CN110003458A - A kind of load type solid body base catalyst and its application - Google Patents
A kind of load type solid body base catalyst and its application Download PDFInfo
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- CN110003458A CN110003458A CN201910355922.7A CN201910355922A CN110003458A CN 110003458 A CN110003458 A CN 110003458A CN 201910355922 A CN201910355922 A CN 201910355922A CN 110003458 A CN110003458 A CN 110003458A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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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- 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
- C08G64/307—General preparatory processes using carbonates and phenols
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Abstract
The invention discloses a kind of load type solid body base catalyst and its application, the catalyst is used to prepare isobide base polycarbonate and its derivative, and the catalyst includes carrier, and is carried on the alkali metal compound of the carrier surface；The carrier is alkaline earth oxide or/and rare-earth oxide, and the alkali metal compound is one of the hydroxide of alkali metal, the carbonate of alkali metal, the halide of alkali metal, the nitrate of alkali metal, the acetate of alkali metal.It is catalyzed based on above-mentioned load type solid body base catalyst, using diphenyl carbonate and dihydroxy compounds as raw material, through ester exchange reaction and polycondensation reaction synthesis isobide base polycarbonate and its derivative.The catalyst is suitable for the synthesis of a variety of polycarbonate, has good universality；The makrolon material of synthesis yield with higher and quality, are remarkably improved Business Economic Benefit.
Description
Technical field
The invention belongs to macromolecule synthesising technology fields, and in particular to a kind of load type solid body base catalyst and its application.
Background technique
Polycarbonate (PC) is to produce engineering plastics with fastest developing speed at present, and yield is only second to polyamide, has been applied to
The fields such as electronic apparatus, optical medium, automobile parts and space material.Bisphenol A polycarbonate (BPA-PC) is purposes in PC
Widest product, this is attributed to its excellent hot property and mechanical property.But the bisphenol-A in current research discovery BPA-PC
(BPA) it can migrate during use, since the structure that BPA molecule has similar estrogen may result in human body hair
Sick change, therefore BPA-PC becomes to be absolutely unsafe when as food packaging and biological medicine material.In addition, petroleum resources are derivative
Raw material BPA's is a large amount of using can not only aggravate petroleum exhaustion, and the non-biodegradable of product BPA-PC can also destroy ecological environment.
The considerations of for this several respect, develops the mainstream that nontoxic reproducible biology base PC is PC research field.Isobide (ISB) is
The chipal compounds as made from renewable resource glucose, the nontoxic molecular structure of rigidity, make it can be used as the ideal of bisphenol-A
Substitute, as constructing the high molecular materials such as polyethers, polyester and PC.
The synthetic method Primary Reference of isobide base polycarbonate has industrialized the production method of BPA-PC at present, including
Phosgenation and ester-interchange method.Wherein phosgenation was gradually eliminated due to the problems such as raw material phosgene is hypertoxic；Ester-interchange method due to
The characteristics of its green high-efficient is PC synthesis technology with fastest developing speed at present.The research of isobide base polycarbonate is concentrated mainly on
Ester-interchange method synthesizes on PC, and wherein the preparation of effective catalyst is the key that ester-interchange method synthesis isobide base polycarbonate.
Catalyst used by ester-interchange method synthesis isobide base polycarbonate reported at present is mainly alkaline nothing
Machine salt catalyst, alkaline molecular sieve catalyst, quaternary ammonium ionic liquid, quaternary phosphonium class ionic liquid, glyoxaline ion liquid, heterocycle
Nitrogenous class catalyst etc..Wherein, alkali metal inorganic salt catalyst includes sodium hydroxide, cesium carbonate, lanthanum acetylacetone, acetylacetone,2,4-pentanedione
Lithium (Journal of Industrial and Engineering Chemistry., 2016,37,42；Polym.Chem.,
2015,6,633)；Alkaline molecular sieve catalyst includes Ca/SBA-15, Mg/SBA-15 (108727578 A of CN)；Quaternary amines from
Sub- liquid includes etamon imidazole salts, etamon carbonate, tetrem ammonium acetate salt (105949451 A of CN)；Imidazole-like ionic liquid
Body includes 1- butyl 3- methylimidazole lactate, 1- butyl 3- methyl imidazolium tetrafluoroborate (ACS Sustainable
Chem.Eng.,2018,6,2684)；Heterocyclic nitrogen class catalyst includes bicyclic (4.4.0) the decyl- 5- alkene of 15 7-, tri- nitrine, 7-
Methyl-1, tri- azabicyclic of 5,7- [4.4.0] decyl- 5- alkene (ACS Sustainable Chem.Eng., 2018,6,2684).
