CN1320590A - Modified ion-exchange resin catalyst with special pore structure for preparing biphenol - Google Patents
Modified ion-exchange resin catalyst with special pore structure for preparing biphenol Download PDFInfo
- Publication number
- CN1320590A CN1320590A CN 00127027 CN00127027A CN1320590A CN 1320590 A CN1320590 A CN 1320590A CN 00127027 CN00127027 CN 00127027 CN 00127027 A CN00127027 A CN 00127027A CN 1320590 A CN1320590 A CN 1320590A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- phenol
- acid
- resin
- agent
- 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.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An ion exchange resin with special pore structure and containing mercapto and sulfo groups is disclosed, which can be used as the catalyst for preparing biphenol by condensation reaction of phenolic compound with carbonyl compound. The application of said modified ion exchange resin catalyst in preparing biphenol is also disclosed.
Description
What the present invention relates to have special pore structure contains sulfydryl and sulfonic ion-exchange resin catalyst, and this catalyzer is produced application in the bis-phenol in the condensation reaction of carrying out phenolate thing and carbonyl compound.
Wherein R can be the monovalent alkyl or the aralkyl of hydrogen, a 1-8 carbon atom by oneself, as methyl, ethyl, propyl group, sec.-propyl, hexyl, 2-ethylhexyl, benzyl etc.; Aryl is as phenyl, naphthyl etc.; Alkaryl is as tolyl etc.; X can respectively do for oneself hydrogen, fluorine or the alkyl identical with above-mentioned R.R and X can be identical, also can be different.
The industrial method of producing bis-phenol mainly contains two kinds, promptly is respectively the hydrogen chloride and the ion-exchange-resin process of catalyzer with hydrogenchloride and storng-acid cation exchange resin.The latter obtains very big development because of advantages such as its technology are simple, no burn into is low to the equipment material requirement, the three wastes are few in recent years, particularly, made it become the vanguard technology method of the raw material dihydroxyphenyl propane of high quality engineering plastics and high insulation level Resins, epoxy along with the updating of ion-exchange resin catalyst performance.
The ion-exchange resin catalyst matrix that adopts is an exchange capacity at least 2.0 at present, best 3.0~5.5 milligramequivalents/gram dried resin, gel-type or macroreticular type, sulfonic acid ion exchange resin, as sulfonated styrene-divinylbenzene copolymer, sulfonated resol, sulfonated benzene-formaldehyde resin etc., the trade names that are suitable for as: Amberlite-118 ,-200 ,-IR ,-XE307; Amberlyst15; Dowex-50 ,-MSC-1; Duolite C-20; Permutit QH; Chempro C-20 etc.
The method that the catalyzer that is used in bisphenol synthesis with aforementioned ion exchange resin matrix modification adopts usually is with helping catalytic group, as sulfydryl, introduces the ion exchange resin matrix, thereby improves its selectivity and speed of response.The study on the modification work of this respect never had been interrupted since the bisphenol synthesis resin method comes out.With regard to introducing sulfydryl (sulfhydrylation), according to reported in literature a lot of methods are arranged, as partial reduction method (USP3,172,916), partial esterification method (USP3,153,001; BP937,072), introduces sulfydryl method (USP4,294,995 through the sulphonamide covalent linkage; USP4,346,247; USP4,396,728) and the part neutralisation.
Owing to have better catalytic performance by the catalyzer that other method obtained by the part neutralisation, can obtain the yield and the purity of higher product bis-phenol, this method has caused people's attention, has worked out in succession with the multiple compound that contains sulfydryl to carry out part neutral method.These compounds (sulfhydrylation agent) that contain sulfydryl have: thiazolidine or thiazolidine (USP3,634,341; USP3,760,006), aryl mercapto-amine or its salt (USP4,045,379), pyridyl alkyl mercaptan (USP4,478,956), N-(2-mercaptoalkyl) acid amides (USP4,595,704; CN85106111), many alkyl mercaptoamines (EP268,318; USP4,820,740), N-alkyl thiol amine (EP144,735) and alkyl thiol amine (USP3,394,089; BP1,183,564) or the like.
