CN115414923B - Heterogeneous TiO for synthesizing polycarbonate diol 2 /SiO 2 Catalyst and preparation method thereof - Google Patents
Heterogeneous TiO for synthesizing polycarbonate diol 2 /SiO 2 Catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 51
- 150000002009 diols Chemical class 0.000 title claims abstract description 39
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 37
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 37
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 88
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 23
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 15
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 14
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 150000003377 silicon compounds Chemical class 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 6
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 239000004408 titanium dioxide Substances 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 239000007787 solid Substances 0.000 description 28
- 238000000967 suction filtration Methods 0.000 description 28
- 238000012512 characterization method Methods 0.000 description 20
- 239000012065 filter cake Substances 0.000 description 20
- 239000002808 molecular sieve Substances 0.000 description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 19
- 238000006068 polycondensation reaction Methods 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 230000001376 precipitating effect Effects 0.000 description 14
- 238000005086 pumping Methods 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- 238000010907 mechanical stirring Methods 0.000 description 13
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 12
- 238000000227 grinding Methods 0.000 description 11
- 239000011148 porous material Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of catalysts, and in particular relates to heterogeneous TiO (titanium dioxide) for synthesizing polycarbonate diol 2 /SiO 2 A catalyst and a method for preparing the same. A heterogeneous TiO is prepared by adopting a hydrolysis method 2 /SiO 2 The catalyst solves the problem of low molecular weight of polycarbonate diol synthesized by the traditional titanium catalyst, and simultaneously realizes controllable molecular weight through reaction time.
Description
Technical Field
The invention belongs to the field of catalysts, and in particular relates to heterogeneous TiO (titanium dioxide) for synthesizing polycarbonate diol 2 /SiO 2 A catalyst and a method for preparing the same.
Background
Polycarbonate diol is an important chemical intermediate, is mainly used as a soft segment structure for synthesizing polyurethane, and has excellent mechanical property, hydrolysis resistance, weather resistance, low-temperature flexibility, biodegradability, wear resistance and oil resistance compared with the traditional polyether diol and polyester diol, so that the polycarbonate diol is used in the wide chemical industry.
The metal catalyst shows excellent performance on the synthetic polycarbonate diol, and mainly comprises the following components: tin catalysts, but the color of the product is darker, and tin compounds are extreme biocides; antimony catalysts, however, antimony compounds are toxic and cause water eutrophication; germanium-based catalysts, however, are scarce in germanium resources, expensive, and are easily volatilized from the reaction system; the titanium catalyst has high activity, low price and easy availability, but titanate is easy to hydrolyze and has influence on subsequent reaction, and polyester obtained by the titanium catalyst is slightly yellow in color, so that the use of the titanium catalyst is limited.
Disclosure of Invention
In order to overcome the technical problems of the existing catalyst pointed out in the background art, the invention provides a preparation method of the catalyst and a synthesis method of polycarbonate diol, simplifies catalyst components, reduces industrial production steps and has industrial value.
The invention follows the aim of green chemistry, has few raw material types of the preparation catalyst, simple reaction process of the catalyst and high yield, further greatly reduces the cost for preparing the polycarbonate diol, and has industrial application prospect.
In order to achieve the purpose, the adopted technical scheme is as follows:
the catalyst for synthesizing the polycarbonate diol is a heterogeneous titanium-silicon composite catalyst, and comprises titanium dioxide and silicon dioxide with the molar ratio of 4:1-1:2, and the specific surface area of the catalyst is 100-300 m 2 And/g, the pore diameter is 2-7 nm. The catalyst can provide active centers in the polycondensation stage, accelerate the reaction process and shorten the reaction time.
The catalyst is prepared by a hydrolysis method of a titanium compound and a silicon compound, and the specific preparation method of the catalyst comprises the following operation steps:
s1, dissolving a titanium compound and a silicon compound in ethanol to prepare a solution A; deionized water and absolute ethyl alcohol are mixed to prepare solution B;
the titanium compound is tetrabutyl titanate or titanium tetrachloride, and the silicon compound is tetraethoxysilane;
the molar ratio of the titanium compound to the silicon compound is 3:1-1:3; the molar ratio of deionized water to ethanol is 1:5;
stirring the titanium compound and the silicon compound at the temperature of 30-60 ℃ and the stirring speed of 100-400 r/min for reaction;
s2, slowly adding the solution B into the solution A, or slowly adding the solution A into the solution B, continuously stirring until the dripping is finished, continuously stirring and aging to obtain a catalyst precursor 1;
aging for 2 hours at the temperature of 30-60 ℃;
s3, washing, suction filtering and drying the catalyst precursor 1 to obtain a catalyst precursor 2, and roasting to obtain heterogeneous TiO 2 /SiO 2 Catalyst
Drying at 60-100 deg.c to eliminate water, grinding, sieving (200 mesh), roasting at 300-600 deg.c for 3 hr, and use.