But these catalyst are applied to there are more problems: basic mineral in the preparation process of isobide base polycarbonate
Salt catalyst is easy to happen side reaction during the preparation process, and inorganic salts remain in the product, and product is caused to turn to be yellow；Alkali molecules
Sieve catalyst it is with high costs, synthesis process is complicated, is unfavorable for large-scale industrialization application；Quaternary ammonium ionic liquid, season
The catalyst such as Phosphorus ionic liquid and glyoxaline ion liquid it is with high costs, and ionic liquid itself has certain poison
Property, it need to be post-processed；The reactivity of Heterocyclic nitrogen class catalyst is low, and catalyst stability is poor.Therefore, exploitation is a kind of living
Property the low and cheap and easy to get catalyst of high, toxicity have extremely important realistic meaning to the industrialization of isobide polycarbonate.
Summary of the invention
The catalyst institute that it is an object of the invention to solve to prepare isobide base polycarbonate machine and its derivative at present
It is existing it is at high price, be easy to happen the problems such as side reaction and polycarbonate products quality be not high, provide that a kind of activity is high, toxicity
Low and cheap and easy to get load type solid body base catalyst.Load-type solid of the invention has in structure and chemical property
Stronger designability can adjust activity over catalysts point by adjusting carrier and alkali metal compound and maturing temperature
Intensity and distribution promote reaction to carry out to positive direction.Therefore, catalytic activity can be greatly improved, furthermore by adjusting load
Body and alkali metal compound and maturing temperature, reduce the number of superpower active site, effectively inhibit Fries rearrangement reaction, heat
The generation of decomposition reaction.And the catalyst is after usage, can be used as inorganic filler and remains in polycarbonate products, i.e.,
It ensure that product quality, and reduce the process flow of subsequent deduction removal of impurities, reduce production cost, it can be large-scale in the industry
Using.
To achieve the goals above, the technical solution adopted by the present invention are as follows: a kind of load type solid body base catalyst, it is described to urge
Agent is used to prepare isobide base polycarbonate and its derivative, and the catalyst includes carrier, and is carried on the load
The alkali metal compound in body surface face；The carrier be alkaline earth oxide or/and rare-earth oxide,
The alkali metal compound is the hydroxide of alkali metal, the carbonate of alkali metal, the halide of alkali metal, alkali gold
One of the nitrate of category, acetate of alkali metal.
Further, the mass ratio of the alkali metal compound and institute's carrier is 0.01~1:1.More preferably, the ratio
For 0.05-0.5:1.
Further, the hydroxide of the alkali metal is lithium hydroxide, in sodium hydroxide, potassium hydroxide, cesium hydroxide
One or more mixing；
The carbonate of the alkali metal is one of lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate or a variety of mixing；
The halide of the alkali metal is one of lithium halide, sodium halide, potassium halide, caesium halide or a variety of mixing；
More preferably, alkali halide is one of sodium fluoride, potassium fluoride, cesium fluoride, cesium fluoride；
The nitrate of the alkali metal is one of lithium nitrate, sodium nitrate, potassium nitrate, cesium nitrate or a variety of mixing；
The acetate of the alkali metal is one of lithium acetate, sodium acetate, potassium acetate, cesium acetate or a variety of mixing.
The alkaline earth oxide is one of magnesia, calcium oxide, barium monoxide, strontium oxide strontia or a variety of mixing；
The rare-earth oxide is one of lanthana, cerium oxide, europium oxide, ytterbium oxide or a variety of mixing.
