CN114106309B - Nano titanium polyester synthesis catalyst and preparation method thereof - Google Patents
Nano titanium polyester synthesis catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN114106309B CN114106309B CN202111516959.7A CN202111516959A CN114106309B CN 114106309 B CN114106309 B CN 114106309B CN 202111516959 A CN202111516959 A CN 202111516959A CN 114106309 B CN114106309 B CN 114106309B
- Authority
- CN
- China
- Prior art keywords
- nano titanium
- titanium dioxide
- catalyst
- mol
- rutile type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- C08G63/87—Non-metals or inter-compounds thereof
Landscapes
- 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
The invention relates to a polyester synthesis catalyst, in particular to a nano titanium polyester synthesis catalyst and a preparation method thereof. Firstly preparing rutile type nano titanium dioxide dispersion liquid, regulating the temperature of the prepared rutile type nano titanium dioxide dispersion liquid, adding silicate aqueous solution, regulating pH value, heat-insulating stirring, then adding titanyl chloride hydrochloric acid solution, continuously heat-insulating stirring, filtering, repeatedly washing to remove impurity ions in filter cake, after washing, drying and pulverizing the obtained filter cake to obtain the nano titanium system polyester synthetic catalyst formed from rutile type titanium dioxide, amorphous titanium dioxide and silicon dioxide. The catalyst has the characteristics of high reaction activity and good hue of the prepared polyester.
Description
Technical Field
The invention relates to a polyester synthesis catalyst, in particular to a nano titanium polyester synthesis catalyst and a preparation method thereof.
Background
Polyesters are a generic term for polymers obtained by polycondensation of polyhydric alcohols and polybasic acids. Mainly refers to thermoplastic resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyarylate and the like, and is an important synthetic fiber raw material and thermoplastic engineering plastic. PET has excellent heat resistance, insulation, resilience, wear resistance, and impact resistance, and is widely used in the fields of fibers, films, packaging materials, electronic and electric appliances, medical hygiene, engineering plastics, and the like.
At present, antimony series, germanium series and titanium series polyester catalysts are mainly applied to synthesis production. The catalyst adopted in 90% of PET production in China is an antimony catalyst with antimony trioxide, antimony acetate and ethylene glycol antimony as main components. Antimony is a heavy metal element, which can adversely affect human and environment during the production, processing, use and recovery of polyester. In recent years, people are more and more conscious of environmental protection, and the requirement for green consumption is higher and higher, so the limit of antimony is stricter and stricter. The use of high-efficiency and environment-friendly catalysts instead of antimony-based catalysts is a necessary trend in the development of the polyester industry.
The germanium catalyst is mainly an organic metal complex of germanium dioxide and germanium, has mild action, less side reaction in the reaction process and stable performance in the production process, but has rare resources and high price, thereby restricting the wide application of the germanium catalyst.
Titanium catalysts are environmentally friendly catalysts, which are classified into the following categories. The first type is mainly titanate and titanate catalysts, and the catalysts have single component, are very easy to hydrolyze, have unstable catalytic effect and have serious yellowing of the product color. The second type is titanium complex catalyst, the components of the catalyst are relatively complex, and most titanium complex catalysts introduce organic acid, so that free hydroxycarboxylic acid in a catalyst system is easy to enter a polymer to cause the increase of the color phase of polyester and the reduction of thermal stability, and simultaneously, the free hydroxycarboxylic acid enters recycled ethylene glycol along with a vacuum system, thereby reducing the quality of the recycled ethylene glycol. The third type is titanium oxide catalyst, which is mainly amorphous and anatase titanium dioxide, and the product still has common yellowing phenomenon. At present, the research on titanium catalysts still focuses on improving the catalytic activity and the product hue.
Disclosure of Invention
The invention provides a nano titanium polyester synthesis catalyst, which consists of rutile titanium dioxide, amorphous titanium dioxide and silicon dioxide, and the specific preparation steps of the material are as follows:
(1) Keeping the temperature at 35-50 ℃, adding titanate into 0.4-1 mol/L titanyl chloride hydrochloric acid solution, cooling to 15-25 ℃ and reacting for 36-72 hours to prepare the rutile type nano titanium dioxide dispersion.
Wherein, the titanate is one of butyl titanate or isopropyl titanate.