The method for synthesizing the polycarbonate diol adopts heterogeneous TiO 2 /SiO 2 The catalyst catalyzes diphenyl carbonate and 1, 4-butanediol to carry out transesterification under the condition of negative pressure to obtain polycarbonate diol; reaction conditions: the temperature is 190-230 ℃; the catalyst consumption is 0.01 to 0.5 percent; the molar ratio of diphenyl carbonate to 1, 4-butanediol is 1:1-1:1.5.
The negative pressure condition range is-0.025 MPa to-0.095 MPa.
The invention has the following beneficial effects:
the catalyst is prepared according to the aim of green chemistry and is used for catalyzing and preparing polycarbonate diol, the yield of the polycarbonate diol reaches 89.8 percent, the weight average molecular weight reaches 15628g/mol, and the number average molecular weight reaches 9125g/mol through changing the reaction conditions. Solves the problems of low yield, low molecular weight and the like of the traditional preparation of the polycarbonate diol, and can effectively control the molecular weight error of the product within 1000g/mol by controlling the reaction time. Meanwhile, the catalyst prepared by the method has few raw material types and simple catalyst reaction process, so that the cost for preparing the polycarbonate diol is greatly reduced.
Drawings
FIG. 1 is a TiO prepared in example 2 2 /SiO 2 SEM image of the catalyst;
FIG. 2 is a TiO prepared in example 6 2 /SiO 2 SEM image of the catalyst.
Detailed Description
In order to further describe the technical means and effects adopted by the invention to achieve the preset aim, the specific implementation, characteristics and effects of the method for synthesizing the polycarbonate diol according to the invention are described in detail below.
Example 1
(1) The preparation method of the catalyst comprises the following steps:
s1, under the condition of stirring, 102g of tetrabutyl titanate and 21g of tetraethoxysilane are dissolved in 500g of absolute ethyl alcohol (solution A);
s2, mixing 30g of deionized water with 371g of absolute ethanol (solution B).
S3, heating the solution A to 30 ℃, dropwise adding the solution B into the solution A at the rate of 8mL/min, aging for 2 hours at 40 ℃ after the dropwise adding is finished, and washing the filter cake twice by deionized water and once by absolute ethyl alcohol.
S4, drying the filter cake at 65 ℃ for 8 hours, grinding (200 meshes), and roasting for 3 hours at 500 ℃ by using a muffle furnace to obtain TiO 2 /SiO 2 A catalyst.
Specific surface area 226.72m of the catalyst prepared by BET characterization 2 3.04nm pore diameter, ICP characterization to obtain TiO 2 /SiO 2 The actual titanium to silicon ratio of the catalyst was 3.96:1.
(2) Evaluation of titanium silicalite molecular sieve catalyst performance:
s1, put 107g of DPC (1 mol) and 50g of BDO (1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S2, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s3, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL.
The yield of PCDL was 67.0%, the number average molecular weight was 5560g/mol, the weight average molecular weight was 8666g/mol, and the PDI was 1.56.
Example 2
(1) The preparation method of the titanium-silicon molecular sieve catalyst comprises the following steps:
s1, 96g of tetrabutyl titanate and 26g of tetraethoxysilane are dissolved in 500g of absolute ethanol (solution A) under stirring
S2, mixing 30g of deionized water with 371g of absolute ethanol (solution B).
S3, heating the solution A to 30 ℃, dropwise adding the solution B into the solution A at the rate of 8mL/min, aging for 2 hours at 40 ℃ after the dropwise adding is finished, and washing the filter cake twice by deionized water and once by absolute ethyl alcohol.
S4, drying the filter cake at 65 ℃ for 8 hours, grinding (200 meshes), and roasting for 3 hours at 500 ℃ by using a muffle furnace to obtain TiO 2 /SiO 2 A catalyst.
By BET characterization, the specific surface area of the catalyst was 258.81m 2 /g, pore size 2.78nm, by ICP characterization gave an actual titanium to silicon ratio of 2.87: tiO 1 2 /SiO 2 A catalyst. .