Though above-mentioned prior art has been developed the various catalytic groups that help with different molecular structures, and these groups are incorporated into correlation method on the base resin skeleton, and these technology have also brought raising to a certain degree for selectivity of catalyst and activity really, but because these technology only limit to change, modulation to the kind that helps catalytic group and the mode of introducing thereof, and do not relate to base resin itself, so catalyst selectivity and active raising degree are limited.For example through the resin catalyst after the modification in the condensation reaction of phenol and acetone, acetone conversion is that the transformation efficiency of dihydroxyphenyl propane all is lower than 50%, product to the selectivity of, right-dihydroxyphenyl propane not as good as 96%, form and aspect are up to 40~50.Even adopt the inventor's disclosed method of modifying in Chinese patent application CN91108831.8, the transformation efficiency of acetone can reach 53%, product reaches 99.23% to the selection performance of, right-dihydroxyphenyl propane, but the form and aspect of product are still up to more than 20.
One of purpose of the present invention is the modified ion-exchange resin catalyst bisphenol synthesis that has special pore structure with a kind of.
Another object of the present invention provides a kind of modified ion-exchange resin catalyst that is used for bisphenol synthesis.
Another purpose of the present invention provides a kind of preparation method who is used for the modified ion-exchange resin catalyst of bisphenol synthesis.
The ion-exchange resin catalyst that the present invention is used for the modification of bisphenol synthesis contain sulfonation styrene-divinylbenzene copolymer, its exchange capacity is 2.8~5.5 milligramequivalents/gram dried resin, and alkyl thiol amine of 10~30% a sulfonic acid group and 1-7 carbon atom is by ammonium sulphonate ionic linkage bonding on it.This catalyzer has the pore structure that contains the micropore district and carry pore network, and it carries pore network to be made of a major trunk roads network and a pore network.The aperture in major trunk roads network duct is 9 * 10 under non-solvent swelling state
3~38 * 10
3Nanometer; The aperture of propping up the pore network duct is 20~150 nanometers; The aperture in duct, micropore district is 5~20 nanometers, and wherein the aperture is that the pore volume in the micropore work duct of 5~10.4 nanometers accounts for more than 50% of the total pore volume of micropore Qu, and the ratio of the pore volume in micropore district and transport net district is 0.25~1.1.
Above-mentioned catalyzer is to prepare by the following method of step:
(1) make vinylbenzene and divinylbenzene according to 3~15%, best 7~12% degree of crosslinking is 54~62 ℃ refined wax and NY-200 what account for monomer weight 20~40% by fusing point
#Carry out suspension polymerization under the existence of the pore-creating agent that solvent oil is formed and obtain white bead, the weight ratio of paraffin and solvent oil is 1: 3~6.1 in the pore-creating agent;
(2) according to the preparation method of conventional sulfonation macroreticular type Zeo-karb, the Archon that polymerization is got carries out following processing successively: remove pore-creating agent, swelling and sulfonation, remove swelling agent and residual acid, resin is made the transition successively is sodium type and Hydrogen;
(3) according to disclosed in the prior art be the part neutralisation of sulfhydrylation agent with the alkyl thiol amine, preferably with reference to part neutralisation described in the Chinese patent CN91108831.8 with above-mentioned sulfonic resin sulfhydrylation, promptly get catalyzed hardware.This sulfhydrylation method is specific as follows:
(as-15~35 ℃) are used the static solvent impregnated resin of sulfhydrylation agent solution or once/are repeatedly passed through resin, washing, drying then at ambient temperature.Used sulfhydrylation agent solution can have following composition (heavy %): the organic or inorganic hydrochlorate of 0.01%~alkyl thiol amine saturated, 1~7 carbon atom; 0.01~50% is selected from the acid of one of tosic acid, formic acid, acetate, oxalic acid, nitric acid or sulfuric acid; 0~98% be selected from C
5Organic swelling agent of one of following alcohol, acetone, phenol, acetone-phenol, methylene dichloride or ethylene dichloride; The water of surplus.Also can be with the acid that is selected from one of tosic acid, formic acid, acetate, oxalic acid, hydrochloric acid, nitric acid or sulfuric acid carry out acidated, pH<5, concentration is the organic or inorganic acid salt aqueous solution of alkyl mercapto aniline 0.005~0.5 heavy %, 1~7 carbon atom.Under this latter event, sulfhydrylation process is advisable in the described device of Chinese patent CN 91111615.X.The resin of desiring to carry out sulfhydrylation can be in drying regime, also can be in by water or above-mentioned organic swelling agent swollen state.