The molar ratio of titanate to titanyl chloride is 2-4:1.
(2) Regulating the temperature of the rutile type nano titanium dioxide dispersion liquid prepared in the step (1) to 80-95 ℃, adding 0.3-1.2 mol/l of silicate aqueous solution until the pH value of the system is 9-11, keeping the temperature and stirring for 0.5-1 hour, then adding 0.5-3 mol/l of titanyl chloride hydrochloric acid solution until the pH value of the system is 4-6, and continuing to keep the temperature and stir for 1-2 hours.
(3) Filtering, repeatedly washing to remove impurity ions in the filter cake, finishing washing when the conductivity of the filtrate is less than 100 mu S/cm, drying and crushing the obtained filter cake to obtain the nano titanium polyester synthesis catalyst.
Wherein the silicate is one of sodium silicate or potassium silicate.
Has the beneficial effects that:
the invention simultaneously deposits amorphous titanium dioxide and silicon dioxide on the surface of rutile type nano titanium dioxide to prepare a novel nano titanium polyester synthesis catalyst, the rutile type titanium dioxide and the amorphous titanium dioxide play a role in concerted catalysis under the regulation and control of the silicon dioxide, and the material has the characteristics of high reaction activity and good hue of the product.
Drawings
FIG. 1 is an electron micrograph of a catalyst prepared in example 1 of the present invention;
fig. 2 is an XRD pattern of the catalyst prepared in example 1 of the present invention.
Detailed Description
Example 1
(1) Keeping the reaction temperature of the system at 35 ℃, adding 0.8 mol of isopropyl titanate into 1000 ml of 0.4 mol/L titanyl chloride hydrochloric acid solution, cooling to 15 ℃ and reacting for 72 hours to prepare the rutile type nano titanium dioxide dispersion.
(2) Adjusting the temperature of the rutile type nano titanium dioxide dispersion liquid prepared in the step (1) to 80 ℃, adding 1.2 mol/L sodium silicate aqueous solution until the pH value of the system is 11, stirring for 1 hour under heat preservation, adding 0.5 mol/L titanyl chloride hydrochloric acid solution until the pH value of the system is 6, and continuing stirring for 2 hours under heat preservation.
(3) Filtering, repeatedly washing to remove impurity ions in the filter cake, finishing washing when the conductivity of the filtrate is 95 MuS/cm, drying and crushing the obtained filter cake, and synthesizing the nano titanium polyester catalyst which consists of rutile type nano titanium dioxide, amorphous titanium dioxide and silicon dioxide.
Example 2
(1) Keeping the reaction temperature of the system at 50 ℃, adding 4 mol of isopropyl titanate into 1000 ml of 1 mol/L titanium oxychloride hydrochloric acid solution, cooling to 25 ℃ and reacting for 36 hours to prepare the rutile type nano titanium dioxide dispersion.
(2) Adjusting the temperature of the rutile type nano titanium dioxide dispersion liquid prepared in the step (1) to 95 ℃, adding 0.3 mol/L sodium silicate aqueous solution until the pH value of the system is 9, keeping the temperature and stirring for 0.5 hour, adding 3 mol/L titanyl chloride hydrochloric acid solution until the pH value of the system is 4, and continuing keeping the temperature and stirring for 1 hour.
(3) Filtering, repeatedly washing to remove impurity ions in the filter cake, finishing washing when the conductivity of the filtrate is 83 mu S/cm, drying and crushing the obtained filter cake to obtain the nano titanium polyester synthetic catalyst, wherein the catalyst consists of rutile type nano titanium dioxide, amorphous titanium dioxide and silicon dioxide.
Example 3
(1) Keeping the reaction temperature of the system at 40 ℃, adding 1.8 mol of isopropyl titanate into 1000 ml of 0.6 mol/L titanyl chloride hydrochloric acid solution, cooling to 20 ℃ and reacting for 48 hours to prepare the rutile type nano titanium dioxide dispersion.
(2) Adjusting the temperature of the rutile type nano titanium dioxide dispersion liquid prepared in the step (1) to 90 ℃, adding 1 mol/L sodium silicate aqueous solution until the pH value of the system is 10, stirring for 40 minutes under heat preservation, adding 1.5 mol/L titanyl chloride hydrochloric acid solution until the pH value of the system is 5, and continuing stirring for 1.5 hours under heat preservation.
