CN104028310B - A kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst - Google Patents
A kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst Download PDFInfo
- Publication number
- CN104028310B CN104028310B CN201410312867.0A CN201410312867A CN104028310B CN 104028310 B CN104028310 B CN 104028310B CN 201410312867 A CN201410312867 A CN 201410312867A CN 104028310 B CN104028310 B CN 104028310B
- Authority
- CN
- China
- Prior art keywords
- mfi
- catalyst
- preparation
- carbonic acid
- synthesis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst.The method, the preparation method of this catalyst intersects MFI conversion molecular sieve with stratiform to become H-MFI molecular sieve, then in H-MFI on grafting transition metal oxide, then grafting organic oxidation tin, obtain stratiform intersection MFI molecular sieve Inorganic whisker hybrid catalyst.The activated carbonyl of the inorganic transition metal oxide of this catalyst grafting can improve the close power of DMC, the activation phenolic hydroxyl group of the organic oxidation tin of grafting improves the nucleophilie nucleus ability of BPA, and then the conversion ratio of BPA can be improved, and selectivity synthesis PC intermediate, can also the effective alkylation suppressing BPA.The catalyst of the present invention's synthesis belongs to typical heterogeneous catalysis, immiscible with product, is applied in synthetic reaction, solves homogeneous catalyst and the not segregative difficult problem of product.
Description
Technical field
The invention belongs to the preparation method of chemical synthesis catalyst, be specially a kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst.
Background technology
Merlon (PC) has the advantages such as heat-resisting, shock resistance, fire-retardant, transparent and good mechanical performance, therefore extensive use in glass assembling industry, auto industry and electronics, electrical equipment industry, office equipment, health care, film and protective equipment etc.PC is the product uniquely in five large-engineering plastics with good transparency, is also the general engineering plastic that growth rate is the fastest in recent years.
PC is prepared primarily of phosgenation, but because its phosgene reaction thing using carrene to be solvent and severe toxicity, all has serious harm to environment and the mankind, therefore urgently carries out the green syt research of PC.
PC green synthesis process comprises: bisphenol-A (BPA) oxidative carbonylation, ester-interchange method.Both have all abandoned the use to hypertoxic phosgene.BPA oxidative carbonylation reaction needed is with the Metal Palladium of costliness for catalyst, and the PC molecular weight of synthesis is general lower.Ester-interchange method comprises diphenyl carbonate (DPC) method and dimethyl carbonate (DMC) method.DPC method needs high temperature, and high temperature causes the generation of a lot of side reaction, and operating procedure is various.Utilize DMC to replace DPC directly react with BPA, the synthesis of intermediate product DPC can be avoided, reduce operating procedure, saving funds, and can the accessory substance of corresponding minimizing polycondensation process generation.
DMC method is with DMC and BPA for starting ester exchange system is for PC intermediate dimethoxy carbonic acid bisphenol A diester (BMBPA), then by BMBPA self polycondensation, and synthesis PC high polymer.Generating portion methoxy bisphenol A mono-ester (MMBPA) in BMBPA building-up process, and generate with part BPA alkylate by-product, MMBPA is unfavorable for synthesis HMW PC, and BPA alkylate has a strong impact on PC performance.Therefore, in DMC method synthesis PC, key issue is selectivity synthesis intermediate polycarbonate BMBPA and suppresses alkylated reaction.
In DMC method building-up process, Problems existing impels scientific research personnel to put forth effort on the catalyst of preparation appropriate configuration, improves catalyst activity, the generation of selectivity synthesis BMBPA and suppression alkylate by-product.The people such as Haba adopt N, N-dimethyl-4-amino-pyridine (DMAP)/(BuSnCl)
2o is catalyst, and adds a certain amount of
molecular sieve separating methanol, driving a reaction carries out to forward, and after reaction 48h, BMBPA yield reaches 22%.In a large number
molecular sieve have the methanol stripper being beneficial to generation, but add stirring difficulty.
The Inorganic whisker hybrid catalyst with stratiform intersection MFI molecular sieve structure has higher specific area, is conducive to the touch opportunity increasing reactant and catalyst.The transition metal oxide of grafting on MFI framework of molecular sieve and organic oxidation tin synergy can selectivity synthesis PC intermediate B MBPA, and can reduce alkylate by-product ratio.