The described device of Chinese patent CN 91111615.X is: one by reactor, strainer, reservoir and pump and the closed cycle system that is connected to form by pipeline, and this device can make resin particle evenly be suspended in the solution and be in slow floating tumbling motion state.Reactor wherein can be reactor, tubular reactor, tower reactor, reaction column, container, jar and bucket.Strainer wherein can be the fluid free-flow is crossed and being prevented the device that particulate matter is passed through of compositions such as porcelain filter, sintered glass, open-cell foamed plastics, glass fibre, plastic optical fibre and fabric thereof, net and porous plate.In reactor and reservoir, flow deflector, guide shell can be set, also can be with heating or cooling jacket.Its loop direction can be from bottom to top with respect to reactor or from top to bottom in whole closed cycle system, also can be horizontal.This closed circulation device as shown in the figure, 1 among the figure is reactor, 2 is strainer; 3 is circulating line, and 4 is reservoir, and 6 is pump.
The condensation reaction of phenolate thing and carbonyl compound can be carried out under the arbitrary temp of about 20~about 110 ℃ of temperature ranges.The suitable temperature range of reaction is 50~110 ℃.Temperature of reaction is low, then needs longer duration of contact with catalyzer.
Mol ratio when phenolate thing and carbonyl compound reaction can be 2: 1 to 20: 1.Yet suitable mol ratio is 4: 1~12: 1.
Because the phenolate thing contacts with the catalyzer with special pore structure of the present invention with carbonyl compound, thereby speed of response is fast, and foreign matter content is extremely low in the product.For example, be 8 in the mol ratio of phenol and acetone, when temperature of reaction is 75 ℃, acetone conversion is that the transformation efficiency of dihydroxyphenyl propane can reach 58~74%, and the selectivity of dihydroxyphenyl propane can reach 99.2~99.7%, and form and aspect can reach below 10.The quality of gained dihydroxyphenyl propane product can reach polymerization-grade, ordinary epoxy resin and insulating epoxy level.
The process of producing of catalyzer of the present invention has adopted the pore-creating agent of specific composition, thereby synthesize base resin particle with special pore structure, adopt specific sulfhydrylation method to solve the broken problem of resin particle that the numerous thiol groups prior art causes and to make sulfydryl can be evenly distributed in resin particle inner and surperficial, this complete preparation method brought outstanding selectivity to resin catalyst in addition.
Accompanying drawing is the device synoptic diagram that is used for the ion exchange resin mercaptolation that can use for invention, described in the CN91111615.X.
Embodiment
Following example will give further instruction to the present invention, but not thereby limiting the invention.
The pore structure of catalyzer is to test on the automatic PORE SIZE APPARATUS FOR of Autopore 9220 types that Micromeritics company (U.S.) makes with mercury penetration method in the example.Phenol and acetone conversion are that the selectivity method of calculation of the transformation efficiency of dihydroxyphenyl propane and purpose product dihydroxyphenyl propane are as follows:
Transformation efficiency C=C
BP(M
P* R+M
A)/M
BPC in * 100% formula
BPBe content of bisphenol A in the product; M
PBe the phenol molecular weight; R is the mol ratio of raw material phenol and ketone, M
ABe acetone molecules amount, M
BPBe the dihydroxyphenyl propane molecular weight.
Selectivity S=C
BP/ (C
BP+ C
2+ C
3+ C
4+ C
5) C in the formula
BP, C
2, C
3, C
4, C
5Be respectively dihydroxyphenyl propane in the reaction product, 2,4-dihydroxyphenyl propane, the content of triphenol, chroman, other impurity.Each components contents all is to adopt high-pressure liquid phase chromatogram therapy determining in the product.The form and aspect of product dihydroxyphenyl propane are to adopt platinum-cobalt spectrophotometer colorimetric method for determining.