(2) The method for preparing polycarbonate diol by using the titanium silicalite molecular sieve catalyst comprises the following steps:
s1, put 107g of DPC (1 mol) and 50g of BDO (1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S2, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s3, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL.
The yield of polycarbonate diol was 73.8%, the number average molecular weight was 6215g/mol, the weight average molecular weight was 11189g/mol, and the PDI was 1.80.
Example 3
(1) The preparation method of the titanium-silicon molecular sieve catalyst comprises the following steps:
s1, 85g of tetrabutyl titanate and 35g of tetraethoxysilane are dissolved in 500g of absolute ethanol (solution A) under stirring
S2, mixing 30g of deionized water with 371g of absolute ethanol (solution B).
S3, heating the solution A to 30 ℃, dropwise adding the solution B into the solution A at the rate of 8mL/min, aging for 2 hours at 40 ℃ after the dropwise adding is finished, and washing the filter cake twice by deionized water and once by absolute ethyl alcohol.
S4, drying the filter cake at 65 ℃ for 8 hours, grinding (200 meshes), and roasting for 3 hours at 500 ℃ by using a muffle furnace to obtain TiO 2 /SiO 2 A catalyst.
By BET characterization, the specific surface area of the catalyst was 226.64m 2 Per g, pore size 2.89nm, by ICP characterization gave an actual titanium to silicon ratio of 2.11: tiO 1 2 /SiO 2 A catalyst.
(2) The method for preparing polycarbonate diol by using the titanium silicalite molecular sieve catalyst comprises the following steps:
s1, put 107g of DPC (1 mol) and 50g of BDO (1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S2, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s3, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL.
The yield of polycarbonate diol was 71.6%, the number average molecular weight was 5099g/mol, the weight average molecular weight was 8821g/mol, and the PDI was 1.73.
Example 4
(1) The preparation method of the titanium-silicon molecular sieve catalyst comprises the following steps:
s1, 36g of titanium tetrachloride and 35g of tetraethoxysilane are dissolved in 500g of absolute ethanol (solution A) under stirring
S2, mixing 30g of deionized water with 371g of absolute ethanol (solution B).
S3, heating the solution A to 30 ℃, dropwise adding the solution B into the solution A at the rate of 8mL/min, aging for 2 hours at 40 ℃ after the dropwise adding is finished, and washing the filter cake twice by deionized water and once by absolute ethyl alcohol.
S4, drying the filter cake at 65 ℃ for 8 hours, grinding (200 meshes), and roasting for 3 hours at 500 ℃ by using a muffle furnace to obtain TiO 2 /SiO 2 A catalyst.
By BET characterization, the specific surface area of the catalyst was 147.57m 2 Per g, pore size 2.59nm, by ICP characterization gives an actual titanium to silicon ratio of 1.02: tiO 1 2 /SiO 2 A catalyst.
(2) The method for preparing polycarbonate diol by using the titanium silicalite molecular sieve catalyst comprises the following steps:
s1, put 107g of DPC (1 mol) and 50g of BDO (1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S2, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s3, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL.
The yield of polycarbonate diol was 20.0%, the number average molecular weight was 687g/mol, the weight average molecular weight was 1202g/mol, and the PDI was 1.75.
Example 5
(1) The preparation method of the titanium-silicon molecular sieve catalyst comprises the following steps:
s1, 43g of tetrabutyl titanate and 69g of tetraethoxysilane are dissolved in 500g of absolute ethanol (solution A) under stirring
S2, mixing 30g of deionized water with 371g of absolute ethanol (solution B).
S3, heating the solution A to 30 ℃, dropwise adding the solution B into the solution A at the rate of 8mL/min, aging for 2 hours at 40 ℃ after the dropwise adding is finished, and washing the filter cake twice by deionized water and once by absolute ethyl alcohol.
S4, drying the filter cake at 65 ℃ for 8 hours, grinding (200 meshes), and roasting for 3 hours at 500 ℃ by using a muffle furnace to obtain TiO 2 /SiO 2 A catalyst.
By means of the BET characterization,specific surface area of catalyst 107.84m 2 3.21nm pore size, and the actual titanium-silicon ratio obtained by ICP characterization is 1:1.96 TiO 2 /SiO 2 A catalyst.
(2) The method for preparing polycarbonate diol by using the titanium silicalite molecular sieve catalyst comprises the following steps:
s1 put 107g of DPC (1 mol) and 50g of BDO (1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S2, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s3, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL.
