CN102936334A - Zinc phenolic hydroxyl complex catalytic agent, preparation method and application thereof - Google Patents
Zinc phenolic hydroxyl complex catalytic agent, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of chemical engineering and specifically relates to a zinc phenolic hydroxyl complex catalytic agent, a preparation method and an application thereof. According to the zinc phenolic hydroxyl complex catalytic agent, zinc acetate, diluted hydrochloric acid, 3, 3', 5, 5'-tetrasubstituted-2, 2'-biphenyl bisphenol and sodium hydroxide are used as initiators and reacted to prepare a zinc phenolic hydroxyl complex through a hydrothermal process, and the dried zinc phenolic hydroxyl complex is subjected to filtering and ageing to obtain the zinc phenolic hydroxyl complex catalytic agent. The obtained zinc phenolic hydroxyl complex catalytic agent is used for catalyzing copolymerization reactions of carbon dioxide and propylene oxide, the zinc phenolic hydroxyl complex catalytic agent is added into an autoclave and then cooled to room temperatures after vacuum drying, the carbon dioxide and the propylene oxide are added, and heating reaction is performed to obtain poly propylene carbonate with number-average molar mass of over 50000. The catalytic agent is convenient to use, catalytic activity is larger than 85 grams of polymer per gram of zinc, catalytic selectivity is good, and the obtained poly propylene carbonate is order in structure and high in molecular mass.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of zinc phenolic hydroxyl group complex compound catalyst and preparation method thereof and application.
Background technology
Epoxy compounds and carbonic acid gas can obtain aliphatic polycarbonate by alternating copolymerization, and wherein lined polymethyl ethylene carbonate is important a kind of, can be widely used in the fields such as low temperature oxygen barrier film, biodegradable plastic, elastomerics, tackiness agent, coating.Synthetic this base polymer is the technology of " killing three birds with one stone ", can effectively utilize on the one hand industrial a large amount of discarded and environment is caused greenhouse gases---the carbonic acid gas of very big harm, the 2nd, the carbonic acid gas energy has been developed and has been alleviated the pressure that traditional energy is exhausted, the 3rd, product has biodegradability, can not bring the discarded white pollution that causes of common plastics, thereby have good economic and social benefit.Now existing lot of documents report carbonic acid gas and oxyethane, propylene oxide etc. carry out copolyreaction, synthetic this base polymer.Catalyst system mainly contains: organic zinc class catalyzer, particularly ZnEt
2Catalyst system with the polyol composition; Aluminum-based catalyst mainly is porphyrin aluminium, rare-earth complexation catalyst etc.At present, the classical catalyst system of this reaction has following a few class: (one) zinc ethyl and the water that waits mole number, the Primary Catalysts zinc ethyl of this system is very responsive to Trace Water Vapor and oxygen, be difficult to operation, need use a large amount of strict dry solvent dioxane, thereby cost is very high and efficient is low.(2) adopt porphyrin metal complex to make catalyzer, although catalytic efficiency is greatly improved, this type of complex compound and raw material preparation thereof are more loaded down with trivial details, and price is also quite high, and the second-order transition temperature of prepared polymkeric substance is very low.(3) adopting the di-carboxylic acid zinc salt to make catalyzer can have satisfied catalytic efficiency, and the copolymerization product alternate degree that generates is high, compound with regular structure, and product property is good.
Because kind and the character of catalyzer have played vital decisive action to carbonic acid gas and epoxy compounds co-polymerization.Since 21 century, epoxy compounds and carbonic acid gas catalysis new technology do not stop to occur, and patent US6,844,287 B2 have improved the catalytic efficiency of pentanedioic acid zinc by load.Patent ZL 03114303.2 obtains inorganic intercalation nano catalyst by intercalation technique, has effectively improved active sites, has improved catalytic effect.Patent ZL200910192496.6 discloses the method for Zinc hydroxy acid complex catalyst and catalysis carbonic acid gas and epoxypropane copolymerization, has developed the new technology of carbonic acid gas and epoxypropane copolymerization.But along with people are familiar with the further requirement that reaches its production efficiency to the intensification of the economic and social benefit of this catalyzed reaction, the update of this key factor of catalyzer is the present market requirement and study hotspot.