The preparation example 1 of bisphenol synthesis catalyst system therefor of the present invention
In 5 liters of there-necked flasks, add 16.5 gram polyvinyl alcohol (Beijing reagent three factories product) and 1600 milligrams of distilled water, add 364.8 gram vinylbenzene (Lanzhou chemical industrial company product), 36.5 gram divinylbenzenes (Lanzhou chemical industrial company product), 40.2 gram benzoyl peroxides (Beijing reagent three factories product), 17.7 gram refined waxs (Daqing petrochemical company product) and 107.4 gram NY-200 more respectively
#Solvent oil (Daqing petrochemical company product).Under agitation, reacted 6 hours down at 90 ℃ again, take out material, wash, dry, make the resin particle that contains paraffin and solvent oil 82 ℃ of reactions 6 hours.
In soxhlet's extractor, divide 3 times above-mentioned Archon to be extracted, in extraction liquid, do not have paraffin (detecting) with refractometry with 1200 milliliters of benzene (Tianjin reagent one factory's product).With 200 gram ethylene dichloride (Tianjin reagent one factory's product) be that swelling agent, 2800 gram concentration are that the sulfuric acid (Tianjin reagent three factory's products) of 94 heavy % be sulphonating agent, reacts 2 hours at 70 ℃ under stirring, and reacts 6 hours under 80 ℃ again.System temperature is risen to 90 ℃ steam ethylene dichloride, continue air distillation 2 hours, underpressure distillation 1 hour down at 110~120 ℃ again.Used water is diluted gradually and is washed residual acid when system is reduced to below 35 ℃ gradually, is neutral up to effluent liquid.Aqueous hydrochloric acid with 5% transfers resin particle to Hydrogen, gets jack 395 grams after the drying.
Get dried resin 180 gram, mercaptoethylamine hydrochloride (Changshu City's medical material factory products) 18 restrains and 360 ml waters place the mercaptolation device, with hydrochloric acid the pH of solution is transferred to 3 again.
At room temperature, take out resin then, be washed with distilled water to effluent liquid and be neutral, filter, 80 ℃ of dryings 6 hours, again 72 ℃ of vacuum-dryings 12 hours resin impregnation 36 hours.
Example 2
Use and example 1 essentially identical material, experimental procedure and operational condition, the ratio that is used solvent oil and paraffin is different.The solvent oil that uses in this example weighs 90.5 grams, and paraffin weighs 30.1 grams.The ratio of the two is 3: 1.
Example 3
Use and example 2 essentially identical materials, experimental procedure and operational condition, the concentration of the sulfhydrylation agent mercaptoethylamine hydrochloride that only is to use is lower, is 0.3% (weight).Corresponding therewith, used long dipping time, be 72 hours.
The relevant results of performance analysis of the catalyzer that above-mentioned example makes is listed in table 1.
Table 1
Example 1 | Example 2 | Example 3 | |
Solvent oil and paraffin weight ratio exchange capacity, milligramequivalent/gram dried resin micropore work duct pore volume accounts for the total pore volume of micropore Qu, % micropore district and transport net pore volume be than sulfhydrylation degree, % catalyzer numbering | ????6.1 ????4.66 ????51 ????0.25 ????16.95 ??????A | ????3.1 ????4.72 ????78 ????1 ????17.2 ?????B | ?3.01 ?4.73 ?65 ?1.1 ?16.8 ???C |
Example 4~6
Use the described device of CN91111615.X to prepare catalyzer provided by the invention
Prepare Archon and with their sulfonation, transition according to method described in the example 1~3.