Research shows: simple stratiform intersection MFI molecular sieve, does not have catalytic activity; The catalytic activity of simple stratiform intersection H-MFI molecular sieve is very low, and does not have inhibitory action to alkylate.Can selectivity synthesis BMBPA and to suppress BPA alkylating be that the stratiform of grafting transition metal oxide and organic oxidation tin intersects MFI molecular sieve, this catalyst is heterogeneous catalysis.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is: provide a kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst.The preparation method of this catalyst intersects MFI conversion molecular sieve with stratiform to become H-MFI molecular sieve, then in H-MFI on grafting transition metal oxide, then grafting organic oxidation tin, obtain stratiform intersection MFI molecular sieve Inorganic whisker hybrid catalyst.The activated carbonyl of the inorganic transition metal oxide of this catalyst grafting can improve the close power of DMC, the activation phenolic hydroxyl group of the organic oxidation tin of grafting improves the nucleophilie nucleus ability of BPA, and then the conversion ratio of BPA can be improved, and selectivity synthesis PC intermediate, can also the effective alkylation suppressing BPA.
The technical scheme that the present invention solve the technical problem is: provide a kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst.This preparation method is specific as follows:
(1) asymmetric Bis-quaternary Ammonium Salt Surfactant C
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2c
mh
2m+1br
2preparation, comprise the following steps: get brominated alkanes C
nh
2n+1br (n=4 ~ 30 are preferably n=7 ~ 25) and N, N, N', N'-tetramethyl-1,6-hexamethylene diamine are dissolved in toluene/acetonitrile mixed solution (C
nh
2n+1br and N, N, N', the mol ratio of N'-tetramethyl-1,6-hexamethylene diamine is 1:1-20), synthetic reaction is carried out in heating, synthesis temperature is 60 ~ 120 DEG C, and generated time is 5 ~ 12h, obtains surfactant-intermediate C after reaction terminates by conventional filtration or centrifugal method
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2br; Get C again
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2br and bromoalkane C
mh
2m+1br (m=2 ~ 15 are preferably m=4 ~ 12) (C
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2br and C
mh
2 m+1br mol ratio is 1:1 ~ 5) under 60 ~ 120 DEG C of conditions, reaction 5 ~ 12h, centrifugal or filtration, and with ether or alkyl halide washing, then dry, obtain asymmetric Bis-quaternary Ammonium Salt Surfactant C
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2c
mh
2m+1br
2;
(2) synthesis of stratiform intersection MFI molecular sieve, comprises the following steps: the mol ratio of synthesis liquid composition is Na
2o:Al
2o
3: SiO
2: C
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2c
mh
2m+1br
2: H
2sO
4: H
2o=30:x:100:y:18:4000 (x=1 ~ 50, y=5 ~ 15, be preferably x=5 ~ 43, y=7 ~ 11), after synthesis stirred at ambient temperature 10 ~ 12h, this mixed system is transferred to in teflon-lined reactor, high temperature crystallization, crystallization temperature 140 ~ 200 DEG C, crystallization time 10 minutes ~ 30 days, filters, washing, drying, calcining, obtains stratiform intersection MFI molecular sieve;
(3) there is the preparation of the Inorganic whisker hybrid catalyst of stratiform chi structure MFI molecular sieve, namely synthesize the preparation of dimethoxy carbonic acid bisphenol A diester catalyst, comprise the following steps:
1. stratiform intersection MFI conversion molecular sieve becomes H-MFI: the MFI molecular sieve that first stratiform obtained intersected is dissolved in 1mol/LNH
4nO
3solution, carries out back flow reaction subsequently, reflux temperature 80 ~ 120 DEG C, return time 2 ~ 4h, centrifugal or filtration, and dry, high-temperature calcination, namely obtains stratiform H-MFI molecular sieve;
2. grafting transition metal oxide on H-MFI molecular sieve: on described H-MFI, grafting transition metal oxide method is: equi-volume impregnating;
3. grafting organic oxidation tin on H-MFI, concrete steps are: the first step, get 3-r-chloropropyl trimethoxyl silane and magnesium rod prepares silane RMgBr; Second step, silane RMgBr prepares tin one type of silane with anhydrous stannic chloride back flow reaction again; 3rd step, gets a NBB, bromocyclohexane, bromobenzene or bromotoluene and magnesium rod reacts, and obtains butyl magnesium bromide, cyclohexyl magnesium bromide, phenyl-magnesium-bromide or benzyl magnesium bromide RMgBr; 4th step, subsequently by second and third step product reaction, and add the stratiform intersection MFI molecular sieve that grafting has transition metal oxide, back flow reaction 2-8 hour, reacts with NaOH or KOH weak solution after product suction filtration, and concentration is 0.5-20mol/L, and reactant liquor Ph is 7-14 after controlling reaction, filter, dry, namely obtain the catalyst synthesizing dimethoxy carbonic acid bisphenol A diester.