A kind of preparation method preparing above-mentioned supported solid catalyst, including, the alkali metal compound is configured to
Aqueous solution, then the carrier is immersed in the aqueous solution, it is uniformly mixed, then the evaporation drying at 60 DEG C~120 DEG C, obtains
To presoma, the presoma roasts to 0.5 at 80 DEG C~900 DEG C~for 24 hours, obtain the catalyst.
The preparation method of a kind of isobide base polycarbonate and its derivative, based on above-mentioned supported solid base catalysis
Agent catalysis synthesizes isobide base through ester exchange reaction and polycondensation reaction using diphenyl carbonate and dihydroxy compounds as raw material
Polycarbonate and its derivative.
Further, the catalyst and the diphenyl carbonate mass ratio are 0.001~5:100.
Further, the temperature of the ester exchange reaction is 80 DEG C~200 DEG C, the air pressure of reaction system is 1.01 ×
105Pa, reaction time 0.5h-5h；The temperature of the polycondensation reaction is 200 DEG C~280 DEG C, and the air pressure of reaction system is greater than 0Pa
Less than or equal to 5 × 102Pa, reaction time 0.5h-6h.It should be noted that in the present invention, the air pressure of reaction system refers to
Absolute pressure.
Further, the dihydroxy compounds be ethylene glycol, 1,2-PD, 1,3-PD, 1,3-BDO, 1,
4- butanediol, 1,5-PD, neopentyl glycol, 1,6- hexylene glycol, 1,3- hexylene glycol, 1,7- heptandiol, 2,2'- oxo diethyls
Alcohol, diglycol, triethylene-glycol, polytetrahydrofuran, 1,3- cyclopentadienyl alcohol, 1,4- cyclohexanediol, 1,4- hexamethylene two
Methanol, 1,10- certain herbaceous plants with big flowers glycol, 2,2,4,4- tetramethyl -1,3- cyclobutanediol, isobide, terephthalyl alcohol, tricyclic decane diformazan
One of alcohol, bisphenol-A and 4,4- (9- fluorenes) biphenol are a variety of.
Further, in the present invention, a kind of isobide base polycarbonate and its derivative are provided, by above-mentioned preparation
Method is made.
Further, the molar ratio of diphenyl carbonate and dihydroxy compounds is 0.5~1.5:1.Preferably, dipheryl carbonate
The molar ratio of ester and dihydroxy compounds dosage is 0.8~1.2:1.
Further, load type solid body base catalyst is the 0.001%~5% of diphenyl carbonate weight, is preferably loaded
Type solid base catalyst is the 0.01%~2.5% of diphenyl carbonate weight, it is further preferable that load type solid body base catalyst is used
Amount is the 0.05%~1% of diphenyl carbonate weight
By adopting the above-described technical solution, the beneficial effects of the present invention are:
(1) catalyst provided by the invention and its synthetic method can be widely applied to isobide type polycarbonate, different mountain
The synthesis of Copolycarbonate between pears alcohol and other dihydroxy compounds Copolycarbonates and other dihydroxy compounds, can
Suitable for the synthesis of a variety of polycarbonate, there is good universality；The makrolon material of synthesis yield with higher and
Quality is remarkably improved Business Economic Benefit；
(2) catalyst provided by the invention and existing quaternary ammonium ionic liquid, quaternary phosphonium class ionic liquid, imidazole-like ionic
Liquid, acetylacetonate, alkali carbonate, solid alkali zeolite are compared with catalyst systems such as organic bases, the activity of catalyst
Height, catalytic efficiency is good, in the preparation process for being applied to polycarbonate, so that the molecule chain growth speed of polycarbonate is fast, it can
Biggish molecular weight is obtained in a relatively short period of time, product is avoided gelatin phenomenon occur, product is caused to turn to be yellow, and influences product color
Pool.