Sulfhydrylation is to carry out in device as shown in Figure 1, reactor wherein is 40 millimeters of internal diameters, high 590 millimeters tower reactor, strainer is sintered porous glass, and circulating line is that internal diameter is 8 millimeters a Glass tubing, and reservoir is 10 liter volumetrical glass lined stills.In reactor, pack the above-mentioned sulfonation of 500 grams into resin, pack in the reservoir acidated, pH=1 with tosic acid (Beijing Chemical Plant's product), be dissolved with the 20 6 premium on currency solution that restrain the mercaptoethylamine hydrochlorides.At room temperature with pump with 14 liters/time flow the sulfhydrylation agent aqueous solution is pumped into resin through filter autoreactor lower end from reservoir contact, flow out to by the upper end then and be back to reservoir again after the filtration and continue to circulate 24 hours.After the loop ends resin washed to effluent liquid and be neutral, filter, 80 ℃ of dryings 6 hours, 72 ℃ of vacuum-drying 12 hours.
The relevant results of performance analysis of above-mentioned catalyzer is listed in table 2.
Table 2
Example 4 | Example 5 | Example 6 | |
Solvent oil and paraffin weight ratio exchange capacity, milligramequivalent/gram dried resin micropore work duct pore volume accounts for the total pore volume of micropore Qu, % micropore district and transport net pore volume be than sulfhydrylation degree, % catalyzer numbering | ????6.1 ????4.66 ????51 ????0.25 ????16.85 ?????D | ????3.1 ????4.72 ????78 ????1 ????17.1 ?????E | ?3.01 ?4.73 ?65 ?1.1 ?16.9 ???F |
Example 7~12
Carry out the condensation reaction of phenolate thing and carbonyl compound in the presence of above-mentioned catalyzer, the reaction formula of main reaction is:
Under same reaction conditions, can reach very high transformation efficiency and very low foreign matter content.Condensation reaction with phenol and acetone is that example is illustrated below.
130 gram phenol (Tianjin reagent one factory's product) and 10 gram acetone (Beijing Chemical Plant's product) are restrained in the presence of the catalyzer in 75 ℃ of stirring reactions 1 hour 20, measure the transformation efficiency that its acetone conversion is a dihydroxyphenyl propane, the selectivity of dihydroxyphenyl propane and the form and aspect of dihydroxyphenyl propane, the results are shown in table 3.
For showing the characteristics that the invention provides catalyzer, replicate(determination) under the same conditions other three that get according to prior art for preparing, as not have catalyst pores structure of the present invention catalyzer, the result also lists in table 3.
Table 3
Catalyzer | A | B | C | D | E | F | Contrast 1 | | |
It is the conversion ratio of bisphenol-A than acetone conversion with the transport net pore volume that micropore work duct pore volume accounts for the total pore volume % of micropore Qu micropore district; Weigh the selective of % bisphenol-A, heavy % bisphenol-A form and aspect | 51 0.25 58.6 99.25 9.8 | 78 1 63.9 99.6 8.4 | 65 1.1 60.2 99.4 8.9 | 51 0.25 73.7 99.3 9 | 78 1 74.1 99.7 8 | 65 1.1 73.8 99.5 8.5 | 32 0.12 49.08 96.1 40 | 48 0.14 53 99.23 22 | 15 1.8 43 92.5 50 |
Claims (11)
1. produce the catalyzer that bis-phenol is used by phenolate thing and carbonyl compound for one kind, described catalyzer be a kind of contain sulfonation the ion exchange resin of styrene diethylene benzene copoly mer,
Wherein R can be alone the monovalent alkyl or the aralkyl of hydrogen, a 1-8 carbon atom, as methyl, ethyl, propyl group, sec.-propyl, hexyl, 2-ethylhexyl, benzyl etc.; Aryl is as phenyl, naphthyl etc.; Alkaryl is as tolyl etc.;
Wherein can respectively do for oneself hydrogen, fluorine of X, or the alkyl identical with above-mentioned R,
Described catalyzer is characterised in that:
(1) its exchange capacity is 2.8-5.5 milligramequivalent/gram dried resin;
(2) alkyl thiol amine of 10~30% sulfonic acid group and 1~7 carbon atom passes through ammonium sulphonate ionic linkage bonding on it;
(3) have the pore structure that contains the micropore district and carry pore network, it carries pore network to be made of a major trunk roads network and a pore network, and the aperture in major trunk roads network duct is 9 * 10 under non-solvent swelling state
3~38 * 10
3The aperture in nanometer, a pore network duct is that the aperture in 20~150 nanometers, duct, micropore district is 5~20 nanometers, wherein the aperture is that the pore volume in the micropore work duct of 5~10.4 nanometers accounts for more than 50% of the total pore volume of micropore Qu, and the ratio of the pore volume in micropore district and transport net district is 0.25~1.1.
