterification is 243 ℃, the pressure is 145KPa and the time is 132min; the temperature of the pre-polycondensation reaction is 253 ℃, the pressure is 1500Pa, and the time is 88min; the final polycondensation reaction was carried out at a temperature of 285℃and a pressure of 70Pa for 150 minutes.
The intrinsic viscosity of the polyester was 0.684, the melting point was 256.4 ℃, the L value was 82.7%, the b value was 2.1, the carboxyl end group content was 8.2mol/t, and the diethylene glycol content was 1.01%.
Example 15
A method for synthesizing polyester comprises the following specific processes: 1661g PTA, 807g EG and 2.194g liquid catalyst prepared in example 6 are mixed and then subjected to esterification, pre-polycondensation and final polycondensation in sequence to obtain polyester, wherein the temperature of the esterification is 241 ℃, the pressure is 150KPa and the time is 140min; the temperature of the pre-polycondensation reaction is 254 ℃, the pressure is 1000Pa, and the time is 85min; the final polycondensation reaction was carried out at 283℃and a pressure of 65Pa for 143min.
The intrinsic viscosity of the polyester was 0.675, the melting point was 256.2 ℃, the L value was 81.9%, the b value was 2, the carboxyl end group content was 6.9mol/t, and the diethylene glycol content was 1.07%.
Example 16
A method for synthesizing polyester comprises the following specific processes: 1661g PTA, 807g EG and 1.757g liquid catalyst prepared in example 7 are mixed and then subjected to esterification, pre-polycondensation and final polycondensation in sequence to obtain polyester, wherein the temperature of the esterification is 233 ℃, the pressure is 160KPa and the time is 133min; the temperature of the pre-polycondensation reaction is 260 ℃, the pressure is 2000Pa, and the time is 94min; the final polycondensation reaction was carried out at a temperature of 281℃and a pressure of 55Pa for 145 minutes.
The intrinsic viscosity of the polyester was 0.668, the melting point was 255.6 ℃, the L value was 83.5%, the b value was 2.3, the carboxyl end group content was 7.3mol/t, and the diethylene glycol content was 0.98%.
Example 17
A method for synthesizing polyester comprises the following specific processes: 1661g PTA, 807g EG and 2.194g liquid catalyst prepared in example 8 are mixed and then subjected to esterification, pre-polycondensation and final polycondensation in sequence to obtain polyester, wherein the temperature of the esterification is 237 ℃, the pressure is 180KPa and the time is 123min; the temperature of the pre-polycondensation reaction is 255 ℃, the pressure is 2000Pa, and the time is 100min; the final polycondensation reaction was carried out at 284℃and a pressure of 70Pa for 145 minutes.
The intrinsic viscosity of the polyester was 0.676, the melting point was 256.6 ℃, the L value was 82.1%, the b value was 2.1, the carboxyl end group content was 8.4mol/t, and the diethylene glycol content was 1.03%.
Example 18
A method for synthesizing polyester comprises the following specific processes: 1661g PTA, 807g EG and 1.816g liquid catalyst prepared in example 9 are mixed and then subjected to esterification, pre-polycondensation and final polycondensation in sequence to obtain polyester, wherein the temperature of the esterification is 235 ℃, the pressure is 155KPa and the time is 125min; the temperature of the pre-polycondensation reaction is 260 ℃, the pressure is 1700Pa, and the time is 90min; the final polycondensation reaction was carried out at 282℃and a pressure of 75Pa for 148 minutes.
The intrinsic viscosity of the polyester was 0.683, the melting point was 256.8 ℃, the L value was 81.6%, the b value was 1.8, the carboxyl end group content was 7.8mol/t, and the diethylene glycol content was 0.96%.
Claims (9)
1. The liquid catalyst is characterized by comprising dihydric alcohol and a cage-shaped polysilsesquioxane titanium catalyst, wherein the dihydric alcohol is dihydric alcohol used for synthesizing polyester, and the cage-shaped polysilsesquioxane titanium catalyst has the following structural formula:
wherein R is a functional group with amino, hydroxyl and carboxyl;
the preparation method of the liquid catalyst comprises the following steps: mixing dihydric alcohol, cage polysilsesquioxane, titanium compound and ethanol, reacting at 70-90 ℃ for 1-4 h, distilling to remove small molecules, adding an acid regulator and a phosphorus compound into a reaction system, reacting at 80-110 ℃ for 2-8 h, distilling to remove small molecules, and obtaining a liquid catalyst;
wherein the cage polysilsesquioxane is octahydroxyalkyl cage polysilsesquioxane, octaaminoalkyl cage polysilsesquioxane or octacarboxyalkyl cage polysilsesquioxane, and the titanium compound is titanium tetrachloride, n-butyl titanate or tetraisopropyl titanate.