(3) Filtering, repeatedly washing to remove impurity ions in the filter cake, finishing washing when the conductivity of the filtrate is 89 mu S/cm, drying and crushing the obtained filter cake, and synthesizing the nano titanium polyester catalyst which consists of rutile type nano titanium dioxide, amorphous titanium dioxide and silicon dioxide.
Example 4
(1) Keeping the reaction temperature of the system at 45 ℃, adding 2 mol of isopropyl titanate into 1000 ml of 0.8 mol/L titanium oxychloride hydrochloric acid solution, cooling to 22 ℃ and reacting for 50 hours to prepare the rutile type nano titanium dioxide dispersion.
(2) Adjusting the temperature of the rutile type nano titanium dioxide dispersion liquid prepared in the step (1) to 88 ℃, adding 0.4 mol/l potassium silicate aqueous solution until the pH value of the system is 9.5, stirring for 50 minutes under heat preservation, adding 1 mol/l titanyl chloride hydrochloric acid solution until the pH value of the system is 4.5, and continuing stirring for 1 hour under heat preservation.
(3) Filtering, repeatedly washing to remove impurity ions in the filter cake, finishing washing when the conductivity of the filtrate is 75 mu S/cm, drying and crushing the obtained filter cake to obtain the nano titanium polyester synthesis catalyst, wherein the catalyst consists of rutile type nano titanium dioxide, amorphous titanium dioxide and silicon dioxide.
Comparative example 1
(1) Keeping the reaction temperature of the system at 40 ℃, adding 1.8 mol of isopropyl titanate into 1000 ml of 0.6 mol/L titanyl chloride hydrochloric acid solution, cooling to 20 ℃ and reacting for 48 hours to prepare the rutile type nano titanium dioxide dispersion.
(2) Adjusting the temperature of the rutile type nano titanium dioxide dispersion liquid prepared in the step (1) to 90 ℃, adding 1 mol/L sodium hydroxide aqueous solution until the pH value of the system is 10, stirring for 40 minutes under heat preservation, adding 1.5 mol/L titanyl chloride hydrochloric acid solution until the pH value of the system is 5, and continuing stirring for 1.5 hours under heat preservation.
(3) Filtering, repeatedly washing to remove impurity ions in the filter cake, finishing washing when the conductivity of the filtrate is 85 mu S/cm, drying and crushing the obtained filter cake, and synthesizing the nano titanium polyester catalyst which consists of rutile type nano titanium dioxide and amorphous titanium dioxide.
Comparative example 2
(1) Keeping the reaction temperature of the system at 40 ℃, adding 1.8 mol of isopropyl titanate into 1000 ml of 0.6 mol/L titanyl chloride hydrochloric acid solution, cooling to 20 ℃ and reacting for 48 hours to prepare the rutile type nano titanium dioxide dispersion.
(2) Adjusting the temperature of the rutile type nano titanium dioxide dispersion liquid prepared in the step (1) to 90 ℃, adding 1 mol/L sodium silicate aqueous solution until the pH value of the system is 10, stirring for 40 minutes under heat preservation, adding 1.5 mol/L hydrochloric acid solution until the pH value of the system is 5, and continuing stirring for 1.5 hours under heat preservation.
(3) Filtering, repeatedly washing to remove impurity ions in the filter cake, finishing washing when the conductivity of the filtrate is 92 mu S/cm, drying and crushing the obtained filter cake, and synthesizing the nano titanium polyester catalyst which consists of rutile type nano titanium dioxide and silicon dioxide.
Comparative example 3
(1) Keeping the reaction temperature of the system at 40 ℃, adding 1.8 mol of isopropyl titanate into 1000 ml of 2 mol/L titanyl sulfate hydrochloric acid solution, cooling to 20 ℃ and reacting for 48 hours to prepare amorphous titanium dioxide dispersion.
(2) Adjusting the temperature of the amorphous titanium dioxide dispersion liquid prepared in the step (1) to 90 ℃, adding 1 mol/L sodium silicate aqueous solution until the pH value of the system is 10, stirring for 40 minutes under heat preservation, adding 1.5 mol/L titanyl chloride hydrochloric acid solution until the pH value of the system is 5, and continuing stirring for 1.5 hours under heat preservation.