The yield of polycarbonate diol was 5.8%, the number average molecular weight was 671g/mol, the weight average molecular weight was 1215g/mol, and the PDI was 1.81.
Example 6
(1) The preparation method of the titanium-silicon molecular sieve catalyst comprises the following steps:
s1, 96g of tetrabutyl titanate and 26g of tetraethoxysilane are dissolved in 500g of absolute ethanol (solution A) under stirring
S2, mixing 30g of deionized water with 371g of absolute ethanol (solution B).
S3, heating the solution B to 30 ℃, dropwise adding the solution A into the solution B at the rate of 8mL/min, aging for 2 hours at 40 ℃ after the dropwise adding is finished, and washing the filter cake twice by deionized water and once by absolute ethyl alcohol.
S4, drying the filter cake at 65 ℃ for 8 hours, grinding (200 meshes), and roasting for 3 hours at 500 ℃ by using a muffle furnace to obtain TiO 2 /SiO 2 A catalyst.
By BET characterization, the specific surface area of the catalyst was 274.50m 2 Per g, pore size 6.75nm, by ICP characterization gave an actual titanium to silicon ratio of 2.87: tiO 1 2 /SiO 2 A catalyst.
(2) The method for preparing polycarbonate diol by using the titanium silicalite molecular sieve catalyst comprises the following steps:
s1 put 107g of DPC (1 mol) and 50g of BDO (1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S2, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s3, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL.
The yield of polycarbonate diol was 89.8%, the number average molecular weight was 9125g/mol, the weight average molecular weight was 15628g/mol, and the PDI was 1.71.
Example 7
(1) The preparation method of the titanium-silicon molecular sieve catalyst comprises the following steps:
s1, 96g of tetrabutyl titanate and 26g of tetraethoxysilane are dissolved in 500g of absolute ethanol (solution A) under stirring
S2, mixing 30g of deionized water with 371g of absolute ethanol (solution B).
S3, heating the solution B to 30 ℃, dropwise adding the solution A into the solution B at the rate of 8mL/min, aging for 2 hours at 40 ℃ after the dropwise adding is finished, and washing the filter cake twice by deionized water and once by absolute ethyl alcohol.
S4, drying the filter cake at 65 ℃ for 8 hours, grinding (200 meshes), and roasting for 3 hours at 300 ℃ by using a muffle furnace to obtain TiO 2 /SiO 2 A catalyst.
By BET characterization, the specific surface area of the catalyst was 231.52m 2 Per g, pore size 5.15nm, by ICP characterization gave an actual titanium to silicon ratio of 2.87: tiO 1 2 /SiO 2 A catalyst.
(2) The method for preparing polycarbonate diol by using the titanium silicalite molecular sieve catalyst comprises the following steps:
s1 put 107g of DPC (1 mol) and 50g of BDO (1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 190 ℃.
S2, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s3, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL.
The yield of polycarbonate diol was 81.9%, the number average molecular weight was 6134g/mol, the weight average molecular weight was 10734g/mol, and the PDI was 1.75.
Example 8
(1) The preparation method of the titanium-silicon molecular sieve catalyst comprises the following steps:
s1, 96g of tetrabutyl titanate and 26g of tetraethoxysilane are dissolved in 500g of absolute ethanol (solution A) under stirring
S2, mixing 30g of deionized water with 371g of absolute ethanol (solution B).
S3, heating the solution B to 30 ℃, dropwise adding the solution A into the solution B at the rate of 8mL/min, aging for 2 hours at 40 ℃ after the dropwise adding is finished, and washing the filter cake twice by deionized water and once by absolute ethyl alcohol.
S4, drying the filter cake at 65 ℃ for 8 hours, grinding (200 meshes), and roasting for 3 hours at 600 ℃ by using a muffle furnace to obtain TiO 2 /SiO 2 A catalyst.
By BET characterization, the specific surface area of the catalyst was 270.98m 2 Per g, pore size 6.32nm, by ICP characterization gave an actual titanium to silicon ratio of 2.87: tiO 1 2 /SiO 2 A catalyst.
(2) The method for preparing polycarbonate diol by using the titanium silicalite molecular sieve catalyst comprises the following steps:
s1 put 107g of DPC (1 mol) and 50g of BDO (1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 230 ℃.
S2, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s3, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL.
The yield of polycarbonate diol was 80.3%, the number average molecular weight was 8105g/mol, the weight average molecular weight was 13211g/mol, and the PDI was 1.63.
Example 9
(1) The preparation method of the titanium-silicon molecular sieve catalyst comprises the following steps:
s1, 96g of tetrabutyl titanate and 26g of tetraethoxysilane are dissolved in 500g of absolute ethanol (solution A) under stirring
S2, mixing 30g of deionized water with 371g of absolute ethanol (solution B).
S3, heating the solution B to 30 ℃, dropwise adding the solution A into the solution B at the rate of 8mL/min, aging for 2 hours at the temperature of 30 ℃ after the dropwise adding is finished, and washing the filter cake twice by deionized water and once by absolute ethyl alcohol.
S4, drying the filter cake at 65 ℃ for 8 hours, grinding (200 meshes), and roasting for 3 hours at 500 ℃ by using a muffle furnace to obtain TiO 2 /SiO 2 A catalyst.
By BET characterization, the specific surface area of the catalyst was 223.41m 2 3.88nm pore size, and the actual titanium-silicon ratio obtained by ICP characterization is 2.87: tiO 1 2 /SiO 2 A catalyst.
(2) The method for preparing polycarbonate diol by using the titanium silicalite molecular sieve catalyst comprises the following steps:
s1 put 107g of DPC (1 mol) and 50g of BDO (1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S2, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s3, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL. Specific data are shown in tables 1 and 2.
Example 10
(1) The preparation method of the titanium-silicon molecular sieve catalyst comprises the following steps:
s1, 96g of tetrabutyl titanate and 26g of tetraethoxysilane are dissolved in 500g of absolute ethanol (solution A) under stirring
S2, mixing 30g of deionized water with 371g of absolute ethanol (solution B).
S3, heating the solution B to 30 ℃, dropwise adding the solution A into the solution B at the rate of 8mL/min, aging for 2 hours at 60 ℃ after the dropwise adding is finished, and washing the filter cake twice by deionized water and once by absolute ethyl alcohol.
S4, drying the filter cake at 65 ℃ for 8 hours, grinding (200 meshes), and roasting for 3 hours at 500 ℃ by using a muffle furnace to obtain TiO 2 /SiO 2 A catalyst.
By BET characterization, the specific surface area of the catalyst was 168.54m 2 Per g, pore size 5.25nm, by ICP characterization gave an actual titanium to silicon ratio of 2.87: tiO 1 2 /SiO 2 A catalyst.
(2) The method for preparing polycarbonate diol by using the titanium silicalite molecular sieve catalyst comprises the following steps:
s1 put 107g of DPC (1 mol) and 50g of BDO (1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S2, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s3, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL. Specific data are shown in tables 1 and 2.
Example 11
S1, using the catalyst of example 6.
S2, 107g of DPC (1 mol) and 50g of BDO (1.1.1 mol) are dosed into 250ml of four with mechanical stirringInto an open flask, 0.107g of TiO was added 2 /SiO 2 (0.1% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S3, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s4, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL. Specific data are shown in tables 1 and 2.
Example 12
S1, using the catalyst of example 6.
S2 put 107g of DPC (1 mol) and 50g of BDO (1.1.1 mol) into a 250ml four-necked flask with mechanical stirring, add 0.535g of TiO 2 /SiO 2 (0.5% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S3, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s4, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL. Specific data are shown in tables 1 and 2.
Example 13
S1, using the catalyst of example 6.
S2, putting 107g of DPC (1 mol) and 45g of BDO (1 mol) into a 250ml four-necked flask with mechanical stirring, adding 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S3, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s4, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL. Specific data are shown in tables 1 and 2.
Example 14
S1, using the catalyst of example 6.
S2 put 107g of DPC (1 mol) and 68g of BDO (1.1.5 mol) into a 250ml four-necked flask with mechanical stirring, add 0.321g of TiO 2 /SiO 2 (0.3% of DPC mass), nitrogen protection, reaction temperature 200 ℃.
S3, in the prepolymerization stage for 3 hours, a large amount of byproduct phenol is distilled out; slowly increasing vacuum degree during polycondensation, maintaining the fraction temperature at 110deg.C, and stopping reaction when vacuum pumping is carried out to-0.095 MPa;
s4, dissolving light yellow solid in the four-neck flask by using dichloromethane after the reaction is finished, precipitating by using ethanol, carrying out suction filtration, and carrying out vacuum drying on the solid after the suction filtration at 50 ℃ for 12 hours to obtain a product PCDL. Specific data are shown in tables 1 and 2.