And load type solid body base catalyst of the invention, can be directly residual directly as inorganic filler after being applied to reaction
It stays in makrolon material, is separated without subsequent processing, the polycarbonate system that need to adulterate inorganic filler can be widely used in
It is standby；
(3) synthetic method craft process provided by the invention is simple and efficient, it is easy to accomplish large-scale production.
Specific embodiment
In order to which those skilled in the art better understand the present invention, following embodiment makees the present invention further detailed
Description.
The number-average molecular weight of isobide base polycarbonate is surveyed using gel permeation chromatograph (GPC) in following example
, wherein being using chloroform as solvent, polystyrene is standard specimen.And the structure and envelope of the polycarbonate by 1H-NMR measurement synthesis
End group group.The yield of polycarbonate are as follows: the ratio of the practical quality for obtaining polymer and Theoretical Mass.
The raw material and maturing temperature of 1 embodiment 1-16 catalyst of table
Embodiment 1-18 prepares different loaded catalysts upper using parameter and raw material different in such as table 1
It states in table 1, mass ratio refers to alkali metal compound and the carrier quality ratio.
Embodiment 1
20-KF/MgO-500 catalyst is synthesized using infusion process: KF is dissolved in deionized water, MgO is added in solution,
12h is stirred at room temperature, evaporation drying at 80 DEG C obtains presoma (white powder), can obtain after roasting 4.0h under the conditions of 500 DEG C
To 20-KF/MgO-500.
Embodiment 2
20-KF/MgO-500 catalyst is synthesized using ultrasonic immersing method: KF being dissolved in deionized water, MgO is added molten
In liquid, ultrasonic reaction 6h, evaporation drying at 80 DEG C obtains presoma (white powder), is roasted after 4.0h under the conditions of 500 DEG C i.e.
20-KF/MgO-500 can be obtained.
Embodiment 3
20-KF/CaO-500 catalyst is synthesized using infusion process: KF is dissolved in deionized water, CaO is added in solution,
12h is stirred at room temperature, evaporation drying at 100 DEG C obtains presoma (white powder), after roasting 3.0h under the conditions of 500 DEG C
Obtain 20-KF/CaO-500.
Embodiment 4
20-KF/La is synthesized using infusion process2O3- 500 catalyst: KF is dissolved in deionized water, by La2O3Solution is added
In, 12h, evaporation drying at 100 DEG C is stirred at room temperature, obtained catalyst precursor (white powder) roasts under the conditions of 500 DEG C
20-KF/La can be obtained after 3.0h2O3-500。
Embodiment 5
20-K is synthesized using infusion process2CO3/ MgO-500 catalyst: by K2CO3It is dissolved in deionized water, MgO is added molten
In liquid, 12h is stirred at room temperature, evaporation drying at 100 DEG C obtains presoma (white powder), after roasting 3.0h under the conditions of 500 DEG C
20-K can be obtained2CO3/MgO-500。
Embodiment 6
20-K is synthesized using infusion process2CO3/ CaO-500 catalyst: K2CO3 is dissolved in deionized water, CaO is added molten
In liquid, 12h is stirred at room temperature, evaporation drying at 100 DEG C obtains presoma (white powder), after roasting 3.0h under the conditions of 500 DEG C
20-K can be obtained2CO3/CaO-500。
Embodiment 7
20-K is synthesized using infusion process2CO3/La2O3- 500 catalyst: by the K of 20wt%2CO3It is dissolved in deionized water, it will
La2O3It is added in solution, 12h, evaporation drying at 100 DEG C, obtained presoma (white powder), in 500 DEG C of conditions is stirred at room temperature
20-K can be obtained after lower roasting 3.0h2CO3/La2O3-500。
Embodiment 8
The preparation method is the same as that of Example 1 for 20-KF/MgO-80 catalyst, the difference is that, presoma (white powder) exists
24.0h is roasted under the conditions of 80 DEG C obtains 20-KF/MgO-80 catalyst.
Embodiment 9
The preparation method of 20-KF/MgO-300 catalyst with embodiment 3, the difference is that, presoma (white powder)
24.0h is roasted under the conditions of 300 DEG C obtains 20-KF/MgO-300 catalyst.
Embodiment 10
The preparation method is the same as that of Example 1 for 20-KF/MgO-400 catalyst, the difference is that, presoma (white powder)
24.0h is roasted under the conditions of 400 DEG C obtains 20-KF/MgO-400 catalyst.
Embodiment 11
The preparation method is the same as that of Example 1 for 20-KF/MgO-600 catalyst, the difference is that, presoma (white powder)
24.0h is roasted under the conditions of 600 DEG C obtains 20-KF/MgO-600 catalyst.
Embodiment 12
The preparation method is the same as that of Example 1 for 20-KF/MgO-700 catalyst, the difference is that, presoma (white powder)
24.0h is roasted under the conditions of 700 DEG C obtains 20%KF/MgO catalyst.
Embodiment 13
The preparation method is the same as that of Example 1 for 5-KF/MgO-500 catalyst, the difference is that, presoma (white powder) exists
24.0h is roasted under the conditions of 500 DEG C obtains 5-KF/MgO-500 catalyst.
Embodiment 14
The preparation method is the same as that of Example 1 for 10-KF/MgO-500 catalyst, the difference is that, presoma (white powder)
24.0h is roasted under the conditions of 500 DEG C obtains 20-KF/MgO-500 catalyst.
Embodiment 15
The preparation method is the same as that of Example 1 for 50-KF/MgO-500 catalyst, the difference is that, presoma (white powder)
24.0h is roasted under the conditions of 500 DEG C obtains 50-KF/MgO-500 catalyst.
Embodiment 16
The preparation method is the same as that of Example 1 for 100-KF/MgO-500 catalyst, the difference is that, presoma (white powder)
24.0h is roasted under the conditions of 500 DEG C obtains 100-KF/MgO-500 catalyst.
It in other embodiments of the invention, can also be by the halogen of the alkali metal such as NaF, LiF, NaCl of the KF in embodiment 1
Compound replaces, correspondingly, BaO also can be used, the alkaline earths/rare earth metal such as strontium oxide strontia, lanthana, cerium oxide, europium oxide, ytterbium oxide
Oxide replaces MgO, is not described in detail herein.
In other embodiments of the invention, potassium carbonate can be also replaced with lithium carbonate, sodium carbonate, cesium carbonate, also can be used
Alkali nitrates, alkali metal acetate replace potassium carbonate.
Synthesize the concrete scheme 1 of isobide type polycarbonate:
Diphenyl carbonate and isobide and above-described embodiment 1-18 catalyst prepared are added in reactor,
Wherein catalyst amount is the 0.01% of diphenyl carbonate total weight.Reactant is heated under normal pressure, N2 atmosphere and is reached
Molten condition；React 2h；Then by the pressure reduction in reactor to 200Pa, at 240 DEG C, 0.5h is reacted；It can be obtained different
Sorb alcohol type polycarbonate (white solid), corresponding label are number.Wherein, when using the catalyst of embodiment 1-16
(i.e. product 1-16), the molar ratio of diphenyl carbonate and isobide are 1:1, product 17, using the catalysis of embodiment 1
Agent, wherein catalyst: the molar ratio of diphenyl carbonate and isobide is 0.9:1.Product 18, the embodiment 1 of use is urged
Agent: the molar ratio of diphenyl carbonate and isobide is 1.1:1.
Using exclusion chromatography, the isobide type polycarbonate of the catalyst synthesis of testing example 1-18 is (right respectively
The product answered 1-18) molecular weight, and by calculating, the yield of product is obtained, result is as shown in table 2 below.
The molecular weight of 2 product of table 1-18
| Product | Molecular weight | Yield (%) | Product | Molecular weight | Yield (%) |
| No. 1 | 75100 | 96 | No. 10 | 48000 | 93 |
| No. 2 | 60600 | 95 | No. 11 | 49500 | 95 |
| No. 3 | 48000 | 95 | No. 12 | 30500 | 97 |
| No. 4 | 35000 | 95 | No. 13 | 30600 | 96 |
| No. 5 | 51000 | 95 | No. 14 | 51600 | 98 |
| No. 6 | 33000 | 95 | No. 15 | 42400 | 96 |
| No. 7 | 43000 | 96 | No. 16 | 37400 | 92 |
| No. 8 | 51800 | 95 | No. 17 | 38200 | 91 |
| No. 9 | 62100 | 94 | No. 18 | 42200 | 90 |
In above-mentioned table 2, the molecular weight of product is the weight average molecular weight of product, and product 1-18 is that white is solid
Body.