(3) Filtering, repeatedly washing to remove impurity ions in the filter cake, finishing washing when the conductivity of the filtrate is 89 mu S/cm, drying and crushing the obtained filter cake, and synthesizing the nano titanium polyester catalyst which consists of amorphous titanium dioxide and silicon dioxide.
The advantages and disadvantages of polyester polycondensation catalysts are evaluated mainly from two points: the activity of the catalyst and the hue of the product.
The activity of the catalyst can be characterized by comparing the length of the polycondensation reaction time, and the shorter the polycondensation reaction time required for reaching a certain intrinsic viscosity, the faster the reaction speed, the higher the activity of the catalyst.
The hue of the polyester product is measured by a color difference meter and evaluated according to L and b in an international standard color system CIE-L, a and b, wherein the value of L is whiteness, the value of b is a yellow index, and generally the larger the value of L is, the smaller the value of b is, the better the hue of the product is.
Evaluation test of catalyst Performance: 350 g of terephthalic acid, 170 g of ethylene glycol and 0.07 g of catalyst (based on the total mass of the raw materials, the mass of the catalyst is 130 ppm) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-250 ℃, the pressure is 0.3MPa, and water generated by the reaction is discharged through a rectifying device. And after the esterification is finished, slowly reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the vacuum degree of the system is lower than 50Pa, gradually increasing the reaction temperature to 275-280 ℃, stopping the reaction when the system reacts until the required viscosity is reached, extruding a reaction product from the bottom of the polymerization kettle, cooling, and granulating for performance test. The test results are shown in table 1.
TABLE 1
Claims (3)
1. A nanometer titanium polyester synthesis catalyst is characterized in that the catalyst consists of rutile titanium dioxide, amorphous titanium dioxide and silicon dioxide;
the preparation method of the nano titanium polyester synthetic catalyst comprises the following steps:
(1) Keeping the temperature at 35 to 50 ℃, adding titanate into 0.4 to 1 mol/L titanyl chloride hydrochloric acid solution, cooling to 15 to 25 ℃, and reacting for 36 to 72 hours to prepare rutile type nano titanium dioxide dispersion liquid;
the molar ratio of the titanate to the titanium oxychloride is 2 to 4;
(2) Adjusting the temperature of the rutile type nano titanium dioxide dispersion liquid prepared in the step (1) to 80-95 ℃, adding 0.3-1.2 mol/L silicate water solution until the pH value of the system is 9-11, stirring for 0.5-1 hour under heat preservation, adding 0.5-3 mol/L titanyl chloride hydrochloric acid solution until the pH value of the system is 4-6, and continuously stirring for 1~2 hours under heat preservation;
(3) And (3) filtering the step (2), repeatedly washing to remove impurity ions in the filter cake, finishing washing when the conductivity of the filtrate is less than 100 mu S/cm, drying the obtained filter cake, and crushing to obtain the nano titanium polyester synthesis catalyst.
2. The nano titanium-based polyester synthesis catalyst according to claim 1, wherein the titanate in step (1) is one of butyl titanate or isopropyl titanate.
3. The nano titanium-based polyester synthesis catalyst according to claim 1, wherein the silicate in step (2) is one of sodium silicate and potassium silicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111516959.7A CN114106309B (en) | 2021-12-13 | 2021-12-13 | Nano titanium polyester synthesis catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111516959.7A CN114106309B (en) | 2021-12-13 | 2021-12-13 | Nano titanium polyester synthesis catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114106309A CN114106309A (en) | 2022-03-01 |
| CN114106309B true CN114106309B (en) | 2023-04-18 |
Family
ID=80365140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111516959.7A Active CN114106309B (en) | 2021-12-13 | 2021-12-13 | Nano titanium polyester synthesis catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114106309B (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3486273B2 (en) * | 1995-09-26 | 2004-01-13 | 三菱化学ポリエステルフィルム株式会社 | White laminated polyester film |
| US6437088B1 (en) * | 2001-08-14 | 2002-08-20 | E. I. Du Pont De Nemours And Company | Process for producing polyester with coated titanium dioxide |
| TWI471355B (en) * | 2009-11-11 | 2015-02-01 | Far Eastern New Century Corp | Titanium oxide composition and the application thereof on poly-esterification |
| CN102702497B (en) * | 2012-06-07 | 2014-03-05 | 昆山天洋热熔胶有限公司 | Preparation method of polyester catalyst |
| CN103224620B (en) * | 2013-04-22 | 2015-02-04 | 常州纳欧新材料科技有限公司 | Polyester catalyst and preparation method thereof |
| CN110606946B (en) * | 2019-09-30 | 2021-06-29 | 常州大学盱眙凹土研发中心 | Preparation method and application of green titanium polyester catalyst |
| CN110724254B (en) * | 2019-10-18 | 2021-02-12 | 常州大学盱眙凹土研发中心 | Rod-shaped amorphous/anatase TiO2Preparation method and application of composite catalyst |
| CN112048059B (en) * | 2020-08-19 | 2023-02-14 | 海宁澜钛新材料有限公司 | Method for catalytically synthesizing polyester by using titanium catalyst |
| CN112812286B (en) * | 2020-12-31 | 2022-05-10 | 浙江恒逸石化有限公司 | Method for preparing polyester titanium catalyst by sol-gel method |
-
2021
- 2021-12-13 CN CN202111516959.7A patent/CN114106309B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114106309A (en) | 2022-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9771474B2 (en) | Hydrostability of polybutylene terephthalate composition | |
| KR101811478B1 (en) | Process for producing dispersion of particles of rutile titanium oxide | |
| CN111087595A (en) | High-activity titanium polyester catalyst and preparation method thereof | |
| CN115490839B (en) | Method for preparing PETG/PCTG copolyester by depolymerizing waste PET through mixed alcohol | |
| CN110606946B (en) | Preparation method and application of green titanium polyester catalyst | |
| CN114106309B (en) | Nano titanium polyester synthesis catalyst and preparation method thereof | |
| CN110204700B (en) | Method for efficiently preparing polytrimethylene terephthalate (PTT) | |
| CN1038188C (en) | Preparation method of high-purity micro-fine rutile-type titanium dioxide | |
| CN102443154A (en) | Aerogel catalyst and preparation method thereof | |
| CN101824143B (en) | Preparation method of high crystallization thermoplastics type polybutylene terephthalate slice | |
| CN113801311A (en) | Process for preparing polyester | |
| CN109666131B (en) | Preparation method of polybutylene terephthalate resin | |
| JP5543575B2 (en) | Process for producing thermoplastic polyester | |
| JP2005187556A (en) | Polyester and manufacturing method of polyester | |
| EP1881019B1 (en) | Titanium oxide sol and process for producing polyalkylene terephthalate therewith | |
| CN116144004A (en) | Heterogeneous titanium catalyst for PBAT polymerization and preparation method and application thereof | |
| CN109503819A (en) | A method of synthesis PBT polyester | |
| CN110724254B (en) | Rod-shaped amorphous/anatase TiO2Preparation method and application of composite catalyst | |
| CN102443155A (en) | Method for preparing fatty group-aromatic copolyester | |
| CN117567730B (en) | Nano-supported solid-phase titanium-based multielement metal catalyst and preparation method and application thereof | |
| CN103224620B (en) | Polyester catalyst and preparation method thereof | |
| CN102443156A (en) | Method for preparing polyester | |
| CN111087593A (en) | Catalyst composition for inhibiting THF (tetrahydrofuran) generation and hydrolysis resistance as well as preparation method and application thereof | |
| CN112708120B (en) | Titanium polyester catalyst with low content of free hydroxycarboxylic acid and preparation method thereof | |
| CN108659210B (en) | Heterogeneous catalyst and application thereof in polyester preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Yao Pengcheng Inventor after: Wang Can Inventor after: Wang Liang Inventor after: Liu Wenjie Inventor after: Zuo Shixiang Inventor after: Yao Chao Inventor after: Li Xiazhang Inventor after: Mao Huihui Inventor after: Gui Guanhao Inventor after: Gao Bingying Inventor after: Wu Fengqin Inventor before: Liu Jingwei Inventor before: Wu Fengqin Inventor before: Wang Can Inventor before: Wang Liang Inventor before: Yao Pengcheng Inventor before: Liu Wenjie Inventor before: Zuo Shixiang Inventor before: Yao Chao Inventor before: Li Xiazhang Inventor before: Mao Huihui Inventor before: Gui Guanhao Inventor before: Gao Bingying |
|
| CB03 | Change of inventor or designer information |