Comparative example 1
This comparative example differs from example 6 in that in the preparation of the catalyst of step (1), S1 is not added with ethyl orthosilicate, 96g of tetrabutyl titanate is weighed and dissolved in 500g of absolute ethanol (solution A);
comparative example 2
This comparative example differs from example 6 in that in the preparation of the catalyst of step (1), no tetrabutyl titanate is added to S1, and 26g of ethyl orthosilicate is weighed and dissolved in 500g of absolute ethanol (solution A);
comparative example 3
This comparative example differs from example 6 in that the catalyst was a commercial ZSM-5.
Table 1 catalyst investigation factors
TABLE 2 optimization of process conditions
Example 13
S1, using the catalyst of example 6.
S2, the reaction temperature is 200 ℃, the catalyst dosage is 0.3wt% of the mass of DPC, the raw material molar feed ratio is DPC: BDO=1:1.1, and PCDL is synthesized. Prepolymerizing for 3h, vacuumizing from-0.025 MPa to-0.095 MPa during polycondensation, continuing to react for 2h,
s3, discussing the molecular weight and distribution of PCDL products of 1h (-0.025 MPa), 2h (-0.060 MPa), 3h (-0.095 MPa), 4h (-0.095 MPa) and 5h (-0.095 MPa) from the polycondensation stage, and carrying out three parallel experiments, wherein the molecular weights of the PCDL obtained at different reaction times are shown in Table 3:
TABLE 3 Table 3
The present invention is not limited to the above-mentioned embodiments, but is not limited to the above-mentioned embodiments, and any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical matters of the present invention can be made by those skilled in the art without departing from the scope of the present invention.
Claims (6)
1. Heterogeneous TiO 2 /SiO 2 The application of the catalyst is characterized in that the catalyst is used for synthesizing polycarbonate diol;
the method for synthesizing the polycarbonate diol comprises the following steps: by heterogeneous TiO 2 /SiO 2 Catalyst for catalyzing diphenyl carbonate and 1, 4-butanediol under negative pressureTransesterification to obtain polycarbonate diol;
the specific surface area of the catalyst is 100-300 m 2 And/g, wherein the aperture is 2-7 nm, and the molar ratio of titanium to silicon is 4:1-2:1;
the preparation method of the catalyst comprises the following steps:
s1, dissolving a titanium compound and a silicon compound in ethanol to prepare a solution A; deionized water and absolute ethyl alcohol are mixed to prepare solution B;
s2, slowly adding the solution B into the solution A, or slowly adding the solution A into the solution B, continuously stirring until the dripping is finished, continuously stirring and aging to obtain a catalyst precursor 1;
s3, washing, suction filtering and drying the catalyst precursor 1 to obtain a catalyst precursor 2, and roasting to obtain heterogeneous TiO 2 /SiO 2 A catalyst.
2. Heterogeneous TiO according to claim 1 2 /SiO 2 The application of the catalyst is characterized in that in the step S1, the titanium compound is tetrabutyl titanate or titanium tetrachloride, and the silicon compound is tetraethoxysilane.
3. Heterogeneous TiO according to claim 1 2 /SiO 2 The application of the catalyst is characterized in that in the step S1, the molar ratio of the titanium compound to the silicon compound is 3:1-1:3; the molar ratio of deionized water to ethanol was 1:5.
4. Heterogeneous TiO according to claim 1 2 /SiO 2 The application of the catalyst is characterized in that in the step S2, the aging condition is 30-60 ℃ and the aging time is 2 h.
5. Heterogeneous TiO according to claim 1 2 /SiO 2 The application of the catalyst is characterized in that the roasting temperature in the step S3 is 300-600 ℃ and the roasting time is 3h.
6. Heterogeneous TiO according to claim 1 2 /SiO 2 Of catalystsThe application is characterized in that the negative pressure condition range is-0.025 MPa to-0.095 MPa; the reaction temperature is 190-230 ℃; the catalyst consumption is 0.01% -0.5%; the molar ratio of diphenyl carbonate to 1, 4-butanediol is 1:1-1:1.5.
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| CN103623808A (en) * | 2013-12-10 | 2014-03-12 | 柳景惠 | Selective catalytic reduction (SCR) catalyst and preparation method thereof |
| CN104001470A (en) * | 2014-05-21 | 2014-08-27 | 华南理工大学 | Ti-Si-O difunctional photocatalysis adsorbent as well as preparation method and application thereof in fuel oil desulphurization |
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