The preparation that product 19:
Based on embodiment 1 prepare catalyst, by molar ratio be 1:1 diphenyl carbonate and dihydroxy based mixtures, (wherein
The 1,4-butanediol and isobide that dihydroxy based mixtures are molar ratio 1:1) and the catalyst for preparing of embodiment 1 be added
Into reactor, catalyst amount is the 0.01% of diphenyl carbonate quality.Normal pressure under N2 atmosphere, increases the temperature in reactor
Degree, until the melting temperature of reaction mass, reacts 2h；Then by the pressure reduction of reactor to 200Pa, controlling reaction temperature is
240 DEG C, react 1h.Poly- carbonic acid butanediol-isobide type polycarbonate block Copolycarbonate is obtained, product is pale yellow colored solid
Body, using the molecular weight Mw=55500 of gel chromatography test polycarbonate, calculating its yield is 92%.
The preparation that product 20:
Based on embodiment 1 prepare catalyst, by molar ratio be 1:1 diphenyl carbonate and dihydroxy based mixtures (wherein
Dihydroxy based mixtures are pentanediol and isobide, and the molar ratio of pentanediol and isobide is 1:1), in condition and product
No. 19 identical, obtains poly- neopentyl glycol carbonate-isobide type polycarbonate block Copolycarbonate, product is pale yellow colored solid
Body.Using the molecular weight Mw=53800 of gel chromatography test polycarbonate, calculating its yield is 94%.
The preparation of product 21:
The difference is that, raw material: the diphenyl carbonate and dihydroxy that molar ratio is 1:1 are mixed with the preparation method of product 19
Object is closed, dihydroxy based mixtures are hexylene glycol and isobide, and wherein the molar ratio of hexylene glycol and isobide is 1:1.Gathered
Carbonic acid hexylene glycol-isobide type polycarbonate block Copolycarbonate, product is faint yellow solid.It is tested using gel chromatography
The molecular weight Mw=36100 of polycarbonate, calculating its yield is 95%.
The preparation of product 22:
The difference is that, raw material: molar ratio is the diphenyl carbonate two and dihydroxy of 1:1 with the preparation method of product 19
Mixture, dihydroxy based mixtures are 1,3- cyclopentadienyl alcohol and isobide, wherein mole of 1,3- cyclopentadienyl alcohol and isobide
Than for 1:1, other conditions are constant, poly- carbonic acid 1 is obtained, 3- cyclopentadienyl alcohol-isobide type polycarbonate block Copolycarbonate,
Product is faint yellow solid.Using the molecular weight Mw=42000 of gel chromatography test polycarbonate, calculating its yield is 92%.
The preparation that product 23
The difference is that, raw material: the diphenyl carbonate and dihydroxy that molar ratio is 1:1 are mixed with the preparation method of product 19
Object is closed, dihydroxy based mixtures are rubbing for Isosorbide-5-Nitrae-cyclohexanedimethanol and isobide, wherein Isosorbide-5-Nitrae-cyclohexanedimethanol and isobide
, than being 1:1, other conditions are constant for you, obtain poly- carbonic acid Isosorbide-5-Nitrae-cyclohexanedimethanol-isobide type polycarbonate block copolymerization carbon
Acid esters, product are faint yellow solid.Using the molecular weight Mw=62800 of gel chromatography test polycarbonate, calculating its yield is
94%.