2. The liquid catalyst of claim 1, wherein the titanium hydrolysis rate is less than 0.5% after 100 hours of hydrolysis of the cage polysilsesquioxane titanium catalyst at 90 ℃.
3. The liquid catalyst according to claim 1, wherein the titanium content of the liquid catalyst is 0.1 to 10wt%.
4. The liquid catalyst according to claim 1, further comprising a phosphorus compound, wherein the content of the phosphorus compound in the liquid catalyst is 3 to 10wt%.
5. The liquid catalyst according to claim 1, further comprising an acid regulator, wherein the liquid catalyst has a pH of 4 to 6.8.
6. The method for preparing the liquid catalyst according to any one of claims 1 to 5, which is characterized in that dihydric alcohol, cage polysilsesquioxane, titanium compound and ethanol are mixed and reacted for 1 to 4 hours at 70 to 90 ℃ to distill off small molecules, then an acid regulator and a phosphorus compound are added into a reaction system to react for 2 to 8 hours at 80 to 110 ℃ to distill off small molecules, and the liquid catalyst is obtained;
wherein the cage polysilsesquioxane is octahydroxyalkyl cage polysilsesquioxane, octaaminoalkyl cage polysilsesquioxane or octacarboxyalkyl cage polysilsesquioxane;
the titanium compound is titanium tetrachloride, n-butyl titanate or tetraisopropyl titanate.
7. The method of claim 6, wherein the alkyl group in the octahydroxyalkyl cage polysilsesquioxane, octaaminoalkyl cage polysilsesquioxane or octacarboxyalkyl cage polysilsesquioxane is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or phenyl.
8. The use of a liquid catalyst according to any one of claims 1 to 5, wherein the polyester is produced by mixing PTA, EG and the liquid catalyst, and then sequentially carrying out an esterification reaction, a pre-polycondensation reaction and a final polycondensation reaction; the L value of the polyester is 70-85%, the b value is 1.2-4, and the carboxyl end group content is 5-25 mol/t.
9. The use according to claim 8, wherein the molar ratio of PTA to EG is 1:1.1 to 1.6; the mass of titanium element in the liquid catalyst is 5-200 ppm of the theoretical yield of polyester.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008144735A1 (en) * | 2007-05-21 | 2008-11-27 | Hybrid Plastics, Inc. | Metallized polyhedral oligomeric silsesquioxanes as catalysts for polyurethanes |
| EP2368894A1 (en) * | 2010-03-01 | 2011-09-28 | Evonik Degussa GmbH | Polysilsesquioxane (POSS)-linked Imidazole-based Carbene and Phosphine Ligands for Transition Metal Catalysts |
| CN105793327A (en) * | 2013-10-28 | 2016-07-20 | 亨茨曼国际有限公司 | Synthesis and use of metalized polyhedral oligomeric silsequioxane catalyst compositions |
| CN109320696A (en) * | 2018-10-12 | 2019-02-12 | 华润化学材料科技有限公司 | A kind of polyester composited activator and its preparation and application |
| CN110511383A (en) * | 2019-08-29 | 2019-11-29 | 北京理工大学 | One kind coordination polymer of polyhedral oligomeric silsesquioxane containing zinc and its preparation method and application |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008144735A1 (en) * | 2007-05-21 | 2008-11-27 | Hybrid Plastics, Inc. | Metallized polyhedral oligomeric silsesquioxanes as catalysts for polyurethanes |
| EP2368894A1 (en) * | 2010-03-01 | 2011-09-28 | Evonik Degussa GmbH | Polysilsesquioxane (POSS)-linked Imidazole-based Carbene and Phosphine Ligands for Transition Metal Catalysts |
| CN105793327A (en) * | 2013-10-28 | 2016-07-20 | 亨茨曼国际有限公司 | Synthesis and use of metalized polyhedral oligomeric silsequioxane catalyst compositions |
| CN109320696A (en) * | 2018-10-12 | 2019-02-12 | 华润化学材料科技有限公司 | A kind of polyester composited activator and its preparation and application |
| CN110511383A (en) * | 2019-08-29 | 2019-11-29 | 北京理工大学 | One kind coordination polymer of polyhedral oligomeric silsesquioxane containing zinc and its preparation method and application |
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