Summary of the invention
The objective of the invention is for the deficiencies in the prior art, the zinc phenolic hydroxyl group that a kind of catalytic efficiency is high, selectivity good, polymerisate lined polymethyl ethylene carbonate molecular weight is high complex compound catalyst is provided.
Another object of the present invention provides the preparation method of this catalyzer.
A further object of the present invention provides the using method of this catalyzer.
The present invention is achieved through the following technical solutions above-mentioned purpose.
A kind of zinc phenolic hydroxyl group complex compound catalyst, its structural formula is suc as formula shown in the I:
Wherein, R
1=CH
3, Cl, Br or C (CH
3)
3R
2=CH
3, Br, NO
2Or C (CH
3)
3
The present invention also provides the preparation method of general formula suc as formula the zinc phenolic hydroxyl group complex compound catalyst shown in the I, may further comprise the steps: with zinc acetate, dilute hydrochloric acid, 3,3 ', 5,5 '-four replace-2,2 '-biphenyl bis-phenol, sodium hydroxide are initiator, prepare zinc phenolic hydroxyl group complex compound through hydro-thermal technique, obtain zinc phenolic hydroxyl group complex compound catalyst after the ageing of zinc phenolic hydroxyl group complex compound behind the filtration drying;
Particularly, above-mentioned preparation method may further comprise the steps: (1) with 3, and 3 ', 5,5 '-four replace-2, and 2 '-biphenyl bis-phenol joins and obtains transparent 3,3 ', 5 in the hot aqueous sodium hydroxide solution, 5 '-four replace-2, and the sodium-salt aqueous solution of 2 '-biphenyl bis-phenol is regulated pH=11～12 with dilute hydrochloric acid; (2) obtain zinc acetate aqueous solution with the deionized water dissolving zinc acetate, again zinc acetate aqueous solution is added drop-wise to 3,3 ', 5,5 '-four replace-2, in the sodium-salt aqueous solution of 2 '-biphenyl bis-phenol, behind 80～100 ℃ of reaction 5～10 h, cooling crystallization zinc phenolic hydroxyl group complex compound; (3) obtain zinc phenolic hydroxyl group complex compound behind the filtration drying, obtain zinc phenolic hydroxyl group complex compound catalyst through after the ageing again.
Preferably, the condition of described ageing is: ageing reagent is toluene, and Aging Temperature is normal temperature, and digestion time is 24～48 h.
Preferably, described 3,3 ', 5,5 '-four replace-2, and 2 '-biphenyl bis-phenol is 3,3 ', 5,5 '-tetramethyl--2,2 '-biphenyl bis-phenol, 3,3 ', 5,5 '-tetrabromobisphenol, 2 '-biphenyl bis-phenol, 3,3 '-two chloro-5,5 '-dinitrobenzene-2,2 '-biphenyl bis-phenol, 3,3 ', 5,5 '-tetra-tert-2, a kind of in 2 '-biphenyl bis-phenol.The above bisphenol hydroxy biphenyl structural of lifting is easy to form the ring-type chelation structure, more is conducive to form zinc phenolic hydroxyl group complex compound.
3,3 ', 5,5 '-four replace-2 among the preparation method of above-mentioned catalyzer, and the mol ratio of 2 '-biphenyl bis-phenol and zinc acetate is 2:1.
Above-mentioned zinc phenolic hydroxyl group complex compound catalyst is specifically designed to catalysis carbonic acid gas and epoxypropane copolymerization reaction, therefore the present invention also provides a kind of method for preparing lined polymethyl ethylene carbonate, may further comprise the steps: (1) adds zinc phenolic hydroxyl group complex compound catalyst in autoclave, be down to room temperature after the vacuum-drying; (2) add propylene oxide, be filled with continuously carbonic acid gas, reacting by heating; (3) obtain the propylene oxide bulk solution of lined polymethyl ethylene carbonate after reaction finishes, add the trichloromethane dilution, use methanol extraction, get crude product, get after drying the final product lined polymethyl ethylene carbonate.