2. the catalyzer used of the production bis-phenol of claim 1, the preparation method of wherein said ion-exchange resin catalyst comprises the following steps:
(1) vinylbenzene and divinylbenzene carry out suspension polymerization and produce Archon in the presence of pore-creating agent; Wherein Vinylstyrene and cinnamic weight ratio are 5~25%: 95~75%, and pore-creating agent is by refined wax and NY-200
#Solvent oil is formed, and the weight ratio of paraffin and solvent is 1: 3~6.1;
(2) extraction and sulfonation Archon
A) remove paraffin and solvent oil in the above-mentioned polymerization gained Archon with extraction agent,
B) use swelling agent and sulphonating agent with above-mentioned resin swelling and sulfonation,
C) remove remaining swelling agent and remaining sulphonating agent and
D) resin is transferred to Na type or H type; And
(3) with sulfhydrylization reagent solution with sulfonation the resin sulfhydrylation, washing then, dry and make catalyzer.
3. the catalyzer of using according to the production bis-phenol of claim 2 is characterized in that the ion exchange resin degree of crosslinking that makes is 3~15%.
4. the catalyzer of using according to the production bis-phenol of claim 2 is characterized in that the ion exchange resin degree of crosslinking that makes is 7~12%.
5. the catalyzer of using according to the production bis-phenol of claim 2, it is characterized in that sulfhydrylation at ambient temperature or once with the static solvent impregnated resin of sulfhydrylation agent solution/repeatedly finish by resin.
6. the catalyzer of using according to the production bis-phenol of claim 5 is characterized in that said sulfhydrylation agent solution has following composition (heavy %): the organic or inorganic hydrochlorate of 0.01% ~ alkyl thiol amine saturated, 1~7 carbon atom; 0.01~50% the acid that is selected from one of tosic acid, formic acid, acetate, oxalic acid, hydrochloric acid, nitric acid or sulfuric acid; 0~98% the organic swelling agent that is selected from C5 one of following alcohol, acetone, phenol, acetone-phenol, methylene dichloride or ethylene dichloride; The water of surplus.
7. the catalyzer of using according to the production bis-phenol of claim 5 is characterized in that said sulfhydrylation agent solution is with being selected from toluenesulphonic acids, formic acid, acetate, oxalic acid, hydrochloric acid.That the acid of one of nitric acid or sulfuric acid is carried out is acidated, pH<5, concentration are the organic or inorganic acid salt aqueous solution of alkyl thiol amine 0.005~0.5 heavy %, 1~7 carbon atom.
8. the catalyzer of using according to the production bis-phenol of claim 6 is characterized in that this sulfhydrylation process is advisable in the described device of Chinese patent CN 91111615.X.
9. the catalyzer of using according to the production bis-phenol of claim 5 is characterized in that desiring the sulfhydrylation resin and can be in drying regime, also can be in by water or organic swelling agent swollen state.
10. the ion-exchange resin catalyst of each of claim 1~9 is by the application in phenolate thing and the carbonyl compound bisphenol synthesis.