Described transition metal oxide is the mixture of titanium dioxide or vanadic anhydride or both arbitrary proportions.Described organic oxidation tin is aryl oxidized tin or alkyl-tin oxide.Described aryl oxidized tin is phenyl tin oxide, benzyl tin oxide or tert-butyl benzene tin oxide.Described alkyl-tin oxide is cyclohexyl tin oxide, butyl tin oxide or tert-butyl group tin oxide.
In addition, comprise the following steps with described catalyst preparing dimethoxy carbonic acid bisphenol A diester: first BPA and catalyst are heated to 120 DEG C ~ 200 DEG C, then constant speed slowly drips DMC, make reaction temperature maintain 120 DEG C ~ 200 DEG C, reaction 4-12h, namely obtains dimethoxy carbonic acid bisphenol A diester.
Beneficial effect of the present invention is: in the method for synthetic catalyst provided by the invention, grafting inorganic transition metal oxide and organic oxidation tin on the MFI molecular sieve of stratiform chi structure first, and the stratiform of preparation is intersected MFI molecular sieve Inorganic whisker hybrid catalyst first Application in the synthesis of dimethoxy carbonic acid bisphenol A diester.The present invention, by the organotin oxides in catalyst and inorganic transition metal oxide synergy catalysis BPA and DMC polymerisation, effectively controls alkylation ratio in polymerization process, and significantly improves the selective of target product.The catalyst of the present invention's synthesis belongs to typical heterogeneous catalysis, immiscible with product, is applied in synthetic reaction, solves homogeneous catalyst and the not segregative difficult problem of product.
Detailed description of the invention
Provide specific embodiments of the invention below.Specific embodiment, only for further describing the present invention, does not limit the protection domain of the application's claim.
Embodiment 1
(1) 15gC is got
22h
45br adds in 192mL toluene in beaker and acetonitrile mixed solution (toluene and acetonitrile volume ratio are 1:1), and stirring and dissolving, is placed in constant pressure funnel, for subsequent use.Get 24.8mLN again, N, N', N'-tetramethyl-1,6-hexamethylene diamine joins in there-necked flask.In 82 DEG C of back flow reaction, in constant pressure funnel, liquid slowly drips, and reaction 10h, filters, dry, obtains C
22h
45n (CH
3)
2(CH
2)
6n (CH
3)
2br.
(2) 20gC is got
22h
45n (CH
3)
2(CH
2)
6n (CH
3)
2br, is dissolved in 107mL acetonitrile solution, then gets 10mLC
6h
13br, adds there-necked flask respectively, 82 DEG C of back flow reaction 10h, filters, dry, obtains C
22h
45n (CH
3)
2(CH
2)
6n (CH
3)
2c
6h
13br
2.
(3) first 4gNaOH is dissolved in 56.25g water, then adds 8.18gC wherein
22h
45n (CH
3)
2(CH
2)
6n (CH
3)
2c
6h
13br
2, 60 DEG C add thermal agitation 1h and make it dissolve, stand-by after this solution (solution 1) is cooled to room temperature.Separately get a beaker, add 24.75g water, then add the dense H of 1.98g
2sO
4(98%), 0.75gAl is taken
2(SO
4)
318H
2o is dissolved in above sulfuric acid solution, obtains the solution (solution 2) containing Al.Solution 2 is joined in solution 1, after adding, in this mixed solution, pour 23.44g ethyl orthosilicate into, beaker mouth seals, 60 DEG C stir pre-crystallization 12h, obtain white gels, then by this gel with in teflon-lined reactor, crystallization 3d at 180 DEG C, filter, washing, dry, calcining, obtains MFI molecular sieve.
