CN109225322A - A kind of method organotitanium preparation and its catalyze and synthesize plasticizer - Google Patents
A kind of method organotitanium preparation and its catalyze and synthesize plasticizer Download PDFInfo
- Publication number
- CN109225322A CN109225322A CN201811157166.9A CN201811157166A CN109225322A CN 109225322 A CN109225322 A CN 109225322A CN 201811157166 A CN201811157166 A CN 201811157166A CN 109225322 A CN109225322 A CN 109225322A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- titanium
- acid
- organotitanium
- preparation
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of methods organotitanium preparation and its catalyze and synthesize plasticizer, it is with organic super acids (including trifluoromethyl acetic acid, trifluoromethane sulfonic acid and its corresponding acid anhydrides) and inorganic titanium base material (including titanium oxide or metal titanium salt) for raw material, the processes such as, precipitation molten through peracid, drying obtain high activity organic acid titanium salt catalyst；A kind of production technology of catalyst system production plasticizer phthalic acid dioctyl ester (DOP) and dioctyl terephthalate (DOTP) using above method preparation, compared with traditional titanate ester catalyst technique, under same catalyst amount, reaction temperature can be greatly lowered, shorten the reaction time, achieve the purpose that reduce energy consumption, reduce octanol consumption, product appearance coloration reduces, yield improves；Meanwhile catalyst prepared by the present invention is recyclable, reuses, effectively reduces process costs, alleviates post-processing pressure.
Description
Technical field
The present invention, which relates to, belongs to catalyst preparation production field, espespecially a kind of to be esterified for being catalyzed phthalic acid and octanol
The novel high-activity method for preparing catalyst and its technique for applying of reaction.
Background technique
Dioctyl phthalate (DOP) and dioctyl terephthalate (DOTP) are the common plasticizer of function admirable,
With good mixing property, plasticizing efficiency is high, volatility is low, low-temperature pliability is good, good water absorption, electrical property are high, heat resistance and resistance to
The features such as time property is good, is processed to polymer, such as resin, acetate resin, ABS resin and rubber etc. are plastics industries
Essential addition auxiliary agent, China have become the first big producer of world's plasticizer and consumption big country.
The production of domestic dioctyl phthalate (DOP) and dioctyl terephthalate (DOTP) at present mainly uses directly
Esterification process is connect, it is raw material that phthalic anhydride and octanol, terephthalic acid (TPA) and octanol, which is respectively adopted, first at 120-150 DEG C
Then lower carry out mono-esterification carries out high temperature ester homogeneously or under heterogeneous catalysis system catalysis using metal oxide, esters etc.
Change, realizes double esterification.Using it is more be butyl titanate system, reaction temperature is in 220-240 DEG C of range, reaction time 6-10
Hour.Since high temperature is esterified for a long time, reaction temperature is higher than octanol boiling point, and octanol is in " evaporation-condensation-reflux " shape always
State, energy consumption is high, reaction efficiency is low；Meanwhile leading to product appearance color burn, to handle by active carbon can be up to standard, gives ring
Bring harm in border；Catalyst cannot recycle, and increase process costs, also bring future trouble to post-processing.
To solve the above problems, different catalyst systems has obtained further research, wherein ionic liquid catalyst systems have
Apparent effect, such as chlorinated butyl pyridine stannous chloride system (CN102001948A), butyl titanate is major catalyst, quaternary ammonium
Ionic liquid is solubilizer system (CN102329233A), and imidazoles and benzimidazole ionic liquid are as solubilizer catalytic body
It is (CN102824929A) etc., by, to the superior solubility performance of organic matter and inorganic matter, making reaction system using ionic liquid
It is changed into homogeneous, raising reaction efficiency by heterogeneous, but cannot achieve industrialized production since ionic liquid is expensive.Its
Its catalyst system also has relevant report, but catalytic activity is unable to satisfy application requirement, is both needed to pyroreaction (230 DEG C or more),
The problems such as not can solve thus bring high energy consumption, complicated last handling process, as supported catalyst system (CN104262158A,
Mesoporous Materials With High Specific polymer supported titanate), composite catalyst system (CN107213914A, halogenated tributyl season phosphine and poly- second
Enol is modified titanate esters) etc..
Therefore, that present invention is generally directed to reaction temperatures under existing catalyst system is high, the reaction time is long, cause high energy consumption, after
The problems such as many and diverse is handled, design has synthesized a kind of high activated catalyst, reaches reduction reaction temperature using the high activity of catalyst system
Degree shortens the reaction time, final to solve the problems such as product color is deep, process energy consumption is high, yield is low, while the recyclable weight of catalyst
It is multiple to use, it reduces production cost, reduce environmental pollution.
Summary of the invention
To solve the above problems, present invention is primarily aimed at when, reaction high for reaction temperature under existing catalyst system
Between it is long, lead to problems such as high energy consumption, post-processing it is many and diverse, a kind of high activated catalyst is provided, is reached using the high activity of catalyst system
To reducing reaction temperature, shortening the reaction time, the problems such as product color is deep, process energy consumption is high, yield is low is finally solved, and realize
Raw material is easy to get, unit is easy to operate, three-waste free discharge, purpose easy to industrialized production, and provides a kind of plasticizer synthesis use
High activated catalyst preparation method and applications technique.Secondly one it is designed to provide a kind of catalyst, can be recycled and reuses,
To reduce production cost, reduce environmental pollution.
To achieve the above object, provided by the present invention to urge the present invention provides a kind of organotitanium preparation method
Change system is to be reacted by titanium base material with organic super acids, and by acid, the technical process such as molten, precipitation, drying are made.
Wherein, preferably:
The titanium base material is titanium oxide (including titanium monoxide, titanium dioxide and titanium sesquioxide), metatitanic acid (hydrogen-oxygen
Change titanium), titanium chloride (match by aqueous solution or organic solvent including two kinds of materials of titanium trichloride and titanium tetrachloride and its various concentration
At solution)；
Organic super acids include trifluoromethyl acetic acid, trichloromethyl acetic acid, trifluoromethane sulfonic acid, trinitrobenzen sulphur
Acid etc. further includes these organic super acids various acid anhydrides accordingly.
The molten technique of acid are as follows: titanium base material and organic super acids are mixed with the ratio of equivalent, suitable quantity of water is added
Stirring, solids completely or partially dissolves at a certain temperature, filters insoluble matter；
The precipitation technique are as follows: insoluble matter is filtered into post mother liquor, sloughed by way of normal pressure or vacuum distillation moisture and
Other fractions；
The drying process are as follows: normal pressure or be dried under reduced pressure residue after precipitation 6~10 hours at 110~130 DEG C.
By above-mentioned acid after molten, precipitation, drying process to get to the present invention prepared by high activated catalyst, catalyst
Appearance white is to grey powder or particle, and the easy moisture absorption, closed to save or save after a certain amount of desiccant is added, desiccant used is
Anhydrous magnesium sulfate or anhydrous sodium sulfate.
The present invention also provides a kind of esterification techniques that catalyst system prepared by the present invention is applied to plasticizer synthesis
Method:
It is that phthalic anhydride or terephthalic acid (TPA) and octanol are put into reaction kettle in the ratio of 1:2.0~3.0 (molar ratio)
In, 145~155 DEG C are warming up to, the catalyst of 0.3~0.8% (weight ratio) is added, insulation reaction 2~4 hours, cooling, catalysis
Recycling is recovered by filtration in agent, and mother liquor alkali cleaning, washing, distillation dealcoholysis obtain target product.
Wherein, preferably:
The octanol includes isooctanol (2-Ethylhexyl Alcohol) and sec-octyl alcohol (octanol-2).
The catalyst of recycling is washed with octanol, and 100~130 DEG C of vacuum drying save, reusable, is catalyzed in the process
Agent is lost less than 5%.
Mother liquor after filtration catalytic agent is washed with 5% sodium hydroxide or 10% sodium carbonate liquor, volume ratio 1:2, liquid separation point
From the recycling of alkali cleaning water phase；Organic phase washes (volume ratio 1:2), and liquid separation separation, water phase reuses or for matching lye；
Organic phase vacuum distillation recycles octanol to get target product plasticizer phthalic acid dioctyl ester (DOP) or terephthalic acid (TPA) is arrived
Dioctyl ester (DOTP).
The beneficial effects of the invention are that anion is organic superpower acid group in catalyst system prepared by the present invention, have
Strong nucleophilic performance and good performance of leaving away, inherently can effective catalytic esterification, be equipped with the special coordination of Titanium
Performance, so that catalyst prepared by the present invention has higher activity compared with titanate esters catalyst system, to reach compared with low temperature
The lower effective esterification for realizing phthalic acid (acid anhydride) and octanol of degree, it is particularly advantageous to which the double esterification process of monoesters, improves double esterification
Reaction speed shortens the reaction time.The titanate esters catalyst system being commonly used is replaced using catalyst system of the invention,
Under conditions of guaranteeing esterification yield, esterification temperature can be greatly lowered to 150 DEG C or less (at present using 220~240 DEG C), simultaneously
Shorten the reaction time to 2~4 hours (titanate esters technique is 6~10 hours), the recyclable recycling of catalyst effectively improves ester
Change efficiency, reduces production cost.
Compared with domestic existing plasticizer production process, using highly active catalytic system prepared by the present invention and work is applied
Skill is down to 150 DEG C by 220~240 DEG C the beneficial effect is that considerably reducing reaction temperature, reduces energy consumption, while by
It is lower than octanol boiling point in reaction temperature, solves the state that octanol is in " evaporation-condensation-reflux " always during the reaction,
Reduce octanol consumption；It is recycled and is reused by catalyst, reduce material cost；Due to the high activity of catalyst system,
Be reduced to the reaction time 2~4 hours by 6~10 hours, reaction temperature reduction and the reaction time shortening, solve due to
High temperature for a long time react caused by product color deepen the problem of, product appearance be improved significantly, optimize last handling process.
Detailed description of the invention
Fig. 1 is existing dioctyl phthalate (DOP) process flow.
Dioctyl phthalate (DOP) process flow of specific embodiment Fig. 2 of the invention.
Specific embodiment
Below with reference to the embodiments and with reference to the accompanying drawing technical solution of the present invention is described in further detail.
Catalyst preparation (catalyst A) of one titanium dioxide of embodiment as titanium-based
In 250ml four-hole bottle (stirring, thermometer, reflux condensing tube), 80g (1mol) Behavior of Ultrafine Titanium Dioxide Particles is added
(gas phase titanium dioxide, partial size are less than 50nm, and 99.5%) content is greater than, then be carefully added into 60g (about 0.5mol) trifluoromethyl second
The solution that acid and 60ml deionized water are made into, is to slowly warm up to flow back, maintains the reflux for state 48 hours or more, be cooled under stirring
Room temperature filters, and recycles titanium dioxide after filtration cakes torrefaction；Mother liquor is evaporated under reduced pressure under the conditions of 0.09~-0.1Mpa and 40~80 DEG C
Solvent is sloughed, then 6 hours dry at 110~130 DEG C, crushing obtains catalyst A powder about 80g, and hermetically drying saves.
Two trifluoromethane sulfonic acid Titanium salt catalyst of embodiment prepares (catalyst B)
In 1-L four-hole bottle (stirring, dropping funel, hydrogen chloride gas-guide tube), the tri-chlorination of 300ml content 15~20% is added
Titanium aqueous solution stirs the lower solution for 100g trifluoromethane sulfonic acid being added dropwise and 100ml deionized water is made into, is stirred at room temperature 48 hours,
Insoluble matter impurity is filtered off, mother liquor is evaporated under reduced pressure under the conditions of 0.09~-0.1Mpa and 60~80 DEG C and slips out to no liquid, will steam
Raffinate is evaporated to be transferred in evaporator, it is 12 hours dry at 110~130 DEG C, catalyst B about 120g, hermetically drying are obtained after crushing
It saves.
Three diisooctyl phthalate of embodiment (DOP) preparation method
In 1000ml four-hole bottle (stirring, thermometer, water segregator, feed opening), phthalic anhydride 125g is added
(0.84mol) is warming up to 145~155 DEG C under isooctanol 365ml (304g, 2.34mol) stirring, catalyst A 0.6g (benzene is added
The 0.5% of acid anhydride weight), it is kept for reaction temperature about 4 hours, divides water about 14ml (theoretical value 15.3ml) in the process.Reaction process
It is middle to utilize TLC (thin-layer chromatography contact plate) method, the progress of reaction is monitored, until phthalic anhydride and phthalic acid mono octyl ester color
Basic disappear of spectrum point is reaction end.
Catalyst is recovered by filtration in cooling, and mother liquor is washed with 5% sodium hydroxide solution 200ml, and liquid separation separation, inorganic phase is mended
Reuse after alkali；Organic phase washs secondary, water phase reuse with deionized water 100ml；Organic phase in 0.09~-0.1Mpa and 135~
Dealcoholysis to no fraction is depressurized under the conditions of 150 DEG C to generate, and obtains colourless to faint yellow target product DOP about 320g, yield 96.4%,
Purity is greater than 98% (gas-chromatography).
Referring to shown in Fig. 1 and Fig. 2, it is known that domestic prior art is catalyzed using butyl titanate, and temperature is added in catalyst
Be 180~185 DEG C, additional amount be raw material phthalic anhydride weight ratio 0.8%, reaction temperature be 230~240 DEG C, the reaction time be 6~
8 hours；Meanwhile after reaction, last handling process needs active carbon decoloring.The present invention and prior art compare, due to reaction
The reduction of temperature and the shortening in reaction time solve the problems, such as that product color caused by being reacted for a long time due to high temperature is deepened,
Product appearance be improved significantly, optimize last handling process.
In a specific embodiment of the present invention, the process conditions of use are as follows:
145~155 DEG C of reaction temperature, the reaction time 2~4 hours, catalyst charge was the 3~5% of phthalic anhydride weight ratio,
And can recycle and reuse, after recycling catalyst, hydrolysis water can be reused；Last handling process is not necessarily to active carbon decoloring.
Example IV di-sec-octyl phthalate preparation method
Since the hydroxyl of sec-octyl alcohol is located at 2 of carbochain, belong to secondary alcohol structure, catalyst activity prepared by the present invention compared with
Height will lead to secondary alcohol and be dehydrated to form alkene, therefore need to use the scheme of stepwise reaction, be formed under conditions of no catalyst first
Then catalyst is added in monoesters, the formation of alkene is controlled by way of alcohol is added dropwise, monoesters is made gradually to be converted into dibasic acid esters.Specifically
It is as follows:
In 500ml four-hole bottle (stirring, thermometer, separatory funnel, water segregator), phthalic anhydride 62.5g is sequentially added
(0.42mol) and 65ml (0.42mol, 54.6g) sec-octyl alcohol is warming up to 145~155 DEG C, keeps reaction 2 hours, utilizes TLC
(thin-layer chromatography contact plate) method, monitors the progress of reaction, until after phthalic anhydride is completely converted into phthalic acid mono octyl ester,
It is added catalyst C 0.3g (the 5% of phthalic anhydride weight ratio), (about each second 1 drips) 65ml sec-octyl alcohol, about 1 is slowly added dropwise
Hour drips off, and the reaction was continued 1 hour.
It is post-processed according to the method for example IV, obtains target product di-sec-octyl phthalate about 145g, received
Rate 87%, 98% or more product purity.
Five Di-2-ethylhexyl terephthalate of embodiment (DOTP) preparation method
In 1000ml four-hole bottle (stirring, thermometer, water segregator, feed opening), it is added terephthalic acid (TPA) 166g (1mol), it is different
145~155 DEG C are warming up under octanol 421ml (351g, 2.7mol) stirring, keeps the temperature about 1~1.5 hour, until solid
All dissolutions are added catalyst B 1.3g (the 0.8% of terephthalic acid (TPA) weight), are kept for reaction temperature about 3~4 hours, utilize
TLC (thin-layer chromatography contact plate) method, monitors the progress of reaction, until terephthalic acid (TPA) and terephthalic acid (TPA) mono octyl ester chromatography point are basic
It disappears, stops reaction, catalyst is recovered by filtration in cooling, and mother liquor is washed with 5% sodium hydroxide solution 200ml, liquid separation separation, nothing
Machine mutually mends reuse after alkali；Organic phase washs secondary, water phase reuse with deionized water 100ml；Organic phase in 0.09~-0.1Mpa and
Dealcoholysis to no fraction is depressurized under the conditions of 135~150 DEG C to generate, and obtains colourless to faint yellow target product dioctyl terephthalate
(DOTP) about 376g, yield 96.2%, purity are greater than 98% (gas-chromatography).
Six terephthalic acid (TPA) di-sec-octyl preparation method of embodiment
Referring to the method for embodiment five, substep esterification is carried out, first mixes equimolar terephthalic acid (TPA) with sec-octyl alcohol,
Under conditions of being added without catalyst, in 140 DEG C or so progress mono-esterifications, TLC method detects terminal, is totally converted to sec-octyl alcohol
After terephthalic acid (TPA) mono octyl ester, catalyst B is added, additional amount is the 0.8% of terephthalic acid (TPA) weight, is instilled equimolar secondary
Octanol, it is terminal that the single pungent rouge of TLC detection, which is completely converted into double monooctyl esters, and cooling is post-processed.
By terephthalic acid, yield is greater than 85%, 98% or more product purity.
It a kind of is urged for being catalyzed phthalic acid and the novel high-activity of octanol esterification in conclusion provided by the invention
Agent preparation method and applications technique synthesizes high active titanium catalyst using organic super acids and inorganic titanium compound as raw material,
Under organic super acids titanium salt catalysis, phthalic anhydride or terephthalic acid (TPA) are as carboxylic acid precursor, isooctanol or sec-octyl alcohol
For octanol raw material, plasticizer phthalic acid dioctyl ester (DOP) and dioctyl terephthalate are realized by esterification
(DOTP) synthetic process.And the titanate esters catalyst system being commonly used is replaced using catalyst system of the invention,
Under conditions of guaranteeing esterification yield, esterification temperature can be greatly lowered to 150 DEG C or less (at present using 220~240 DEG C), together
When shorten the reaction time to 2~4 hours (titanate esters technique be 6~10 hours), the recyclable recycling of catalyst effectively improves
Esterifying efficiency reduces production cost.
The above embodiments are merely illustrative of the technical scheme of the present invention and are not intended to be limiting thereof, although referring to above-described embodiment pair
The present invention is described in detail, it should be understood by a person of ordinary skill in the art that still can be to of the invention specific
Embodiment is modified or replaced equivalently, and without departing from any modification of spirit and scope of the invention or equivalent replacement,
It is intended to be within the scope of the claims of the invention.
Claims (10)
1. a kind of organotitanium preparation method, which is characterized in that the catalyst is anti-by titanium base material and organic super acids
It answers, by acid, molten, precipitation, drying process are made.
2. a kind of organotitanium preparation method according to claim 1, which is characterized in that the titanium base material is
Titanium oxide, metatitanic acid, titanium chloride.
3. a kind of organotitanium preparation method according to claim 2, which is characterized in that the titanium oxide is one
Titanium oxide, titanium dioxide or titanium sesquioxide, metatitanic acid are titanium hydroxide, and the titanium chloride is titanium trichloride or titanium tetrachloride.
4. a kind of organotitanium preparation method according to claim 1, which is characterized in that organic super acids
The group constituted selected from trifluoromethyl acetic acid, trichloromethyl acetic acid, trifluoromethane sulfonic acid, trinitrobenzene sulfonic acid and its corresponding acid anhydrides
Group.
5. a kind of organotitanium preparation method according to claim 1, which is characterized in that the molten technique of acid
Are as follows: titanium base material and organic super acids are mixed with the ratio of equivalent, suitable quantity of water stirring is added, makes at a predetermined temperature solid
Body object completely or partially dissolves, and filters insoluble matter.
6. a kind of organotitanium preparation method according to claim 5, which is characterized in that the precipitation technique
Are as follows: insoluble matter is filtered into post mother liquor, moisture and other fractions are sloughed by way of normal pressure or vacuum distillation.
7. a kind of organotitanium preparation method according to claim 1, which is characterized in that the drying process
Are as follows: residue after precipitation normal pressure or is dried under reduced pressure 6~10 hours at 110~130 DEG C.
8. organotitanium described in a kind of above-mentioned any claim is applied to the method for the esterification technique of plasticizer synthesis,
It is characterized in that, this method is that the ratio of 1:2.0~3.0 investment is anti-in molar ratio by phthalic anhydride or terephthalic acid (TPA) and octanol
It answers in kettle, is warming up to 145~155 DEG C, the catalyst of weight ratio 0.3~0.8% is added, it is insulation reaction 2~4 hours, cooling, it urges
Recycling is recovered by filtration in agent, and mother liquor alkali cleaning, washing, distillation dealcoholysis obtain target product.
9. the method for the esterification technique of plasticizer according to claim 8 synthesis, it is characterised in that: the octanol includes
Isooctanol and sec-octyl alcohol.
10. the method for the esterification technique of plasticizer synthesis according to claim 8, it is characterised in that: the catalyst of recycling
It is washed with octanol, is dried in vacuo through 100~130 DEG C, saved, to make in technical process catalyst loss less than 5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811157166.9A CN109225322A (en) | 2018-09-30 | 2018-09-30 | A kind of method organotitanium preparation and its catalyze and synthesize plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811157166.9A CN109225322A (en) | 2018-09-30 | 2018-09-30 | A kind of method organotitanium preparation and its catalyze and synthesize plasticizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109225322A true CN109225322A (en) | 2019-01-18 |
Family
ID=65054991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811157166.9A Pending CN109225322A (en) | 2018-09-30 | 2018-09-30 | A kind of method organotitanium preparation and its catalyze and synthesize plasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109225322A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393289A (en) * | 2020-05-09 | 2020-07-10 | 安徽灵达高新材料有限公司 | Method for preparing fluorinated acrylate from fluorinated alcohol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989008079A1 (en) * | 1988-03-02 | 1989-09-08 | Trustees Of Boston University | Catalytic process for degradation of organic materials in aqueous and organic fluids to produce environmentally compatible products |
| US5767215A (en) * | 1991-05-09 | 1998-06-16 | Borealis Holding A/S | Coarse-grained polyolefin, its production method and a catalyst used in the method |
| CN104529780A (en) * | 2014-12-19 | 2015-04-22 | 河南奥思达新材料有限公司 | Method for producing DOP by use of composite lewis acid catalyzing method |
| CN105985532A (en) * | 2015-03-06 | 2016-10-05 | 镇江市凯普化学科技有限公司 | Method for producing compound plasticizer from fumaric acid production wastewater |
-
2018
- 2018-09-30 CN CN201811157166.9A patent/CN109225322A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989008079A1 (en) * | 1988-03-02 | 1989-09-08 | Trustees Of Boston University | Catalytic process for degradation of organic materials in aqueous and organic fluids to produce environmentally compatible products |
| US5767215A (en) * | 1991-05-09 | 1998-06-16 | Borealis Holding A/S | Coarse-grained polyolefin, its production method and a catalyst used in the method |
| CN104529780A (en) * | 2014-12-19 | 2015-04-22 | 河南奥思达新材料有限公司 | Method for producing DOP by use of composite lewis acid catalyzing method |
| CN105985532A (en) * | 2015-03-06 | 2016-10-05 | 镇江市凯普化学科技有限公司 | Method for producing compound plasticizer from fumaric acid production wastewater |
Non-Patent Citations (3)
| Title |
|---|
| KAZUHIKO SAIGO ET AL: "Facile Synthesis of Selectively Monoprotected Unsymmetrical 1,3-Diketones from 2,2-Dimethoxyethyl Esters", 《SYNTHETIC COMMUNICATIONS》 * |
| ROXALD E. SOFTLE，GEORGE H. CL4DY: "Preparation and Properties of Some New Trifluoromethanesulfonates", 《INORGANIC CHEMISTRY》 * |
| 丁玉兴, 王家喜, 李爱红, 钟正伟: "新型负载钛酸酯催化剂催化合成邻苯二甲酸二异辛酯", 《河北化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393289A (en) * | 2020-05-09 | 2020-07-10 | 安徽灵达高新材料有限公司 | Method for preparing fluorinated acrylate from fluorinated alcohol |
| CN111393289B (en) * | 2020-05-09 | 2022-09-13 | 安徽灵达高新材料有限公司 | Method for preparing fluorinated acrylate from fluorinated alcohol |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105344341B (en) | A kind of preparation method of solid catalyst for Synthesis of dimethyl carbonate | |
| CN109516971A (en) | A kind of synthetic method of LITHIUM BATTERY sulfuric acid vinyl ester | |
| WO2018045938A1 (en) | Crude cyclic ester purification method | |
| CN105111461A (en) | Method for preparing lignin ester by mechanical activation- solid reaction | |
| Yuan et al. | Metal− organic frameworks as recyclable catalysts for efficient esterification to synthesize traditional plasticizers | |
| CN109225322A (en) | A kind of method organotitanium preparation and its catalyze and synthesize plasticizer | |
| CN110642718B (en) | Heterogeneous catalyst for synthesizing diphenyl carbonate and preparation method thereof | |
| CN105646570A (en) | Novel organic titanate butanediol titanium, and synthesis method and application thereof | |
| EP3377554A1 (en) | Production of esters of 3-hydroxypropionic acid and acrylic acid | |
| CN101837296B (en) | Solid super acid for esterification of rosin esterification and preparation method thereof | |
| CN107778175A (en) | The synthesis technique of the tricaprylate of Isosorbide-5-Nitrae cyclohexanedimethanol two | |
| CN102850303B (en) | New application and using method of mesoporous solid acid catalyst | |
| CN112830869A (en) | Preparation method of high-purity octabromoether | |
| CN102381947B (en) | Synthesis method of chiral 2,2 '- di-alkoxy-1, 1'-binaphthyl | |
| CN104086466A (en) | Preparation method of 2-chloro-4-methylsulfonylbenzoic acid | |
| CN108218699A (en) | The method that presence of acidic ionic liquid catalyst synthesizes the positive hexadecyl ester of 3,5- di-tert-butyl-4-hydroxybenzoic acids | |
| CN105330545B (en) | The method that triazine ring cyclization mother liquid bits mesoxalic acid is recycled using stannic chloride as catalyst | |
| CN110776484A (en) | Preparation method of vitamin C palmitate | |
| CN101973870B (en) | Preparation of glycollic acid from oxalaldehyde by intramolecular disproportionation method | |
| CN1483713A (en) | Method for synthesizing beta-ionone | |
| CN105749967A (en) | Method for preparing tributyl citrate in presence of bamboo-charcoal-based solid sulfonic acid catalyst | |
| CN105085892A (en) | Method for preparing catalysts for manufacturing polycarbonate diols | |
| CN114507132B (en) | Catalytic method for synthesizing citrate | |
| CN110143861A (en) | A kind of preparation method of brufen | |
| CN104513162A (en) | Hydroxyethyl acrylate preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190118 |
|
| RJ01 | Rejection of invention patent application after publication |