Preferably, the weight ratio of zinc phenolic hydroxyl group complex compound catalyst and propylene oxide add-on is 1:60～1:250.Carbonic acid gas is after reaching specified reaction pressure, and continuously supply keeps reaction pressure, until reaction finishes.
Preferably, the described vacuum drying temperature of step (1) is 70～80 ℃.
Preferably, the temperature of the described reaction of step (2) is 60～80 ℃, and the pressure of reaction is 3.0～6.0 MPa, and the time of reaction is 20～40 h.
After reaction finished, residual air was also discharged in cooling, took out product after driving still.
Compared with prior art, the present invention has following beneficial effect:
Zinc phenolic hydroxyl group complex compound catalyst preparation technology of the present invention is simple, and hydro-thermal technique does not have the participation of other organic solvents, and ageing reagent is reused, and does not have environmental pollution.The catalytic selectivity of the zinc phenolic hydroxyl group complex compound catalyst of the present invention's preparation is good, and polymer architecture is regular, and molecular weight is high.Catalytic activity is greater than 85g polymkeric substance/g zinc within the scope of the invention, and polymkeric substance is carbonic acid gas and the complete alternating structure of propylene oxide, and the number-average molecular weight of polymkeric substance is greater than 50,000.
Embodiment
Embodiment 1
4.84 g(0.02 mol) 3,3 ', 5,5 '-tetramethyl--2,2 '-biphenyl bis-phenol join obtain in the hot aqueous sodium hydroxide solution of 25 mL 2M transparent 3,3 ', 5,5 '-tetramethyl--2,2 '-biphenyl bisphenol sodium salt aqueous solution is regulated pH=11 with dilute hydrochloric acid; With 10 mL deionized water dissolvings, 1.83 g(0.01 mol) zinc acetate, then zinc acetate aqueous solution is added drop-wise to above-mentioned 3,3 ', 5,5 '-tetramethyl--2 is in 2 '-biphenyl bisphenol-salt solution, 90 ℃ of reaction 10 h, cooling is placed 10 h and is separated out zinc phenolic hydroxyl group complex compound Zn
2+[(CH
3)
4C
12H
6O
2]
2, deionized water wash three times, Büchner funnel are collected, and dry to carry out ultimate analysis with organic element analyzer, theoretical value afterwards: C, 70.39; H, 5.91.Test value: C, 70.45; H, 5.95.Zinc 3,3 ', 5 after drying, 5 '-tetramethyl--2,2 '-biphenyl bis-phenol complex compound is normal temperature ageing 24 h in toluene, and Büchner funnel is collected, and obtains zinc 3 behind the vacuum drying, 3 ', 5,5 '-tetramethyl--2,2 '-biphenyl bis-phenol complex compound catalyst is put into moisture eliminator for subsequent use.
Catalytically active assessment: the zinc 3 that in the 500ml autoclave, adds 2.5 g, 3 ', 5,5 '-tetramethyl--2,2 '-biphenyl bis-phenol complex compound catalyst, behind 70 ℃ of lower vacuum-drying 24 h, be cooled to room temperature, then add propylene oxide (PO) 300 ml, be filled with carbonic acid gas and heating, finally make the still internal pressure reach 4.5 MPa, 70 ℃ of temperature in the kettle continue to pass into carbonic acid gas, keep the still internal pressure, residual air is discharged in cooling after reacting 30 h, open the propylene oxide bulk solution that takes out the product lined polymethyl ethylene carbonate behind the still, add the trichloromethane dilution, use methanol extraction, get crude product, get after drying final product lined polymethyl ethylene carbonate 26.6 g(90.9 g polymkeric substance/g zinc), the number-average molecular weight of GPC test polymer is 7.2 ten thousand
1The H-NMR test polymer is carbonic acid gas and the complete alternating structure of propylene oxide.
Embodiment 2
10.04 g(0.02 mol) 3,3 ', 5,5 '-tetrabromobisphenol, 2 '-biphenyl bis-phenol join obtain in the hot aqueous sodium hydroxide solution of 25 mL 2M transparent 3,3 ', 5,5 '-tetrabromobisphenol, 2 '-biphenyl bisphenol sodium salt aqueous solution is regulated pH=12 with dilute hydrochloric acid; 1.83 g(0.01 mol) zinc acetate is with 10 mL deionized water dissolvings, then zinc acetate aqueous solution is added drop-wise to above-mentioned 3,3 ', 5,5 '-tetrabromobisphenol, 2 '-biphenyl bisphenol sodium salt aqueous solution, 80 ℃ of reaction 8 h, cooling is placed 10 h and is separated out zinc phenolic hydroxyl group complex compound Zn
2+(C
12H
6Br
4O
2)
2, deionized water wash three times, Büchner funnel are collected, and dry to carry out ultimate analysis with organic element analyzer, theoretical value afterwards: C, 27.07; H, 0.76; Br, 60.03.Test value: C, 27.12; H, 0.72; Br, 60.01.Zinc 3,3 ', 5 after drying, 5 '-tetrabromobisphenol, 2 '-biphenyl bis-phenol complex compound is at normal temperature ageing 36 h in toluene, and Büchner funnel is collected, and obtains zinc 3 behind the vacuum drying, 3 ', 5,5 '-tetrabromobisphenol, 2 '-biphenyl bis-phenol complex compound catalyst is put into moisture eliminator for subsequent use.
Catalytically active assessment: the zinc 3 that in the 500ml autoclave, adds 1.0 g, 3 ', 5,5 '-tetrabromobisphenol, 2 '-biphenyl bis-phenol complex compound catalyst, behind 80 ℃ of lower vacuum-drying 24 h, be cooled to room temperature, then add propylene oxide (PO) 300 ml, be filled with carbonic acid gas and heating, finally make the still internal pressure reach 6.0 MPa, 60 ℃ of temperature in the kettle continue to pass into carbonic acid gas, keep the still internal pressure, residual air is discharged in cooling after reacting 20 h, open the propylene oxide bulk solution that takes out the product lined polymethyl ethylene carbonate behind the still, add the trichloromethane dilution, use methanol extraction, get crude product, get after drying final product lined polymethyl ethylene carbonate 14.6 g(94.7g polymkeric substance/g zinc), the number-average molecular weight of GPC test polymer is 6.5 ten thousand
1The H-NMR test polymer is carbonic acid gas and the complete alternating structure of propylene oxide.
Embodiment 3
7.90 g(0.02mol) 3,3 '-two chloro-5,5 '-dinitrobenzene-2,2 '-biphenyl bis-phenol joins and obtains 3,3 '-two transparent chloro-5,5 '-dinitrobenzene-2 in the hot aqueous sodium hydroxide solution of 25 mL 2M, 2 '-biphenyl bisphenol sodium salt aqueous solution is regulated pH=11 with dilute hydrochloric acid; 1.83 g(0.01 mol) then zinc acetate is added drop-wise to zinc acetate aqueous solution above-mentioned 3,3 '-two chloro-5 with 10 mL deionized water dissolvings, 5 '-dinitrobenzene-2,2 '-biphenyl bisphenol sodium salt aqueous solution, 80 ℃ of reaction 5h, cooling is placed 10 h and is separated out zinc phenolic hydroxyl group complex compound Zn
2+[C
12H
6C
L2(NO
2)
2O
2]
2, deionized water wash three times, Büchner funnel are collected, and dry to carry out ultimate analysis with organic element analyzer, theoretical value afterwards: C, 38.36; H, 1.07; Cl, 18.87; N, 7.45.Test value: C, 38.32; H, 1.05; Cl, 18.89; N, 7.43.Zinc 3,3 '-two chloro-5 after drying, 5 '-dinitrobenzene-2,2 '-biphenyl bis-phenol complex compound is normal temperature ageing 24 h in toluene, Büchner funnel is collected, and obtains zinc 3 behind the vacuum drying, 3 '-two chloro-5,5 '-dinitrobenzene-2,2 '-biphenyl bis-phenol complex compound catalyst is put into moisture eliminator for subsequent use.
Catalytically active assessment: the zinc 3 that in the 500ml autoclave, adds 4.0 g, 3 '-two chloro-5,5 '-dinitrobenzene-2,2 '-biphenyl bis-phenol complex compound catalyst, behind 70 ℃ of lower vacuum-drying 24 h, be cooled to room temperature, then add propylene oxide (PO) 300 ml, be filled with carbonic acid gas and heating, finally make the still internal pressure reach 3.0 MPa, 80 ℃ of temperature in the kettle, continue to pass into carbonic acid gas, keep the still internal pressure, react 40 h after cooling discharge residual air, open the propylene oxide bulk solution that takes out the product lined polymethyl ethylene carbonate behind the still, add the trichloromethane dilution, use methanol extraction, get crude product, get after drying final product lined polymethyl ethylene carbonate 21.3 g(97.7g polymkeric substance/g zinc), the number-average molecular weight of GPC test polymer is 6.4 ten thousand
1The H-NMR test polymer is carbonic acid gas and the complete alternating structure of propylene oxide.
Embodiment 4
8.20 g(0.02 mol) 3,3 ', 5,5 '-tetra-tert-2,2 '-biphenyl bis-phenol joins and obtains transparent 3,3 ', 5 in the hot aqueous sodium hydroxide solution of 25 mL 2M, 5 '-tetra-tert-2,2 '-biphenyl bisphenol sodium salt aqueous solution is regulated PH=12 with dilute hydrochloric acid; 1.83 g(0.01 mol) then zinc acetate is added drop-wise to zinc acetate aqueous solution above-mentioned 3,3 ' with 10 mL deionized water dissolvings, 5,5 '-tetra-tert-2 is in 2 '-biphenyl bisphenol sodium salt aqueous solution, 100 ℃ of reaction 10 h, cooling is placed 10 h and is separated out zinc phenolic hydroxyl group complex compound Zn
2+[(C (CH
3)
3)
4C
12H
6O
2]
2, deionized water wash three times, Büchner funnel are collected, and dry to carry out ultimate analysis with organic element analyzer, theoretical value afterwards: C, 76.20; H, 9.14.Test value: C, 76.12; H, 9.08.Zinc 3,3 ', 5 after drying, 5 '-tetra-tert-2,2 '-biphenyl bis-phenol complex compound is normal temperature ageing 48 h in toluene, and Büchner funnel is collected, and obtains zinc 3 behind the vacuum drying, 3 ', 5,5 '-tetra-tert-2,2 '-biphenyl bis-phenol complex compound catalyst is put into moisture eliminator for subsequent use.
Catalytically active assessment: the zinc 3 that in the 500ml autoclave, adds 2.5 g, 3 ', 5,5 '-tetra-tert-2,2 '-biphenyl bis-phenol complex compound catalyst, behind 75 ℃ of lower vacuum-drying 24 h, be cooled to room temperature, then add propylene oxide (PO) 300 ml, be filled with carbonic acid gas and heating, finally make the still internal pressure reach 4.5 MPa, 75 ℃ of temperature in the kettle continue to pass into carbonic acid gas, keep the still internal pressure, residual air is discharged in cooling after reacting 35 h, open the propylene oxide bulk solution that takes out the product lined polymethyl ethylene carbonate behind the still, add the trichloromethane dilution, use methanol extraction, get crude product, get after drying final product lined polymethyl ethylene carbonate 15.8 g(85.6 g polymkeric substance/g zinc), the number-average molecular weight of GPC test polymer is 7.6 ten thousand
1The H-NMR test polymer is carbonic acid gas and the complete alternating structure of propylene oxide.
Claims (9)
1. zinc phenolic hydroxyl group complex compound catalyst is characterized in that structural formula is suc as formula shown in the I:
Wherein, R
1=CH
3, Cl, Br or C (CH
3)
3R
2=CH
3, Br, NO
2Or C (CH
3)
3
2. the preparation method of the described zinc phenolic hydroxyl group of claim 1 complex compound catalyst is characterized in that may further comprise the steps:
(1) with 3,3 ', 5,5 '-four replace-2, and 2 '-biphenyl bis-phenol joins and obtains 3,3 ', 5,5 '-four transparent replacements-2 in the hot aqueous sodium hydroxide solution, and the sodium-salt aqueous solution of 2 '-biphenyl bis-phenol is regulated pH=11～12 with dilute hydrochloric acid;
(2) obtain zinc acetate aqueous solution with the deionized water dissolving zinc acetate, again zinc acetate aqueous solution is added drop-wise to 3,3 ', 5,5 '-four replace-2, in the sodium-salt aqueous solution of 2 '-biphenyl bis-phenol, at 80～100 ℃ of reaction 5～10 h, the zinc phenolic hydroxyl group complex compound of cooling crystallization;
(3) obtain zinc phenolic hydroxyl group complex compound behind the filtration drying, obtain zinc phenolic hydroxyl group complex compound catalyst through after the ageing again.