The preparation of product 24:
The difference is that, raw material: the diphenyl carbonate and dihydroxy that molar ratio is 1:1 are mixed with the preparation method of product 19
Object is closed, dihydroxy based mixtures are the pure and mild isobide of terephthaldehyde, and wherein the molar ratio of terephthalyl alcohol and isobide is 1:
1, other conditions are constant, obtain poly- carbonic acid terephthalyl alcohol-isobide type polycarbonate block Copolycarbonate, and product is light
Yellow solid.Using the molecular weight Mw=43100 of gel chromatography test polycarbonate, calculating its yield is 89%.
The preparation of product 25:
The difference is that, raw material: the diphenyl carbonate and dihydroxy that molar ratio is 1:1 are mixed with the preparation method of product 19
Closing object, dihydroxy based mixtures are bisphenol-A and isobide, wherein be 1:1 to the molar ratio of bisphenol-A and isobide, other
Part is constant, and obtaining poly- carbonic acid bisphenol-A-isobide type polycarbonate block Copolycarbonate product is faint yellow solid.It adopts
With the molecular weight Mw=23 of gel chromatography test polycarbonate, 200, calculating its yield is 91%.
Comparative example 1
Using etamon imidazole salts as catalyst, preparation method is identical as the preparation method of No. 1 product, obtains different sorb
Alcohol type polycarbonate (white solid), using the molecular weight Mw=23000 of gel chromatography test polycarbonate, calculating its yield is
95%.
Comparative example 2
It is catalyst for Ca/SBA-15, other conditions are identical as comparative example 1, and it is (white to obtain isobide type polycarbonate
Color solid), molecular weight Mw=38000, calculating its yield is 94%.
Comparative example 3
Using tetraethyl ammonium hydroxide as catalyst, other conditions are identical as comparative example 1, obtain the poly- carbonic acid of isobide type
Ester (white solid), molecular weight Mw=21500, calculating its yield is 91%.
Comparative example 4
Using Li2CO3 as catalyst, other conditions are constant, the molecular weight Mw=28 of gained polycarbonate, and 900, calculate its receipts
Rate is 90%.
Comparative example 5
With comparative example 1, used catalyst is CsCO3 catalyst, and other conditions are identical as comparative example 1, obtain different sorb
Alcohol type polycarbonate (white solid), molecular weight Mw=44000, calculating its yield is 93%.
Comparative example 6
Using lanthanum acetylacetone as catalyst, other conditions are identical as comparative example 1, obtain isobide type polycarbonate
(white solid), molecular weight Mw=29500, calculating its yield is 89%.
Comparative experimental example 1-5 uses existing catalyst, identical as No. 1 preparation method of product, is made in comparative example 1-5
Product molecular weight between 23000-44000, compared compared to using product 1-18 of catalyst preparation of the invention,
The molecular weight of product of the invention is being apparently higher than comparative experimental example, wherein the molecular weight of No. 1, No. 2 and No. 9 product is above
60000, in the synthesis process due to isobide base polycarbonate, isobide base leads to the growth of strand as heterocycle
Difficulty then needs the longer reaction time if you need to reach longer strand, but as the reaction time increases, has more
Side reaction occurs, and gel occurs, causes product color poor.Using the product of the catalyst preparation of the embodiment of the present invention 1-16
No. 1-18, higher weight average molecular weight is obtained in a short time, illustrates catalyst of the invention activity with higher, is catalyzed
High-efficient, the speed of the molecule chain growth of polycarbonate is fast, compared with the catalyst of comparative experimental example 1-6, catalysis of the invention
The excellent catalytic effect of agent.And loaded catalyst of the invention is using alkaline earth/rare-earth oxide as carrier, alkali metal
Hydroxide, halide, nitrate, acetate are active material, and alkali metal compound and carrier interact, in the table of carrier
Face generates new object phase, increases active site, improves the catalytic efficiency of catalyst.
The above, only presently preferred embodiments of the present invention, are not intended to limit the invention, patent protection model of the invention
It encloses and is subject to claims, it is all to change with equivalent structure made by description of the invention, similarly should all include
Within the scope of the present invention.
