CN104276948A - Preparation method of tert-butyl (methyl)acrylate - Google Patents
Preparation method of tert-butyl (methyl)acrylate Download PDFInfo
- Publication number
- CN104276948A CN104276948A CN201410448289.3A CN201410448289A CN104276948A CN 104276948 A CN104276948 A CN 104276948A CN 201410448289 A CN201410448289 A CN 201410448289A CN 104276948 A CN104276948 A CN 104276948A
- Authority
- CN
- China
- Prior art keywords
- methyl
- tert
- butylene
- iso
- butyl acrylate
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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)
Abstract
The invention provides a preparation method of tert-butyl (methyl)acrylate. (Methyl)acrylic acid and isobutylene are subjected to addition reaction under the action of an acidic catalyst to generate the tert-butyl (methyl)acrylate. The technique belongs to an ideal atomic economic reaction, simplifies the process route, and needs fewer appliances. Besides, no byproduct is generated in the whole preparation process, so the method is a low-carbon environment-friendly technique. The adopted acidic catalyst is non-toxic and harmless, so the production process is environment-friendly. Therefore, the olefine acid addition esterification method can be widely used and is suitable for substituting the alkyd esterification method.
Description
Technical field
The present invention relates to the chemical field of olefin(e) acid legal system for ester, refer in particular to one (methyl) tert-butyl acrylate preparation method.
Background technology
(methyl) tert-butyl acrylate is a kind of very important Elementary Chemical Industry raw material and intermediate, because it has uniqueness and active strong polar molecule, unsaturated double-bond and carboxylicesters (-COOR) structure, therefore the polymer formulators that many kinds have superperformance can be derived, and prepare plasticity, the polymkeric substance such as crosslinked through processing modes such as letex polymerization, solution polymerization, copolymerization.Also can autohemagglutination or with other vinyl monomer copolymerization, as vinylbenzene, vinyl acetate, methyl methacrylate, vinyl cyanide, acrylamide, vinylchlorid etc.The carbon-to-carbon double bond of (methyl) tert-butyl acrylate carries out the polymkeric substance that polyreaction obtains, water white transparency, there is good chemical property and the physicals such as excellent light stability, weathering resistance, water-fast, oil resistant, chemicals-resistant, cohesiveness is strong, transparency is good, film forming is clear, thus obtains applying more and more widely in coating, synthon, synthetic rubber, plastics, leather, papermaking, tackiness agent, wrapping material, water treatment, metallurgical mining, daily chemical product etc.
But, in traditional technology, in order to prepare (methyl) tert-butyl acrylate, its method mainly adopts (methyl) vinylformic acid and trimethyl carbinol lactate synthesis under sulfuric acid catalysis effect, namely uses (methyl) vinylformic acid to be that raw material and the trimethyl carbinol carry out esterification.Then through processing steps such as extraction, recovery, rectifying, the finished product are obtained.There is equipment corrosion, side reaction and waste reaction solution and be difficult to the problems such as process in this technique.Prepare in the process of tertiary alcohol ester at carboxylic acid and corresponding alcohol esterification in addition, because the space steric effect of the trimethyl carbinol is larger, elimination reaction is more prone in esterification and these two competing reactions of cancellation, do not reach the object of esterification, therefore the esterification of the tertiary alcohol is more much more difficult than primary alconol, secondary alcohol, and the yield of real reaction is very low.
Summary of the invention
Technical problem to be solved by this invention is:
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of (methyl) tert-butyl acrylate preparation method, comprise mol ratio be (methyl) vinylformic acid of 1.0:1.0 ~ 5.0:1.0 and iso-butylene together with an acidic catalyst under the condition of 40 DEG C ~ 120 DEG C temperature, 1.0MPa ~ 5.0MPa reaction pressure with volume space velocity 0.5/h ~ 5.0/h lactate synthesis (methyl) tert-butyl acrylate of iso-butylene.
Present invention also offers another kind of scheme is: a kind of (methyl) tert-butyl acrylate preparation method, comprise by (methyl) vinylformic acid and liquefied petroleum gas (LPG) together with an acidic catalyst under the condition of 40 DEG C ~ 120 DEG C temperature, 1.0MPa ~ 5.0MPa reaction pressure with volume space velocity 0.5/h ~ 5.0/h lactate synthesis (methyl) tert-butyl acrylate of iso-butylene; The mol ratio of the iso-butylene in described (methyl) vinylformic acid and liquefied petroleum gas (LPG) is 1.0:1.0 ~ 5.0:1.0;
In above-mentioned, described liquefied petroleum gas (LPG) comprises C4 hydrocarbon mixture, and C4 hydrocarbon mixture comprises the iso-butylene that content is not less than 5%;
In above-mentioned, described an acidic catalyst is strongly acidic ion-exchange resin catalyst;
In above-mentioned, described strongly acidic ion-exchange resin catalyst is macropore sulfonic acid ion exchange resin;
In above-mentioned, described macropore sulfonic acid ion exchange resin is the poly styrene polymer of divinylbenzene crosslink;
In above-mentioned, the poly styrene polymer of described divinylbenzene crosslink is at least one in Amberlyst-15 (A-15), Amberlyst-35 (A-35), LewatitK2631, Bayer K2631, D-72, S-54, D005, Z/H00, QRE type resin catalyst;
In above-mentioned, the volume space velocity of described iso-butylene is 1.0/h ~ 2.0/h;
In above-mentioned, the mol ratio of described (methyl) vinylformic acid and iso-butylene is 1.0:1.0 ~ 3.0:1.0;
In above-mentioned, the temperature of described reaction conditions is 50 DEG C ~ 70 DEG C, and reaction pressure is 1.5MPa ~ 2.5MPa.
Beneficial effect of the present invention is: pioneering olefin(e) acid addition esterification process produces (methyl) tert-butyl acrylate, by carrying out addition reaction generation (methyl) tert-butyl acrylate with (methyl) vinylformic acid and iso-butylene under an acidic catalyst effect.This technique belongs to desirable atomic economy reaction, both simplifies operational path, and whole appliance arrangement quantity is also less, and in addition, whole preparation process no coupling product is low-carbon environment-friendly technique, and the acid catalyst wherein adopted is nontoxic, and production process is environmentally friendly.Therefore olefin(e) acid addition esterification process can be widely adopted, the suitable Esterification method of substituted alcohols.
Embodiment
By describing technology contents of the present invention, structural attitude in detail, being realized object and effect, be explained in detail below in conjunction with embodiment.
The design of most critical of the present invention is: adopt (methyl) vinylformic acid of perfect atomic economic response and iso-butylene under an acidic catalyst effect, carry out addition reaction generation (methyl) tert-butyl acrylate.
The invention provides one (methyl) tert-butyl acrylate preparation method, comprise mol ratio be (methyl) vinylformic acid of 1.0:1.0 ~ 5.0:1.0 and iso-butylene together with an acidic catalyst under the condition of 40 DEG C ~ 120 DEG C temperature, 1.0MPa ~ 5.0MPa reaction pressure with volume space velocity 0.5/h ~ 5.0/h lactate synthesis (methyl) tert-butyl acrylate of iso-butylene.
From foregoing description, beneficial effect of the present invention is: pioneering olefin(e) acid addition esterification process produces (methyl) tert-butyl acrylate, by carrying out addition reaction generation (methyl) tert-butyl acrylate with (methyl) vinylformic acid and iso-butylene under the acid catalyst action of positively charged ion.This technique belongs to desirable atomic economy reaction, both simplifies operational path, and whole appliance arrangement quantity is also less, and in addition, whole preparation process no coupling product is low-carbon environment-friendly technique, and the acid catalyst wherein adopted is nontoxic, and production process is environmentally friendly.Therefore olefin(e) acid addition esterification process can be widely adopted, the suitable Esterification method of substituted alcohols.
Embodiment 1:
In above-mentioned, described an acidic catalyst is strongly acidic ion-exchange resin catalyst.
Embodiment 2:
In above-mentioned, described strongly acidic ion-exchange resin catalyst is macropore sulfonic acid ion exchange resin.
Embodiment 3:
In above-mentioned, described macropore sulfonic acid ion exchange resin is the poly styrene polymer of divinylbenzene crosslink.
Embodiment 4:
In above-mentioned, the poly styrene polymer of described divinylbenzene crosslink is at least one in Amberlyst-15 (A-15), Amberlyst-35 (A-35), LewatitK2631, Bayer K2631, D-72, S-54, D005, Z/H00, QRE type resin catalyst.
In the present embodiment, Amberlyst-15 (A-15), Amberlyst-35 (A-35), LewatitK2631, Bayer K2631 type are the external resin type catalyst mostly adopted.D-72, S-54, D005, Z/H00, QRE type resin catalyst state then researches and develops voluntarily for China.
Embodiment 5:
Through the great many of experiments of applicant in conjunction with the comparison repeatedly of result, best: in above-mentioned, the volume space velocity of described iso-butylene is 1.0/h ~ 2.0/h.
Embodiment 6:
Through the great many of experiments of applicant in conjunction with the comparison repeatedly of result, best: in above-mentioned, the mol ratio of described (methyl) vinylformic acid and iso-butylene is 1.0:1.0 ~ 3.0:1.0.
Embodiment 7:
Through the great many of experiments of applicant in conjunction with the comparison repeatedly of result, best: in above-mentioned, the temperature of described reaction conditions is 50 DEG C ~ 70 DEG C, and reaction pressure is 1.5MPa ~ 2.5MPa.
The concrete example of preparation method:
A kind of (methyl) tert-butyl acrylate preparation method, comprises step:
S1) an acidic catalyst is filled in reactor;
S2) (methyl) vinylformic acid is added;
S3) iso-butylene is added with volume space velocity 0.5/h ~ 5.0/h;
S4) reaction pressure is controlled at 1.0MPa ~ 5.0MPa;
S5) temperature is controlled at 40 DEG C ~ 120 DEG C;
S6) control iso-butylene and acrylic acid raw materials components mole ratio are at 1.0:1.0 ~ 5.0:1.0;
S7) (methyl) tert-butyl acrylate is obtained after stable reaction certain hour.
Present invention also offers another kind (methyl) tert-butyl acrylate preparation method, comprise by (methyl) vinylformic acid and liquefied petroleum gas (LPG) together with an acidic catalyst under the condition of 40 DEG C ~ 120 DEG C temperature, 1.0MPa ~ 5.0MPa reaction pressure with volume space velocity 0.5/h ~ 5.0/h lactate synthesis (methyl) tert-butyl acrylate of iso-butylene; The mol ratio of the iso-butylene in described (methyl) vinylformic acid and liquefied petroleum gas (LPG) is 1.0:1.0 ~ 5.0:1.0;
Commonly known, in refining of petroleum or petrochemical process, the a certain amount of liquefied petroleum gas (LPG) containing hydrocarbon mixture of by-product, at present to the application of liquefied petroleum gas (LPG), or produces the blend component of stop bracket gasoline by processes such as superimposed, alkylation, aromizing or etherificates; Or directly it can be used as fuel to burn.The former is for the purpose of the blend component producing stop bracket gasoline, and the latter wastes a large amount of low-carbon alkene resources especially.This preparation method then can carry out the preparation of (methyl) tert-butyl acrylate using the liquefied petroleum gas (LPG) in refining of petroleum one-tenth or petrochemical process as raw material.From foregoing description, beneficial effect of the present invention is: the iso-butylene made full use of in the carbon four of petrochemical complex manufacturing enterprise by-product carries out addition reaction synthesis (methyl) tert-butyl acrylate with (methyl) vinylformic acid, resource utilization is 100%, raw materials cost reduces greatly, in addition technique belongs to desirable atomic economy reaction, both operational path was simplified, whole appliance arrangement quantity is also less, moreover, whole preparation process no coupling product, be low-carbon environment-friendly technique, the acid catalyst wherein adopted is nontoxic, and production process is environmentally friendly.Therefore olefin(e) acid addition esterification process can be widely adopted, the suitable Esterification method of substituted alcohols.
Embodiment 1:
In above-mentioned, described liquefied petroleum gas (LPG) comprises C4 hydrocarbon mixture (mixed c 4), and C4 hydrocarbon mixture comprises the iso-butylene that content is not less than 5%.
In the art of this patent, the iso-butylene that liquefied petroleum gas (LPG) contains is not less than 5% and can be prepared.In order to ensure good effect, preferably, the iso-butylene in liquefied petroleum gas (LPG) should be at least 15%, and best should be at least 20%.
Embodiment 2:
In above-mentioned, described an acidic catalyst is strongly acidic ion-exchange resin catalyst.
Embodiment 3:
In above-mentioned, described strongly acidic ion-exchange resin catalyst is macropore sulfonic acid ion exchange resin.
Embodiment 4:
In above-mentioned, described macropore sulfonic acid ion exchange resin is the poly styrene polymer of divinylbenzene crosslink.
Embodiment 5:
In above-mentioned, the poly styrene polymer of described divinylbenzene crosslink is at least one in Amberlyst-15 (A-15), Amberlyst-35 (A-35), LewatitK2631, Bayer K2631, D-72, S-54, D005, Z/H00, QRE type resin catalyst.
In the present embodiment, Amberlyst-15 (A-15), Amberlyst-35 (A-35), LewatitK2631, Bayer K2631 type are the external resin type catalyst mostly adopted.D-72, S-54, D005, Z/H00, QRE type resin catalyst state then researches and develops voluntarily for China.
Embodiment 6:
Through the great many of experiments of applicant in conjunction with the comparison repeatedly of result, best: in above-mentioned, the volume space velocity of described iso-butylene is 1.0/h ~ 2.0/h.
Embodiment 7:
Through the great many of experiments of applicant in conjunction with the comparison repeatedly of result, best: in above-mentioned, the mol ratio of described (methyl) vinylformic acid and iso-butylene is 1.0:1.0 ~ 3.0:1.0.
Embodiment 8:
Through the great many of experiments of applicant in conjunction with the comparison repeatedly of result, best: in above-mentioned, the temperature of described reaction conditions is 50 DEG C ~ 70 DEG C, and reaction pressure is 1.5MPa ~ 2.5MPa.
The concrete example of preparation method:
A kind of (methyl) tert-butyl acrylate preparation method, comprises step:
S1) an acidic catalyst is filled in reactor;
S2) (methyl) vinylformic acid is added;
S3) liquefied petroleum gas (LPG) is added with volume space velocity 0.5/h ~ 5.0/h;
S4) reaction pressure is controlled at 1.0MPa ~ 5.0MPa;
S5) temperature is controlled at 40 DEG C ~ 120 DEG C;
S6) iso-butylene that adds in liquefied petroleum gas (LPG) and acrylic acid raw materials components mole ratio is controlled at 1.0:1.0 ~ 5.0:1.0;
S7) (methyl) tert-butyl acrylate is obtained after stable reaction certain hour
Concrete exemplifying embodiment 1:
By Z/H00 type packed catalyst in fixed-bed reactor, fixed-bed reactor are the tubular reactor of 3 series connection, reactor height 12000mm, diameter 150mm.
First enter vinylformic acid, when vinylformic acid is completely after all reactors, start into appropriate mixed c 4, iso-butylene content 21% in mixed c 4, air speed starts to control at 1/h, is controlled pressure at 2.0MPa by exhaust and reducing valve.Start preheater, the temperature of fixed-bed reactor is controlled at 50 DEG C, after temperature-stable, iso-butylene and acrylic acid raw materials components mole ratio control at 1:1.5, the recycle ratio that fixed bed adopts is 5:1, sample after 2h after stable reaction, analyze with Agilent 7820 pairs of mixed c 4s, wherein the transformation efficiency of iso-butylene is 72%.
Concrete exemplifying embodiment 2:
With under concrete exemplifying embodiment 1 simulated condition, changing temperature is 60 DEG C, and other remain unchanged, and the transformation efficiency of iso-butylene is 78%.
Concrete exemplifying embodiment 3:
With under concrete exemplifying embodiment 1 simulated condition, changing temperature is 70 DEG C, and other remain unchanged, and the transformation efficiency of iso-butylene is 69%.
Concrete exemplifying embodiment 4:
With under concrete exemplifying embodiment 1 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change pressure is 1.5MPa, and the transformation efficiency of iso-butylene is 53%.
Concrete exemplifying embodiment 5:
With under concrete exemplifying embodiment 1 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change pressure is 2.5MPa, and the transformation efficiency of iso-butylene is 46%.
Concrete exemplifying embodiment 6:
With under concrete exemplifying embodiment 1 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change sour alkene than being 1:1, the transformation efficiency of iso-butylene is 74%.
Concrete exemplifying embodiment 7:
With under concrete exemplifying embodiment 1 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change sour alkene than being 2:1, the transformation efficiency of iso-butylene is 74.5%.
Concrete exemplifying embodiment 8:
With under concrete exemplifying embodiment 1 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change sour alkene than being 2.5:1, the transformation efficiency of iso-butylene is 76%.
Concrete exemplifying embodiment 9:
With under concrete exemplifying embodiment 1 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change sour alkene than being 3:1, the transformation efficiency of iso-butylene is 78%.
Concrete exemplifying embodiment 10:
By Z/H00 packed catalyst in fixed-bed reactor, fixed-bed reactor are the tubular reactor of 3 series connection, reactor height 12000mm, diameter 150mm.
First (methyl) vinylformic acid is entered, when (methyl) vinylformic acid is completely after all reactors, start into appropriate mixed c 4, wherein containing iso-butylene is 21%, air speed starts to control at 1/h, is controlled pressure at 2.0MPa by exhaust and reducing valve.Start preheater, the temperature of fixed-bed reactor is controlled at 50 DEG C, after temperature-stable, the raw materials components mole ratio of iso-butylene and methacrylic acid controls at 1:1.5, the recycle ratio that fixed bed adopts is 5:1, sample after 2h after stable reaction, analyze with Agilent 7820 pairs of mixed c 4s, wherein the transformation efficiency of iso-butylene is 47%.Specifically see following comparative's table 1.
| Raw material | Catalyzer | Pressure (Mpa) | Temperature (DEG C) | Olefin(e) acid ratio (mol ratio) | Isobutene conversion |
| Vinylformic acid+iso-butylene | ZH-100 | 2 | 50 | 1∶1.5 | 72％ |
| Vinylformic acid+iso-butylene | ZH-100 | 2 | 60 | 1∶1.5 | 78％ |
| Vinylformic acid+iso-butylene | ZH-100 | 2 | 70 | 1∶1.5 | 69％ |
| Vinylformic acid+iso-butylene | ZH-100 | 1.5 | 60 | 1∶1.5 | 53％ |
| Vinylformic acid+iso-butylene | ZH-100 | 2.5 | 60 | 1∶1.5 | 46％ |
| Vinylformic acid+iso-butylene | ZH-100 | 2.5 | 60 | 1∶1 | 74％ |
| Vinylformic acid+iso-butylene | ZH-100 | 2 | 60 | 2∶1 | 74.5％ |
| Vinylformic acid+iso-butylene | ZH-100 | 2 | 60 | 2.5∶1 | 76％ |
| Vinylformic acid+iso-butylene | ZH-100 | 2 | 60 | 3∶1 | 78％ |
| Methacrylic acid+iso-butylene | ZH-100 | 2 | 50 | 1∶1.5 | 47％ |
| Methacrylic acid+iso-butylene | ZH-100 | 2 | 60 | 1∶1.5 | 55％ |
| Methacrylic acid+iso-butylene | ZH-100 | 2 | 70 | 1∶1.5 | 53％ |
| Methacrylic acid+iso-butylene | ZH-100 | 1.5 | 60 | 1∶1.5 | 49％ |
| Methacrylic acid+iso-butylene | ZH-100 | 2.5 | 60 | 1∶1.5 | 51％ |
| Methacrylic acid+iso-butylene | ZH-100 | 2 | 60 | 1∶1 | 44％ |
| Methacrylic acid+iso-butylene | ZH-100 | 2 | 60 | 2∶1 | 56％ |
| Methacrylic acid+iso-butylene | ZH-100 | 2 | 60 | 2.5∶1 | 50％ |
| Methacrylic acid+iso-butylene | ZH-100 | 2 | 60 | 3∶1 | 58％ |
Contrast table 1
Concrete exemplifying embodiment 11:
With under concrete exemplifying embodiment 10 simulated condition, changing temperature is 60 DEG C, and other remain unchanged, and the transformation efficiency of iso-butylene is 55%.
Concrete exemplifying embodiment 12:
With under concrete exemplifying embodiment 10 simulated condition, changing temperature is 70 DEG C, and other remain unchanged, and the transformation efficiency of iso-butylene is 53%.
Concrete exemplifying embodiment 13:
With under concrete exemplifying embodiment 10 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change pressure is 1.5MPa, and the transformation efficiency of iso-butylene is 49%.
Concrete exemplifying embodiment 14:
With under concrete exemplifying embodiment 10 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change pressure is 2.5MPa, and the transformation efficiency of iso-butylene is 51%.
Concrete exemplifying embodiment 15:
With under concrete exemplifying embodiment 10 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change sour alkene than being 1:1, the transformation efficiency of iso-butylene is 44%.
Concrete exemplifying embodiment 16:
With under concrete exemplifying embodiment 10 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change sour alkene than being 2:1, the transformation efficiency of iso-butylene is 56%.
Concrete exemplifying embodiment 17:
With under concrete exemplifying embodiment 10 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change sour alkene than being 2.5:1, the transformation efficiency of iso-butylene is 50%.
Concrete exemplifying embodiment 18:
With under concrete exemplifying embodiment 10 simulated condition, the temperature of fixed-bed reactor controlled at 60 DEG C, change sour alkene than being 3:1, the transformation efficiency of iso-butylene is 58%.
The scheme of concrete exemplifying embodiment 1-18 and isobutene conversion compare see shown in above-mentioned contrast table 1.
Contrast exemplifying embodiment 1:
Throw vinylformic acid 72kg, stopper 160g, toluene 20kg, tosic acid 5kg, in the enamel reaction still of 500L, be heated to about 80 DEG C, starts to drip trimethyl carbinol 148kg, and carry out esterification dehydration 12h, during dehydration, temperature controls at 80-120 DEG C.It is 5% that sampling detects tert-butyl acrylate content, and the transformation efficiency of the trimethyl carbinol is 10.4%.
Contrast exemplifying embodiment 2:
Throw methacrylic acid 86kg, stopper 160g, toluene 20kg, tosic acid 5kg, in the enamel reaction still of 500L, be heated to about 80 DEG C, drips trimethyl carbinol 148kg, and carry out esterification dehydration 12h, during dehydration, temperature controls at 80-120 DEG C.Then sampling detects the transformation efficiency 8.6% of Tert-butyl Methacrylate content 4% and the trimethyl carbinol.
The comparison of contrast exemplifying embodiment 1,2 is see shown in contrast table 2:
Contrast table 2
Can be learnt by above embodiment table and comparative example table, the method of standby (methyl) tert-butyl acrylate of olefin(e) acid legal system is practicable, under certain temperature, pressure condition, acid alkene mol ratio is larger, isobutene conversion is higher, in temperature, under acid alkene mol ratio certain condition, pressure is larger, isobutene conversion is larger, and compared with it prepares (methyl) tert-butyl acrylate with existing acid alcohol esterification process, its transformation efficiency is high, yield is also high, is the method for standby (methyl) tert-butyl acrylate of a kind of economic environment-friendlyenergy.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. (methyl) tert-butyl acrylate preparation method, is characterized in that: comprise mol ratio be (methyl) vinylformic acid of 1.0:1.0 ~ 5.0:1.0 and iso-butylene together with an acidic catalyst under the condition of 40 DEG C ~ 120 DEG C temperature, 1.0MPa ~ 5.0MPa reaction pressure with volume space velocity 0.5/h ~ 5.0/h lactate synthesis (methyl) tert-butyl acrylate of iso-butylene.
2. (methyl) tert-butyl acrylate preparation method, is characterized in that: comprise by (methyl) vinylformic acid and liquefied petroleum gas (LPG) together with an acidic catalyst under the condition of 40 DEG C ~ 120 DEG C temperature, 1.0MPa ~ 5.0MPa reaction pressure with volume space velocity 0.5/h ~ 5.0/h lactate synthesis (methyl) tert-butyl acrylate of iso-butylene; The mol ratio of the iso-butylene in described (methyl) vinylformic acid and liquefied petroleum gas (LPG) is 1.0:1.0 ~ 5.0:1.0.
3., as (methyl) tert-butyl acrylate preparation method that claim 2 is stated, it is characterized in that: described liquefied petroleum gas (LPG) comprises C4 hydrocarbon mixture, C4 hydrocarbon mixture comprises the iso-butylene that content is not less than 5%.
4. (methyl) tert-butyl acrylate preparation method as claimed in claim 1 or 2, is characterized in that: described an acidic catalyst is strongly acidic ion-exchange resin catalyst.
5. (methyl) tert-butyl acrylate preparation method as claimed in claim 4, is characterized in that: described strongly acidic ion-exchange resin catalyst is macropore sulfonic acid ion exchange resin.
6. (methyl) tert-butyl acrylate preparation method as claimed in claim 5, is characterized in that: described macropore sulfonic acid ion exchange resin is the poly styrene polymer of divinylbenzene crosslink.
7. (methyl) tert-butyl acrylate preparation method as claimed in claim 6, is characterized in that: the poly styrene polymer of described divinylbenzene crosslink is at least one in Amberlyst-15 (A-15), Amberlyst-35 (A-35), LewatitK2631, Bayer K2631, D-72, S-54, D005, Z/H00, QRE type resin catalyst.
8. (methyl) tert-butyl acrylate preparation method as claimed in claim 1 or 2, is characterized in that: the volume space velocity of described iso-butylene is 1.0/h ~ 2.0/h.
9. (methyl) tert-butyl acrylate preparation method as claimed in claim 1 or 2, is characterized in that: the mol ratio of described (methyl) vinylformic acid and iso-butylene is 1.0:1.0 ~ 3.0:1.0.
10. (methyl) tert-butyl acrylate preparation method as claimed in claim 1 or 2, is characterized in that: the temperature of described reaction conditions is 50 DEG C ~ 70 DEG C, and reaction pressure is 1.5MPa ~ 2.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410448289.3A CN104276948A (en) | 2014-09-04 | 2014-09-04 | Preparation method of tert-butyl (methyl)acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410448289.3A CN104276948A (en) | 2014-09-04 | 2014-09-04 | Preparation method of tert-butyl (methyl)acrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104276948A true CN104276948A (en) | 2015-01-14 |
Family
ID=52252355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410448289.3A Pending CN104276948A (en) | 2014-09-04 | 2014-09-04 | Preparation method of tert-butyl (methyl)acrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104276948A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844455A (en) * | 2015-04-13 | 2015-08-19 | 徐德良 | Method used for catalyzed synthesis of tert-butyl acrylate |
| CN105601510A (en) * | 2015-12-21 | 2016-05-25 | 山东金城医药化工股份有限公司 | Catalytic synthesis method of tert-butyl alpha-bromoisobutyrate by using cation exchange resin |
| CN108620094A (en) * | 2017-03-21 | 2018-10-09 | 广州凌玮科技股份有限公司 | A kind of preparation method of four esterification catalyst sulfonation silica gel of carbon |
| CN110270323A (en) * | 2018-03-15 | 2019-09-24 | 上海华谊新材料有限公司 | The preparation method of (methyl) tert-butyl acrylate |
| CN110950760A (en) * | 2019-12-11 | 2020-04-03 | 福州大学 | Process for synthesizing tert-butyl acrylate |
| CN114213244A (en) * | 2022-01-10 | 2022-03-22 | 苏州和创化学有限公司 | Method for efficiently synthesizing tert-butyl methacrylate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3037052A (en) * | 1959-04-29 | 1962-05-29 | Rohm & Haas | Catalyzing reactions with cation exchange resin |
| US6242640B1 (en) * | 1999-10-07 | 2001-06-05 | Arco Chemical Technology, L.P. | Tertiary alkyl ester preparation using large-pore zeolite catalysts |
| CN101155771A (en) * | 2005-02-07 | 2008-04-02 | 三菱丽阳株式会社 | Method for synthesizing t-butyl (meth)acrylate |
-
2014
- 2014-09-04 CN CN201410448289.3A patent/CN104276948A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3037052A (en) * | 1959-04-29 | 1962-05-29 | Rohm & Haas | Catalyzing reactions with cation exchange resin |
| US6242640B1 (en) * | 1999-10-07 | 2001-06-05 | Arco Chemical Technology, L.P. | Tertiary alkyl ester preparation using large-pore zeolite catalysts |
| CN101155771A (en) * | 2005-02-07 | 2008-04-02 | 三菱丽阳株式会社 | Method for synthesizing t-butyl (meth)acrylate |
Non-Patent Citations (1)
| Title |
|---|
| 陈中华: "酸烯法合成乙酸叔丁酯的工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 June 2013 (2013-06-15), pages 014 - 113 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844455A (en) * | 2015-04-13 | 2015-08-19 | 徐德良 | Method used for catalyzed synthesis of tert-butyl acrylate |
| CN104844455B (en) * | 2015-04-13 | 2016-06-22 | 徐德良 | A kind of technique catalyzing and synthesizing tert-butyl acrylate |
| CN105601510A (en) * | 2015-12-21 | 2016-05-25 | 山东金城医药化工股份有限公司 | Catalytic synthesis method of tert-butyl alpha-bromoisobutyrate by using cation exchange resin |
| CN108620094A (en) * | 2017-03-21 | 2018-10-09 | 广州凌玮科技股份有限公司 | A kind of preparation method of four esterification catalyst sulfonation silica gel of carbon |
| CN108620094B (en) * | 2017-03-21 | 2021-01-05 | 广州凌玮科技股份有限公司 | Preparation method of carbon tetra-esterification catalyst sulfonated silica gel |
| CN110270323A (en) * | 2018-03-15 | 2019-09-24 | 上海华谊新材料有限公司 | The preparation method of (methyl) tert-butyl acrylate |
| CN110270323B (en) * | 2018-03-15 | 2023-06-02 | 上海华谊新材料有限公司 | Preparation method of tert-butyl (methyl) acrylate |
| CN110950760A (en) * | 2019-12-11 | 2020-04-03 | 福州大学 | Process for synthesizing tert-butyl acrylate |
| CN110950760B (en) * | 2019-12-11 | 2021-09-24 | 福州大学 | Process for synthesizing tert-butyl acrylate |
| CN114213244A (en) * | 2022-01-10 | 2022-03-22 | 苏州和创化学有限公司 | Method for efficiently synthesizing tert-butyl methacrylate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104276948A (en) | Preparation method of tert-butyl (methyl)acrylate | |
| CN101332432B (en) | Load-type solid acid catalyst with selective oligomerisation for mixed C4 | |
| CN104030919B (en) | A kind of processing method of continuous processing preparation (methyl) tert-butyl acrylate | |
| CN1603290A (en) | Process for the preparation of tert.-butanol | |
| CN102659514A (en) | Method for producing sec-butyl alcohol | |
| CN107434762A (en) | A kind of preparation of ethylene glycol mono-tert-butyl ether and process for purification | |
| CN102344364A (en) | Method for producing sec-butyl acetate by synthesizing acetic acid and mixed C4 | |
| CN104478644A (en) | Method for preparing isobutylene from tert-butanol | |
| CN103073426B (en) | A kind of take storng-acid cation exchange resin as the preparation technology of catalyst synthesizing propylene tert-butyl acrylate | |
| CN104311390A (en) | Method for synthesizing sec-butyl alcohol | |
| CN106986753A (en) | A kind of preparation method of glycerine tertbutyl ether | |
| CN102924271B (en) | Method for producing tert-butyl ester compound by esterification, rectification and coupling of organic carboxylic acid and isobutene | |
| CN102757341A (en) | Preparation method of ethyl acetate and/or isopropyl acetate | |
| CN102911043B (en) | Method for preparing sec-butyl acetate by using acetic acid and butane | |
| CN104250204B (en) | A kind of complex etherified technique | |
| CN103086830B (en) | Production method of butadiene | |
| CN203007176U (en) | Alcoholysis device system for preparing dioctyl terephthalate from Dacron wastes | |
| CN103342640B (en) | Method for synthesizing secbutyl acetate by acetic acid and mixed C4 | |
| CN103508884B (en) | One utilizes C after ether 4cut prepares the method for 2-butyl acetate | |
| CN103739423A (en) | Process for recovering C5 from etherified liquefied gas | |
| CN103787843B (en) | A kind of method preparing tert amyl methyl ether(TAME) | |
| CN110075920A (en) | A kind of preparation method and applications of multi-stage porous silicon ball load heteropoly phosphorus molybdenum tungstic acid catalyst | |
| CN204897786U (en) | Methyl tert butyl ether production facility | |
| CN104707591A (en) | Oxide catalyst for converting ethanol to prepare isobutene and preparation method thereof | |
| CN103965007B (en) | The method of mixed c 4 volume increase divinyl |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150114 |