3. preparation method as claimed in claim 2, it is characterized in that the condition of described ageing is: ageing reagent is toluene, and Aging Temperature is normal temperature, and digestion time is 24～48 h.
4. preparation method as claimed in claim 2 is characterized in that described 3,3 ', 5,5 '-four replace-2, and 2 '-biphenyl bis-phenol is 3,3 ', 5,5 '-tetramethyl--2,2 '-biphenyl bis-phenol, 3,3 ', 5,5 '-tetrabromobisphenol, 2 '-biphenyl bis-phenol, 3,3 '-two chloro-5,5 '-dinitrobenzene-2,2 '-biphenyl bis-phenol, 3,3 ', 5,5 '-tetra-tert-2, a kind of in 2 '-biphenyl bis-phenol.
5. preparation method as claimed in claim 2 is characterized in that described 3,3 ', 5,5 '-four replace-2, and the mol ratio of 2 '-biphenyl bis-phenol and zinc acetate is 2:1.
6. method for preparing lined polymethyl ethylene carbonate is characterized in that may further comprise the steps:
(1) in autoclave, adds zinc phenolic hydroxyl group complex compound catalyst claimed in claim 1, be down to room temperature after the vacuum-drying;
(2) add propylene oxide, be filled with continuously carbonic acid gas, reacting by heating;
(3) obtain the propylene oxide bulk solution of lined polymethyl ethylene carbonate after reaction finishes, add the trichloromethane dilution, use methanol extraction, get crude product, get after drying the final product lined polymethyl ethylene carbonate.
7. the method for preparing as claimed in claim 6 lined polymethyl ethylene carbonate, the weight ratio that it is characterized in that described zinc phenolic hydroxyl group complex compound catalyst and propylene oxide add-on is 1:60～1:250.
8. the method for preparing as claimed in claim 6 lined polymethyl ethylene carbonate is characterized in that the described vacuum drying temperature of step (1) is 70～80 ℃.
9. the method for preparing as claimed in claim 6 lined polymethyl ethylene carbonate, the temperature that it is characterized in that the reaction of step (2) is 60～80 ℃, and the pressure of reaction is 3.0～6.0 MPa, and the time of reaction is 20～40 h.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090211445A1 (en) * | 2007-12-17 | 2009-08-27 | Northwestern University | Amorphous infinite coordination polymer microparticles and use for hydrogen storage |
| CN101759849A (en) * | 2009-09-18 | 2010-06-30 | 广州科梦催化材料有限公司 | Zinc hydroxy acid complex catalyst for copolymerization of carbon dioxide and propylene oxide and preparation method |
| CN102199286A (en) * | 2011-04-08 | 2011-09-28 | 南京航空航天大学 | Metal coordination compounds with zinc (II) and platinum (II) in different doping proportions of based on poly-Salen ligands as well as preparation methods and applications thereof |
-
2012
- 2012-11-20 CN CN201210470886.7A patent/CN102936334B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090211445A1 (en) * | 2007-12-17 | 2009-08-27 | Northwestern University | Amorphous infinite coordination polymer microparticles and use for hydrogen storage |
| CN101759849A (en) * | 2009-09-18 | 2010-06-30 | 广州科梦催化材料有限公司 | Zinc hydroxy acid complex catalyst for copolymerization of carbon dioxide and propylene oxide and preparation method |
| CN102199286A (en) * | 2011-04-08 | 2011-09-28 | 南京航空航天大学 | Metal coordination compounds with zinc (II) and platinum (II) in different doping proportions of based on poly-Salen ligands as well as preparation methods and applications thereof |
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