(4) get 2gMFI molecular sieve, be dissolved into 50mL1mol/LNH
4nO
3in solution, 102 DEG C of backflow 2h, filter, and dry, calcining, obtains H-MFI molecular sieve.
(5) get 1.2gH-MFI and be placed in graduated cylinder, drip 0.5mL ethyl orthosilicate, then add ethanol, reach liquid and solid equal-volume state, normal temperature dipping 24h, dry, calcining, obtains H-MFI-TiO
2.
(6) be solvent with dry toluene, in there-necked flask, add 0.5mLClCH
2cH
2cH
2si (OCH
3)
3with 0.65g magnesium rod, 110 DEG C of backflow 24h, obtain silane RMgBr.Dropwise being added by the product obtained is equipped with in the there-necked flask of anhydrous stannic chloride, drips after terminating, at 110 DEG C of backflow 2h.Reaction terminates backward its and adds 4gH-MFI-TiO
2, continue backflow 6h.Product suction filtration, and use NaOH solution back flow reaction, the solid after end reaction is extracted 24h in apparatus,Soxhlet's, dry.Obtain mesoporous silane stannic chloride class catalyst (1).
(7) be solvent with anhydrous tetrahydro furan, in there-necked flask, add 6g mono-NBB, 1.05g magnesium rod, 65 DEG C of back flow reaction 2h, obtain butyl magnesium bromide RMgBr CH
3(CH
2)
3mgBr.Mesoporous silane stannic chloride class catalyst (1) is added butyl magnesium bromide RMgBr CH
3(CH
2)
3in MgBr, backflow 6h, product suction filtration, adds excessive 1mol/LNaOH solution reaction.By the solid filtering after end reaction, filter, dry, obtain grafting Inorganic whisker hybrid catalyst: MFI-TiO
2-(CH
2)
3-SnO-C
4h
9.
By 0.3gMFI-TiO
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, takes 5.7gBPA and adds in there-necked flask, be first warming up to 160 DEG C, slowly drip DMC again, system temperature controls at 160 DEG C, and the by-product carbinol that reaction generates is removed by distillation mode, and utilizes heat recirculated water to control reactor outlet temperature between 65-85 DEG C, by-product carbinol is distillated, and dimethyl carbonate is back in reactant liquor, reaction 8h, filters, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 85%.
Embodiment 2
Method for preparing catalyst, with example 1, just changes the butyl bromide in step (7) into benzyl chloride, prepares catalyst: MFI-TiO
2-(CH
2)
3-SnO-CH
2-Ph.
By 0.3gMFI-TiO
2-(CH
2)
3-SnO-CH
2-Ph catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield is 82%.
Embodiment 3
Method for preparing catalyst, with embodiment 1, just changes the butyl bromide in step (7) into bromocyclohexane, prepares catalyst: MFI-TiO
2-(CH
2)
3-SnO-C
6h
12.
By 0.3gMFI-TiO
2-(CH
2)
3-SnO-C
6h
12catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield is 86%.
Embodiment 4
Method for preparing catalyst, with embodiment 1, just changes the ethyl orthosilicate in step (5) into ammonium metavanadate, and 4gH-MFI-TiO in step (6)
2change 4gH-MFI-V into
2o
5, prepare catalyst: MFI-V
2o
5-(CH
2)
3-SnO-C
4h
9
By 0.3gMFI-V
2o
5-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 85%.
Embodiment 5
Method for preparing catalyst, with embodiment 1, just changes the ethyl orthosilicate in step (5) into ammonium metavanadate, and 4gH-MFI-TiO in step (6)
2change 4gH-MFI-V into
2o
5, change the butyl bromide in step (7) into benzyl bromine, prepare catalyst: MFI-V
2o
5-(CH
2)
3-SnO-CH
2-Ph.
By 0.3gMFI-V
2o
5-(CH
2)
3-SnO-CH
2-Ph catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 78%.
Embodiment 6
Method for preparing catalyst, with embodiment 1, just changes the ethyl orthosilicate in step (5) into ammonium metavanadate, and 4gH-MFI-TiO in step (6)
2change 4gH-MFI-V into
2o
5, change the butyl bromide in step (7) into bromocyclohexane, prepare catalyst: MFI-V
2o
5-(CH
2)
3-SnO-C
6h
12.
By 0.3gMFI-V
2o
5-(CH
2)
3-SnO-C
6h
12catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 86%.
Embodiment 7
Method for preparing catalyst, with embodiment 1, prepares catalyst by step (4): H-MFI.
0.3gH-MFI catalyst is added in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 35%.
Embodiment 8
Method for preparing catalyst, with embodiment 1, prepares catalyst by step (5): H-MFI-TiO
2.
By 0.3gH-MFI-TiO
2catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 65%.
Embodiment 9
By the MFI-TiO obtained in 0.3g embodiment 1
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 120 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 86%.
Embodiment 10
By the MFI-TiO obtained in 0.3g embodiment 1
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 140 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 87%.
Embodiment 11
By the MFI-TiO obtained in 0.3g embodiment 1
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 150 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 87%.
Embodiment 12
By the MFI-TiO obtained in 0.3g embodiment 1
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 170 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 87%.
Embodiment 13
By the MFI-TiO obtained in 0.3g embodiment 1
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 180 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 88%.
Embodiment 14
By the MFI-TiO obtained in 0.3g embodiment 1
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 200 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 8h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 89%.
Embodiment 15
By the MFI-TiO obtained in 0.3g embodiment 1
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 4h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 75%.
Embodiment 16
By the MFI-TiO obtained in 0.3g embodiment 1
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 6h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 82%.
Embodiment 17
By the MFI-TiO obtained in 0.3g embodiment 1
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 10h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 89%.
Embodiment 18
By the MFI-TiO obtained in 0.3g embodiment 1
2-(CH
2)
3-SnO-C
4h
9catalyst adds in 50mL there-necked flask, taking 5.7gBPA adds in there-necked flask, first 160 DEG C are warming up to, slowly drip DMC again, system temperature controls at 160 DEG C, and vapor (steam) temperature is guaranteed to be no more than 90 DEG C, reaction 12h, filter, namely obtain intermediate polycarbonate dimethoxy carbonic acid bisphenol A diester, yield reaches 91%.
Claims (8)
1. synthesize a preparation method for dimethoxy carbonic acid bisphenol A diester catalyst, this preparation method is specific as follows:
(1) asymmetric Bis-quaternary Ammonium Salt Surfactant C
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2c
mh
2m+1br
2preparation, comprise the following steps: get brominated alkanes C
nh
2n+1br and N, N, N', N'-tetramethyl-1,6-hexamethylene diamine is dissolved in toluene/acetonitrile mixed solution heating and carries out synthetic reaction, and synthesis temperature is 60 ~ 120 DEG C, and generated time is 5 ~ 12h, obtains surfactant-intermediate C after reaction terminates by conventional filtration or centrifugal method
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2br; Get C again
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2br and bromoalkane C
mh
2m+1br, under 60 ~ 120 DEG C of conditions, reacts 5 ~ 12h, centrifugal or filtration, and with ether or alkyl halide washing, then dry, obtain asymmetric Bis-quaternary Ammonium Salt Surfactant C
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2c
mh
2m+1br
2; Described n=4 ~ 30; Described m=2 ~ 15; Described C
nh
2n+1the mol ratio of Br and N, N, N', N'-tetramethyl-1,6-hexamethylene diamine is 1:1-20; Described C
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2br and C
mh
2m+1br mol ratio is 1:1 ~ 5;
(2) synthesis of stratiform intersection MFI molecular sieve, comprises the following steps: the mol ratio of synthesis liquid composition is Na
2o:Al
2o
3: SiO
2: C
nh
2n+1n (CH
3)
2(CH
2)
6n (CH
3)
2c
mh
2m+1br
2: H
2sO
4: H
2o=30:x:100:y:18:4000, after synthesis stirred at ambient temperature 10 ~ 12h, this mixed system is transferred to in teflon-lined reactor, high temperature crystallization, crystallization temperature 140 ~ 200 DEG C, crystallization time 10 minutes ~ 30 days, filter, washing, dry, calcining, obtains stratiform intersection MFI molecular sieve; Described x=1 ~ 50, y=5 ~ 15;
(3) there is the preparation of the Inorganic whisker hybrid catalyst of stratiform chi structure MFI molecular sieve, namely synthesize the preparation of dimethoxy carbonic acid bisphenol A diester catalyst, comprise the following steps:
stratiform intersection MFI conversion molecular sieve becomes H-MFI: the MFI molecular sieve that first stratiform obtained intersected is dissolved in 1mol/LNH
4nO
3solution, carries out back flow reaction subsequently, reflux temperature 80 ~ 120 DEG C, return time 2 ~ 4h, centrifugal or filtration, and dry, high-temperature calcination, namely obtains stratiform H-MFI molecular sieve;
grafting transition metal oxide on H-MFI molecular sieve: on described H-MFI, grafting transition metal oxide method is: equi-volume impregnating;
h-MFI upper grafting organic oxidation tin, concrete steps are: the first step, get 3-r-chloropropyl trimethoxyl silane and magnesium rod prepares silane RMgBr; Second step, silane RMgBr prepares tin one type of silane with anhydrous stannic chloride back flow reaction again; 3rd step, gets a NBB, bromocyclohexane, bromobenzene or bromotoluene and magnesium rod reacts, and obtains butyl magnesium bromide, cyclohexyl magnesium bromide, phenyl-magnesium-bromide or benzyl magnesium bromide RMgBr; 4th step, subsequently by second and third step product reaction, and add the stratiform intersection MFI molecular sieve that grafting has transition metal oxide, back flow reaction 2-8 hour, reacts with NaOH or KOH weak solution after product suction filtration, NaOH or KOH weak solution concentration is 0.5-20mol/L, and reactant liquor pH is 7-14 after controlling reaction, filter, dry, namely obtain the catalyst synthesizing dimethoxy carbonic acid bisphenol A diester.
2. the preparation method of synthesis dimethoxy carbonic acid bisphenol A diester catalyst according to claim 1, is characterized in that described n=7 ~ 25.
3. the preparation method of synthesis dimethoxy carbonic acid bisphenol A diester catalyst according to claim 1, is characterized in that described m=4 ~ 12.
4. the preparation method of synthesis dimethoxy carbonic acid bisphenol A diester catalyst according to claim 1, is characterized in that described x=5 ~ 43, y=7 ~ 11.
5. the preparation method of synthesis dimethoxy carbonic acid bisphenol A diester catalyst according to claim 1, is characterized in that described transition metal oxide is the mixture of titanium dioxide or vanadic anhydride or both arbitrary proportions.
6. the preparation method of synthesis dimethoxy carbonic acid bisphenol A diester catalyst according to claim 1, is characterized in that described organic oxidation tin is aryl oxidized tin or alkyl-tin oxide.
7. the preparation method of synthesis dimethoxy carbonic acid bisphenol A diester catalyst according to claim 6, is characterized in that described aryl oxidized tin is phenyl tin oxide, benzyl tin oxide or tert-butyl benzene tin oxide.
8. the preparation method of synthesis dimethoxy carbonic acid bisphenol A diester catalyst according to claim 6, is characterized in that described alkyl-tin oxide is cyclohexyl tin oxide, butyl tin oxide or tert-butyl group tin oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410312867.0A CN104028310B (en) | 2014-07-02 | 2014-07-02 | A kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410312867.0A CN104028310B (en) | 2014-07-02 | 2014-07-02 | A kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104028310A CN104028310A (en) | 2014-09-10 |
| CN104028310B true CN104028310B (en) | 2016-04-06 |
Family
ID=51459444
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410312867.0A Active CN104028310B (en) | 2014-07-02 | 2014-07-02 | A kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104028310B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105749971B (en) * | 2016-03-09 | 2018-01-16 | 天津工业大学 | A kind of catalyst for synthesizing dimethoxy carbonic acid bisphenol A diester and preparation method thereof |
| CN107308984A (en) * | 2016-04-27 | 2017-11-03 | 中国科学院成都有机化学有限公司 | It is a kind of to be used for dimethyl carbonate and the immobilized organotin catalysts of silica and preparation method of phenol ester exchange |
| CN108816213B (en) * | 2018-07-02 | 2019-10-22 | 天津工业大学 | A kind of preparation method for the heterogeneous catalyst synthesizing dimethoxy carbonic acid bis-phenol diester |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442911A (en) * | 2011-11-17 | 2012-05-09 | 天津工业大学 | Preparation method of intermediate dimethoxy carbonic acid bisphenol A diester |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7132575B2 (en) * | 2003-07-01 | 2006-11-07 | General Electric Company | Process for the synthesis of bisphenol |
-
2014
- 2014-07-02 CN CN201410312867.0A patent/CN104028310B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442911A (en) * | 2011-11-17 | 2012-05-09 | 天津工业大学 | Preparation method of intermediate dimethoxy carbonic acid bisphenol A diester |
Non-Patent Citations (2)
| Title |
|---|
| 二环己基氧化锡催化合成二甲氧基碳酸双酚A二酯的研究;丁敏等;《天津工业大学学报》;20130831;第32卷(第4期);第43-47页 * |
| 双酚A型聚碳酸酯的合成与性能研究进展;苏坤梅等;《科技导报》;20091231;第27卷(第8期);第80-86页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104028310A (en) | 2014-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104028310B (en) | A kind of preparation method synthesizing dimethoxy carbonic acid bisphenol A diester catalyst | |
| CN104496959B (en) | Utilize the method that normal pressure carbon dioxide and epoxide reaction prepare cyclic carbonate | |
| CN106905305A (en) | A kind of En Gelie net preparation method | |
| CN103641811B (en) | Method for preparing cyclic carbonate | |
| CN103058845A (en) | Dibenzoylmethane preparation method | |
| CN108530660B (en) | A kind of quaternized polyfluorene ether ketone compound of local dense and preparation method thereof | |
| CN104801340B (en) | Catalytic membrane reaction preparation technology for diphenyl carbonate | |
| CN102766166B (en) | A kind of preparation method of flame retardant hexaphenoxy cyclotriphosphazene compound | |
| CN101613461A (en) | The method of preparing fluorine-containing epoxy resin by phase transfer catalyst | |
| CN106243344A (en) | A kind of epoxy radicals end capped polyether continuous open loop production technology | |
| CN108772102A (en) | Miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester | |
| CN106588611A (en) | Process for producing benzophenone ultraviolet ray absorbent | |
| CN108690081A (en) | A kind of preparation method of hexaphenoxycyclotriphosphazene | |
| CN114011459A (en) | Titanium series double-acid type ionic liquid catalyst, preparation method and application | |
| CN101659611A (en) | Method for preparing 2, 4, 5-trifluoro-phenylacetic-acid | |
| CN103086899B (en) | Synthesizing method of 2-amino-4'-fluoro-benzophenone | |
| CN102531854B (en) | Synthesis method for 4-bromo-2, 6-difluoro-trifluoromethoxybenzene | |
| CN102659509B (en) | Preparation method of biphenyl liquid crystal compound | |
| CN102442911B (en) | Preparation method of intermediate dimethoxy carbonic acid bisphenol A diester | |
| CN102701974B (en) | Method for synthesizing cinnamate derivatives | |
| CN104892658B (en) | The preparation method of the silicon fluoride of diphenyl two | |
| CN101357889B (en) | Methyl ethyl carbonate preparation method | |
| CN104262131A (en) | Production method of 2-(4'-tertpentylbenzoyl)benzoic acid | |
| CN104529726B (en) | A kind of preparation method of o-hydroxyacetophenone | |
| CN102382059A (en) | Method for preparing N-vinyl imidazole |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |