CN105523928B - The method that methyl acetate produces vinyl acetate - Google Patents

Abstract

The present invention relates to the method for methyl acetate production vinyl acetate, mainly solves the problems, such as that methyl acetate is successively low through being carbonylated, cracking the yield of vinyl acetate and selectivity when route prepares vinyl acetate.It is main to use the technical scheme comprised the following steps：Methyl acetate carbonylation obtains ethylidene diacetate；Ethylidene diacetate obtains vinyl acetate through cracking；Carbonylating catalyst includes major catalyst and co-catalyst, and major catalyst includes carrier, active component；The activearm uses the compound of rhodium；The co-catalyst is iodide；The carrier is polymer；The polymer is selected from least one of poly- (N vinyl pyrrolidones), poly- (maleic anhydride of styrene), ammonification poly- (maleic anhydride of styrene) and benzylamine negative resin polymer of certain degree of cross linking.

Description

The method that methyl acetate produces vinyl acetate

Technical field

The present invention relates to the method for methyl acetate production vinyl acetate.

Background technology

Vinyl acetate (VAc) is one of 50 kinds of maximum industrial chemicals of world wide production, is total to by autohemagglutination or with other monomers It is poly-, polyvinyl alcohol (PVA), polyvinyl acetate (PVAc) emulsion, vinyl acetate-ethylene copolymerization emulsions (VAE) or common can be generated The derivatives such as poly resin (EVA), vinyl acetate-chloride copolymer (EVC).These derivatives are widely used in adhesive, built Cementing agent, coating, ink, leather processing, fiber process, emulsifying agent, water-solubility membrane and the soil for building coating, paper or fabric change Good dose etc..

Ethene vapor phase method and acetylene in gas phase method technique are used inside and outside the producing country of vinyl acetate, belongs to petrochemical process Route, from after rising C1 chemistry, in the 1980s, U.S. Ha Erkang (Halcon) companies and BP (BP) company are successively It is proposed is prepared new technology-carbonyl process synthesizing vinyl acetate of vinyl acetate by methanol and synthesis gas.The technique is independent of oil Work raw material, but by methyl acetate and the carbonylation of synthesis gas, synthetic intermediate ethylidene diacetate (EDDA), then pass through Cross thermal cracking production vinyl acetate and acetic acid.The novel part of whole technique is the hydroformylation reaction of methyl acetate, is catalyzed Agent radium chloride is simultaneously modified with beta-picoline and iodomethane, and carbon monoxide intercalation reaction is the key point of whole technology.

United States Patent (USP) US5354886 is (entitled：Catalysts on inorganic carriers for Producing ethylidene diacetate) mention RhCl₃Or rhodium compound is supported on diatomite, titanium oxide, oxygen Change and loaded catalyst is made on magnesium, aluminum oxide and zinc oxide.Using methyl acetate, carbon monoxide and hydrogen as raw material, in polarity Under solvent condition, the reaction synthesis ethylidene diacetate under above-mentioned catalyst.US4843170 is (entitled：Process for Produing vinyl acetate) in mention utilize halogen acids, sulfuric acid, nitric acid, polyphosphoric acid, benzene sulfonic acid, alkyl sulfonic acid etc. make The catalyst of vinyl acetate is prepared for ethylidene diacetate cracking.Acetic acid second during synthesizing vinyl acetate be present in the above method The problem of alkene yield is low and selective not high.

The content of the invention

The problem of technical problems to be solved by the invention are that vinyl acetate yield is low and selectivity is not high, there is provided Yi Zhongxin Methyl acetate production vinyl acetate method, this method have vinyl acetate high income and selectivity it is high the characteristics of.

In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Methyl acetate production vinyl acetate Method, comprise the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as raw material, carried out in the presence of carbonylating catalyst Carbonylation obtains ethylidene diacetate；(2) in the presence of catalyst for cracking, ethylidene diacetate cracking is made to obtain acetic acid second Alkene；Wherein, the carbonylating catalyst includes major catalyst and co-catalyst, and major catalyst includes carrier, active component；Activity Component uses the compound of rhodium；The co-catalyst is iodide；The carrier is polymer；It is poly- that the polymer is selected from crosslinking (NVP) (abbreviation PNVP), it is crosslinked poly- (phenylethylene-maleic anhydride) (abbreviation PMAn), the crosslinking poly- (benzene of ammonification Ethylene-maleic acid) at least one of (abbreviation APMAn) and crosslinking benzylamine negative resin polymer；The polymer preferably passes through Oxidation processes.

The compound of rhodium described in above-mentioned technical proposal is preferably RhCl₃.The iodide are preferably iodomethane.It is described poly- The degree of cross linking of compound is preferably 1~60%.

In above-mentioned technical proposal, the adoptable preparation method of major catalyst, comprise the following steps：

1. the polymer support is carried out into oxidation processes, oxidation processes carrier is dried to obtain；

2. by the composition of catalyst by RhCl₃Compound is configured to the aqueous solution and is immersed on the oxidation processes carrier；

3. standing, drying, the major catalyst is obtained.

1. and 3. described drying temperature is preferably independently 80~120 DEG C to step in above-mentioned technical proposal.More preferably 100 ~120 DEG C.

The key of the inventive method is the selection of the major catalyst, after major catalyst is obtained, by making to sponsor Agent contacts with the co-catalyst and can obtain heretofore described carbonylating catalyst.Major catalyst connects with co-catalyst Tactile mode is not particularly limited, and the opportunity for contacting both is also not particularly limited.Such as it can be catalyzed by the present invention Agent is used to before chemically reacting make both contact form the catalyst, can also make what both were applied in catalyst of the present invention Contact makes catalyst in-situ preparation in reaction system.

Another key of the present invention is that oxidation processes have been carried out to polymer, the preferred dioxygen of oxidant of oxidation processes At least one of water, nitric acid, hypochlorous acid, chloric acid and perchloric acid.More preferably hydrogen peroxide and perchloric acid hybrid oxidant.

It was found by the inventors of the present invention that in above-mentioned technical proposal, activity component impregnation is used into hydrogen peroxide and height at the same time The catalyst obtained on the APMAn and benzylamine negative resin polymer support of chloric acid hybrid oxidant oxidation processes is either selective Or vinyl acetate yield has reached best.

The key of the present invention is the selection of carbonylating catalyst, and skilled person will know how true according to being actually needed Determine the proportioning of suitable reaction temperature, reaction time, reaction pressure and material.But the temperature reacted in above-mentioned technical proposal Preferably 130~200 DEG C；The pressure of reaction is preferably 3.0~10.0MPa；The time of reaction is preferably 3.0~10.0h.One oxygen The mol ratio for changing carbon and hydrogen is preferably 0.10~10.0.

In the method for methyl acetate synthesis vinyl acetate of the present invention, after step (1) terminates, carbonylation can be mixed Compound carries out separation acquisition target product ethylidene diacetate and carries out step (2) again, can also the double acetic acid Asias second of step (1) generation Do not separated after ester and directly carry out step (2).The suitable catalyst for cracking of the known selection of those skilled in the art and determination are closed Suitable cracking reaction temperature, time and material proportion.Conventional catalyst for cracking have Bronsted acid (such as HI, HBr, HCl, HF, H₂SO₄、H₃PO₄、HNO₃、H₃BO₃、HClO₃、HBrO₃、HIO₃, polyphosphoric acid, alkyl sulfonic acid, benzene sulfonic acid etc.), lewis acid (such as IIA, IIIA, IVA, VA, VIA, IIIB, IVB, VB, VIB, VIIB, VIII metal halogen compound).Preferred benzene sulphur in the present invention Acid is used as catalyst for cracking, and suitable cracking temperature is preferably 100~180 DEG C；Cleavage reaction pressure preferably 0~1.0MPa；Split It is preferably 10~60min to solve the reaction time；Benzene sulfonic acid catalyst for cracking accounts for the 3.0~7.0% of raw material total amount；The preferred acetic acid of solvent At least one of with aceticanhydride.

Product of the present invention is analyzed after cooling down, depressurize, separate using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), is pressed Row formula calculates the conversion ratio of methyl acetate and the yield and selectivity of vinyl acetate：

Compared with prior art, key of the invention is that the carrier of step (1) carbonylating catalyst has used oxidation processes Polymer afterwards, be advantageous to improve the activity and stability of major catalyst, so as to improve the yield of vinyl acetate and selectivity.

Test result indicates that the vinyl acetate yield prepared by the present invention reaches 60.18%, selectively reach 83.30%, Achieve preferable technique effect.Especially hydrogen peroxide and perchloric acid mixing oxygen are used in step (1) carbonylation catalyst agent carrier When agent carries out oxidation processes collaboration to APMAn and benzylamine negative resin polymer, more prominent technique effect is achieved, can be used In the industrial production of vinyl acetate.Below by embodiment, the present invention is further elaborated.

Embodiment

【Embodiment 1】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH₃)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.18%, and selectivity is 83.30%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Comparative example 1】

For【Embodiment 1】Comparative example.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, by a diameter of 5.6mm of 1.0L spherical sio2 carrier impregnation in above-mentioned maceration extract, 3h is stood in 30 DEG C of dryings, is obtained The major catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 50.31%, and selectivity is 75.47%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Comparative example 2】

For【Embodiment 1】Comparative example.

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH3)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

The preparation of major catalyst is carbonylated：RhCl33H2O containing 7.50gRh is dissolved in pure water, obtains maceration extract 500ml, 1.0L polymer supports precursor I and above-mentioned maceration extract are sufficiently mixed, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 51.92%, and selectivity is 75.21%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Comparative example 3】

For【Embodiment 1】Comparative example.

The preparation of carrier:By a diameter of 5.6mm of 1.0L spherical SiO₂Concentration with double weight is 5wt% hydrogen peroxide The aqueous solution is mixed, and carries out oxidation processes 4h, and oxidizing temperature is kept for 35 DEG C, the carrier after being dried to obtain oxidation processes at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, by SiO after 1.0L oxidation processes₂Carrier is sufficiently mixed with maceration extract, is stood 3h in 30 DEG C of dryings, is obtained described sponsor Agent.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 51.74%, and selectivity is 75.38%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

The catalyst carrier used by can be seen that the present invention compared with Example 1, using oxidant to polymer supported The performance of body oxidation processes rear catalyst than using conventional silica supports, than only using the not oxidised processing of polymer support Carrier, than only, the choosing of vinyl acetate more excellent to the performance of catalyst made of the carrier of Normal silica with oxidant Selecting property and yield will be high, and this can be seen that from the data of embodiment 1, comparative example 1~3 illustrates to use from oxidizing Polymer support after reason has more preferable peptizaiton to catalyst activity component.

【Embodiment 2】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, PNVP Preparation process is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.Take 13ml vinylpyrrolidones (PVP) and 7ml divinylbenzenes (DVB) It is 35% single phase to be well mixed and be made into the degree of cross linking, adds the azodiisobutyronitrile (AIBN) of amount of monomer 0.5% (mass fraction) Initiator be allowed to fully dissolving occur to suspend it is solidifying close reaction, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, PNVP polymer supports are dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L PNVP polymer supports and above-mentioned maceration extract are sufficiently mixed, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.25%, and selectivity is 83.39%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Embodiment 3】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, PMAn Preparation process is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction) is allowed to fully dissolve generation and suspend to coagulate to close to react, through cleaning, Wash, be dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, PMAn polymer supports are dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L PMAn polymer supports and above-mentioned maceration extract are sufficiently mixed, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.38%, and selectivity is 83.34%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Embodiment 4】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, APMAn preparation process is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction), which is allowed to fully dissolve to occur to suspend to coagulate to close, to react, and reaction terminates Afterwards, the ammoniacal liquor that 50ml concentration is 27wt% is instilled into its flask, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, APMAn polymer supports are dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L APMAn polymer supports and above-mentioned maceration extract are sufficiently mixed, stand 3h 30 DEG C of dryings of vacuum, obtained described Major catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.47%, and selectivity is 83.54%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Embodiment 5】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH₃)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the aqueous solution of nitric acid that the concentration of double weight is 5wt%, carries out oxidation processes 4h, oxidizing temperature are kept for 35 DEG C, benzylamine negative resin carrier are dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.25%, and selectivity is 83.49%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Embodiment 6】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH₃)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the hypochloric acid water solution that the concentration of double weight is 2wt%, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.62%, and selectivity is 83.43%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Embodiment 7】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH₃)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the chloric acid aqueous solution that the concentration of double weight is 5wt%, carries out oxidation processes 4h, oxidizing temperature are kept for 35 DEG C, benzylamine negative resin carrier are dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.21%, and selectivity is 83.19%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Embodiment 8】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH₃)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the high chloro acid solution that the concentration of double weight is 2wt%, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.46%, and selectivity is 83.28%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Embodiment 9】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, APMAn preparation process is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl for adding aqueous phase quality 2% is warming up to 50 DEG C.18ml styrene (St) is taken to be well mixed with 2ml divinylbenzenes (DVB) It is 1% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction), which is allowed to fully dissolve to occur to suspend to coagulate to close, to react, and reaction terminates Afterwards, the ammoniacal liquor that 50ml concentration is 27wt% is instilled into its flask, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, APMAn polymer supports are dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L APMAn polymer supports and above-mentioned maceration extract are sufficiently mixed, stand 3h 30 DEG C of dryings of vacuum, obtained described Major catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.07%, and selectivity is 82.82%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Embodiment 10】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, APMAn preparation process is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.8ml styrene (St) is taken to be well mixed with 12ml divinylbenzenes (DVB) It is 60% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction), which is allowed to fully dissolve to occur to suspend to coagulate to close, to react, and reaction terminates Afterwards, the ammoniacal liquor that 50ml concentration is 27wt% is instilled into its flask, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, APMAn polymer supports are dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L APMAn polymer supports and above-mentioned maceration extract are sufficiently mixed, stand 3h 30 DEG C of dryings of vacuum, obtained described Major catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.58%, and selectivity is 83.12%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Embodiment 11】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl for adding aqueous phase quality 2% is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH₃)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

By the hydrogen peroxide and perchloric acid mixed aqueous solution (wherein hydrogen peroxide of polymer support precursor I and double weight Concentration be 2.5wt%, the concentration of perchloric acid is 2.5wt%) mixing, carry out oxidation processes 4h, oxidizing temperature keep 35 DEG C, 100 DEG C are dried to obtain benzylamine negative resin carrier.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 62.37%, and selectivity is 84.86%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

Found out on year-on-year basis by embodiment 11 and embodiment 1 and embodiment 8, improving the selectivity of vinyl acetate and yield side Face, hydrogen peroxide and perchloric acid oxidation's atmosphere have synergy.

【Embodiment 12】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH₃)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, APMAn preparation process is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction), which is allowed to fully dissolve to occur to suspend to coagulate to close, to react, and reaction terminates Afterwards, the ammoniacal liquor that 50ml concentration is 27wt% is instilled into its flask, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, APMAn polymer supports are dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 0.6L benzylamine negative resins carrier, 0.4L APMAn polymer supports are sufficiently mixed with above-mentioned maceration extract, it is true to stand 3h Empty 30 DEG C of dryings, obtain the major catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 62.43%, and selectivity is 84.93%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 4, improving the selectivity of vinyl acetate and yield side Face, benzylamine negative resin carrier and APMAn polymer supports have synergy.

【Embodiment 13】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH₃)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

By the hydrogen peroxide and perchloric acid mixed aqueous solution (wherein hydrogen peroxide of polymer support precursor I and double weight Concentration be 2.5wt%, the concentration of perchloric acid is 2.5wt%) mixing, carry out oxidation processes 4h, oxidizing temperature keep 35 DEG C, 100 DEG C are dried to obtain benzylamine negative resin carrier.

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, APMAn preparation process is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, then 2.35g maleic anhydrides are added into above-mentioned single phase, is stirring evenly and then adding into amount of monomer Benzoyl peroxide (BPO) initiator of 0.5% (mass fraction), which is allowed to fully dissolve to occur to suspend to coagulate to close, to react, and reaction terminates Afterwards, the ammoniacal liquor that 50ml concentration is 27wt% is instilled into its flask, through cleaning, washing, being dried to obtain polymer support precursor I.

By the hydrogen peroxide and perchloric acid mixed aqueous solution (wherein hydrogen peroxide of polymer support precursor I and double weight Concentration be 2.5wt%, the concentration of perchloric acid is 2.5wt%) mixing, carry out oxidation processes 4h, oxidizing temperature keep 35 DEG C, 100 DEG C are dried to obtain APMAn polymer supports.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 0.6L benzylamine negative resins carrier, 0.4L APMAn polymer supports are sufficiently mixed with above-mentioned maceration extract, it is true to stand 3h Empty 30 DEG C of dryings, obtain the major catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 6.8MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 172 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 2:After 1, sustained response 8.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 64.78%, and selectivity is 86.31%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

Found out on year-on-year basis by embodiment 13 and embodiment 11 and embodiment 12, improving the selectivity and yield of vinyl acetate Aspect, benzylamine negative resin carrier, APMAn polymer supports and hydrogen peroxide, perchloric acid oxidation's atmosphere have synergy.

【Embodiment 14】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH₃)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 3.0MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 130 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 1:After 10, sustained response 3.0h, stop reaction.Reactor is dropped To room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 54.32%, and selectivity is 78.95%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

【Embodiment 15】

The preparation of polymer support：According to (the monodisperse porous St/ of Shang Yuanyan, Zhu Yihua, Hu Ling, Yang Xiao tinkling of pieces of jade such as Shang Yuanyan Preparation [J] Journal of Functional Polymers of DVB copolymerization microspheres, 2005,18,7-11.) preparation method for the polymer mentioned, benzylamine The preparation process of negative resin is as follows：

The PVA aqueous solution that 250ml concentration is 0.5wt% is added in the three-necked flask of 500ml capacity first, in aqueous phase The NaCl of aqueous phase quality 2% is added, is warming up to 50 DEG C.13ml styrene (St) is taken to be well mixed with 7ml divinylbenzenes (DVB) It is 35% single phase to be made into the degree of cross linking, and benzoyl peroxide (BPO) initiator for adding amount of monomer 0.5% (mass fraction) is allowed to Abundant dissolving occurs the solidifying conjunction reaction of suspension and obtains polystyrene bulb.After bulb is activated, swelling is dried with ClCH₂OCH₃、 (CH₃)₂After NH reactions, through cleaning, washing, being dried to obtain polymer support precursor I.

Polymer support precursor I is mixed with the concentration of double weight for 5wt% aqueous hydrogen peroxide solutions, carried out at oxidation 4h is managed, oxidizing temperature is kept for 35 DEG C, benzylamine negative resin carrier is dried to obtain at 100 DEG C.

The preparation of major catalyst is carbonylated：By the RhCl containing 7.50gRh₃·3H₂O is dissolved in pure water, obtains maceration extract 500ml, 1.0L benzylamine negative resin carriers are sufficiently mixed with above-mentioned maceration extract, stand 3h 30 DEG C of dryings of vacuum, obtain the master Catalyst.For the major catalyst through icp analysis, Rh contents are 7.50g/L.

The synthesis of vinyl acetate：

Step (1)：By 0.5mol acetic acid, 0.02mol carbonylations major catalyst, 0.02mol iodomethane and 0.15mol acetic acid Methyl esters is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to carbon monoxide With hydrogen until pressure 10.0MPa, improves mixing speed to 1500rpm, while agitating and heating is warming up to reaction temperature, and control is anti- It is 200 DEG C to answer temperature, and the mol ratio of carbon monoxide and hydrogen is 10:After 1, sustained response 10.0h, stop reaction.By reactor Room temperature is down to, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, acetic acid second are removed through rectification and purification Ester, acetaldehyde and other accessory substances, obtain ethylidene diacetate.

Step (2)：It is 150ml that above-mentioned ethylidene diacetate 20ml, aceticanhydride 30ml, 0.01mol benzene sulfonic acid are added into volume The rectification process tower of reactor, first discharged with argon gas and be pressurized to 0.28MPa in kettle after air, raising mixing speed to 600rpm, Agitating and heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 143 DEG C, after sustained response 40min, stops reaction.

Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter Compose combined instrument (GC-MASS) analysis.

The yield for being computed vinyl acetate is 60.94%, and selectivity is 82.98%, for convenience of description and is compared, will be poly- Compound carrier is prepared and oxidation processes condition, the preparation condition of catalyst, reaction condition, material inlet amount, the receipts of vinyl acetate Rate and selectivity are listed in Tables 1 and 2 respectively.

Table 1

Table 2

Claims (9)

1. the method for methyl acetate synthesis vinyl acetate, comprises the following steps：(1) using methyl acetate, carbon monoxide and hydrogen as Raw material, carbonylation acquisition ethylidene diacetate is carried out in the presence of carbonylating catalyst；(2) exist in catalyst for cracking Under, ethylidene diacetate cracking is obtained vinyl acetate；Wherein, the carbonylating catalyst includes major catalyst and co-catalysis Agent, major catalyst include carrier, active component；The activearm uses the compound of rhodium；The co-catalyst is iodide；Institute It is polymer to state carrier；The polymer, which is selected from, is crosslinked poly- (NVP), the poly- (styrene-maleic acid of crosslinking Acid anhydride), crosslinking ammonification poly- (phenylethylene-maleic anhydride) and be crosslinked at least one of benzylamine negative resin polymer；The main catalytic Agent is prepared using the method comprised the following steps：

1. the polymer support is carried out into oxidation processes, oxidation-treated carrier is dried to obtain；

2. by the composition of catalyst by RhCl₃Compound is configured to the aqueous solution and is immersed on the oxidation-treated carrier；

3. standing, drying, the major catalyst is obtained；

Wherein, the oxidation processes wherein described in step use the hybrid oxidant being made up of hydrogen peroxide and perchloric acid.

2. according to the method for claim 1, it is characterised in that the compound of the rhodium is RhCl₃。

3. according to the method for claim 1, it is characterised in that the iodide are iodomethane.

4. according to the method for claim 1, it is characterised in that the degree of cross linking of the polymer is 1~60%.

5. according to the method for claim 1, it is characterised in that the temperature of the carbonylation is 130~200 DEG C.

6. according to the method for claim 1, it is characterised in that the pressure of the carbonylation is 3.0~10.0MPa.

7. according to the method for claim 1, it is characterised in that carbon monoxide and hydrogen volume ratio in the carbonylation For 0.10~10.0.

8. according to the method for claim 1, it is characterized in that the time of the carbonylation is 3.0~10.0h.

9. according to the method for claim 1, it is characterised in that step 1. and 3. described drying temperature independently elect 80 as~ 120℃。