Claims (10)
1. a kind of load type solid body base catalyst, it is characterised in that: the catalyst includes carrier, and is carried on the carrier
The alkali metal compound on surface；The carrier be alkaline earth oxide or/and rare-earth oxide,
The alkali metal compound is the hydroxide of alkali metal, the carbonate of alkali metal, the halide of alkali metal, alkali metal
One of nitrate, acetate of alkali metal.
2. load type solid body base catalyst according to claim 1, it is characterised in that: the alkali metal compound with it is described
The mass ratio of carrier is 0.01~1:1.
3. load type solid body base catalyst according to claim 1, it is characterised in that: the hydroxide of the alkali metal is
One of lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide or a variety of mixing；
The carbonate of the alkali metal is one of lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate or a variety of mixing；
The halide of the alkali metal is one of lithium halide, sodium halide, potassium halide, caesium halide or a variety of mixing；
The nitrate of the alkali metal is one of lithium nitrate, sodium nitrate, potassium nitrate, cesium nitrate or a variety of mixing；
The acetate of the alkali metal is one of lithium acetate, sodium acetate, potassium acetate, cesium acetate or a variety of mixing.
4. load type solid body base catalyst according to claim 1, it is characterised in that: the alkaline earth oxide is oxygen
Change one of magnesium, calcium oxide, barium monoxide, strontium oxide strontia or a variety of mixing；
The rare-earth oxide is one of lanthana, cerium oxide, europium oxide, ytterbium oxide or a variety of mixing.
5. a kind of preparation method of load type solid body base catalyst as described in claim 1, it is characterised in that: including,
The alkali metal compound is configured to aqueous solution, then the carrier is immersed in the aqueous solution, is uniformly mixed, so
The evaporation drying at 60 DEG C~120 DEG C afterwards, obtains presoma, the presoma roasts to 0.5 at 80 DEG C~900 DEG C~for 24 hours,
Obtain the catalyst.
6. the preparation method of a kind of isobide base polycarbonate and its derivative, which is characterized in that based on such as claim 1 or
Catalyst described in 5 synthesizes different mountain through ester exchange reaction and polycondensation reaction using diphenyl carbonate and dihydroxy compounds as raw material
Pears alcohol radical polycarbonate and its derivative.
7. the preparation method of isobide base polycarbonate according to claim 6 and its derivative, which is characterized in that institute
It states catalyst and the diphenyl carbonate mass ratio is 0.001~5:100.
8. the preparation method of isobide base polycarbonate according to claim 6 and its derivative, which is characterized in that institute
The temperature for stating ester exchange reaction is 80 DEG C~200 DEG C, and the air pressure of reaction system is 1.01 × 105Pa, reaction time 0.5h-5h；
The temperature of the polycondensation reaction is 200 DEG C~280 DEG C, and the air pressure of reaction system is greater than 0Pa and is less than or equal to 5 × 102Pa, when reaction
Between be 0.5h-6h.
9. the preparation method of isobide base polycarbonate according to claim 6 and its derivative, it is characterised in that: institute
Stating dihydroxy compounds is ethylene glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, 1,5- penta 2
Alcohol, neopentyl glycol, 1,6- hexylene glycol, 1,3- hexylene glycol, 1,7- heptandiol, 2,2'- oxo diethanols, diglycol, two
Contracting triethylene glycol, polytetrahydrofuran, 1,3- cyclopentadienyl alcohol, 1,4- cyclohexanediol, 1,4- cyclohexanedimethanol, 1,10- certain herbaceous plants with big flowers glycol, 2,
2,4,4- tetramethyl -1,3- cyclobutanediol, isobide, terephthalyl alcohol, tricyclic decane dimethanol, bisphenol-A and 4,4- (9-
Fluorenes) one of biphenol or a variety of.
10. a kind of isobide base polycarbonate and its derivative, it is characterised in that: any described different by claim 6-9
The preparation method of sorb alcohol radical polycarbonate and its derivative is made.
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| CN111138650A (en) * | 2020-01-16 | 2020-05-12 | 中国科学院过程工程研究所 | High-molecular-weight high-flexibility bio-based polycarbonate copolymer and preparation method thereof |
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