11., wherein use phenol to contact with above-mentioned catalyzer and produce dihydroxyphenyl propane with acetone according to the application of claim 10.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 00127027 CN1320590A (en) | 2000-09-13 | 2000-09-13 | Modified ion-exchange resin catalyst with special pore structure for preparing biphenol |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 00127027 CN1320590A (en) | 2000-09-13 | 2000-09-13 | Modified ion-exchange resin catalyst with special pore structure for preparing biphenol |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN96105072A Division CN1092628C (en) | 1996-04-24 | 1996-04-24 | producing bisphenol by using modified ion exchange rerin with special porous structure as catalyst |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1320590A true CN1320590A (en) | 2001-11-07 |
Family
ID=4592110
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 00127027 Pending CN1320590A (en) | 2000-09-13 | 2000-09-13 | Modified ion-exchange resin catalyst with special pore structure for preparing biphenol |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1320590A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101927185A (en) * | 2010-08-09 | 2010-12-29 | 上海华震科技有限公司 | Preparation of macroporous strong-acid cation-exchange resin catalyst and use thereof in catalytic synthesis of methyl 2-keto-L-gulonate |
CN101186719B (en) * | 2007-12-04 | 2012-02-29 | 南京大学 | Composite function resin, preparation method thereof, and method for treating phthalate pollution of water body |
CN106563502A (en) * | 2016-11-04 | 2017-04-19 | 凯瑞环保科技股份有限公司 | Bisphenol A synthetic resin catalyst and preparation method thereof |
-
2000
- 2000-09-13 CN CN 00127027 patent/CN1320590A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101186719B (en) * | 2007-12-04 | 2012-02-29 | 南京大学 | Composite function resin, preparation method thereof, and method for treating phthalate pollution of water body |
CN101927185A (en) * | 2010-08-09 | 2010-12-29 | 上海华震科技有限公司 | Preparation of macroporous strong-acid cation-exchange resin catalyst and use thereof in catalytic synthesis of methyl 2-keto-L-gulonate |
CN106563502A (en) * | 2016-11-04 | 2017-04-19 | 凯瑞环保科技股份有限公司 | Bisphenol A synthetic resin catalyst and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1038395C (en) | Ion exchange resin catalyzer for synthesising bisphenol and preparation thereof | |
Ford et al. | Polymer-supported phase transfer catalysts: Reaction mechanisms | |
CN1426990A (en) | Metal doped sulfunated ion exchange resin catalyst | |
CN1865302A (en) | Composite functional super high cross-linked adsorption resin containing quaternary amine group, and its preparation method | |
CN105504128A (en) | Adsorbent resin used for treating phenolic wastewater and preparing method and application thereof | |
RU97108127A (en) | CATALYST ON THE BASIS OF ION EXCHANGE RESIN FOR SYNTHESIS OF BISPHENOLS AND METHOD OF ITS PRODUCTION | |
US5354831A (en) | Shaped organopolysiloxanes containing sulfonate groups, a process for their production and their use | |
CN103122044B (en) | Sulphonic acid type macroporous ion exchange resin and preparation method thereof | |
CN86102001A (en) | The processing method of strongly acidic cation exchange catalysts | |
CN106478980A (en) | Click on the preparation method of the hybridization porous monolithic material of polyreaction based on sulfydryl-epoxy | |
CN1092628C (en) | producing bisphenol by using modified ion exchange rerin with special porous structure as catalyst | |
CN105521823A (en) | Mesoporous-silica-gel surface bonded alkylsulfonic acid catalyst and preparation and catalysis methods therefor | |
CN1320590A (en) | Modified ion-exchange resin catalyst with special pore structure for preparing biphenol | |
CN109180850A (en) | A kind of composite pore-forming is preparing the application in macroreticular ion exchange resin | |
CN100523055C (en) | Process for producing bisphenol A | |
CN108409778A (en) | The preparation method and applications of high refractive index modified silane | |
Widdecke | Polystyrene‐supported acid catalysis | |
CN1202914C (en) | Bisphenol A synthesis catalyst and its preparation method | |
CN1181922C (en) | Synthesis method of quaternary phosphonium type anion-exchange resin for catalyzing epoxyethane hydration | |
CN115093585A (en) | Waste plastic-based super-crosslinked polymer prepared from waste polystyrene plastic, and preparation method and application thereof | |
CN102319586B (en) | Resin catalyst used in alkylation reaction of isobutene and butylene and preparation method thereof | |
CN103121934B (en) | Method for reducing iodide impurity content in acetic acid | |
CN1583269A (en) | Macroporous cationic exchanging resin, preparing method and use in synthetic bisphenol A catalyst | |
CN111574720B (en) | Preparation method of molecularly imprinted polymer microspheres suitable for complex water sample analysis | |
CN113845631B (en) | Preparation method and application of molecularly imprinted polymer with bio-based macromolecules |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication |