CN100349852C - A (methyl) higher aliphatic acrylate preparation method - Google Patents
A (methyl) higher aliphatic acrylate preparation method Download PDFInfo
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- CN100349852C CN100349852C CNB2005100291741A CN200510029174A CN100349852C CN 100349852 C CN100349852 C CN 100349852C CN B2005100291741 A CNB2005100291741 A CN B2005100291741A CN 200510029174 A CN200510029174 A CN 200510029174A CN 100349852 C CN100349852 C CN 100349852C
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Abstract
The present invention provides a method for preparing higher (methyl) acrylic acid fatty alcohol ester. Under the existence of at least one inhibitor and entrainer, (methyl) acrylic acid and higher fatty alcohol (above dodecyl alcohol), and higher (methyl) acrylic acid fatty alcohol ester is synthesized through direct esterification under the action of acidic catalysts. Redundant entrainers and water of reaction products are removed through post-treatment, pressure reduction and distillation after esterification reaction is completed, the purity of products is larger than 98%, acidity is smaller than 0.03%, and colority is smaller than 100(APHA). The method provided by the present invention has the advantages of simple operation high yield and good quality of products, and can realize industrialization production.
Description
Technical field
The present invention relates to the preparation method of a kind of (methyl) vinylformic acid high fatty alcohol ester, relate in particular to the synthetic and method of purification of a kind of (methyl) vinylformic acid high fatty alcohol ester.
Background technology
(methyl) vinylformic acid high fatty alcohol ester, or be called (methyl) long-chain aliphatic acrylate, be important fine chemical product of a class and high molecular polymerization monomer, contain hydrophobicity long-chain fat hydrocarbon skeleton, have the characteristics of anti-marquis, water-fast, low cohesiveness, flexibility, rigid, shock resistance, purposes is widely all arranged in fields such as coating, pour point depressant, plastics, papermaking and leather, chemical industry.(methyl) vinylformic acid high fatty alcohol ester can improve the water tolerance of emulsion as one of monomer of polyacrylate dispersion; The multipolymer (PAHE) of (methyl) vinylformic acid high fatty alcohol ester or (methyl) vinylformic acid high fatty alcohol ester and other monomeric multipolymer are the important pour point depressant for crude oil of a class, can improve the low-temperature fluidity of crude oil, use in fields such as exploitation mainly defeated at the pipeline collection of crude oil, viscous crude, can be used as processed oil stream again and change agent; The homopolymer of (methyl) vinylformic acid high fatty alcohol ester or can be used as plastic plasticizer with monomeric multipolymers such as vinylbenzene, maleic anhydrides, be used as the paper coating agent at paper industry, leather industry is as leather tanning agent, also can be used as the auxiliary agent of makeup, daily necessities and water treatment scale agent etc.
(methyl) vinylformic acid lower aliphatic alcohol ester such as methyl esters, ethyl ester, butyl ester and 2-ethylhexyl etc. adopt ester-interchange method or direct esterification method synthetic usually.But during with ester-interchange method preparation (methyl) vinylformic acid high fatty alcohol ester, the raw material lower member ester uses (methyl) methyl acrylate mostly, because its boiling point is low, reaction can only be carried out at a lower temperature, makes the reaction times lengthening; In addition, the copolymerization or the homopolymerization of (methyl) methyl acrylate and (methyl) vinylformic acid high fatty alcohol ester can make the productive rate of (methyl) vinylformic acid high fatty alcohol ester reduce, and therefore general stopper add-on is more, consider that from cost and aftertreatment two aspects this method is not too suitable.At present, the domestic patent report that does not almost synthesize the aspect about (methyl) vinylformic acid high fatty alcohol ester.
The invention provides a kind of is raw material with (methyl) vinylformic acid and high fatty alcohol, by the method for synthetic (methyl) vinylformic acid high fatty alcohol ester of direct esterification.Method provided by the invention is simple to operate, the yield height, and good product quality can be realized suitability for industrialized production.
Summary of the invention
The method that the purpose of this invention is to provide a kind of (methyl) vinylformic acid of preparation with high yield high fatty alcohol ester.The preparation method of (methyl) provided by the invention vinylformic acid high fatty alcohol ester comprises:
(1) in the presence of at least a stopper and entrainer, be raw material with (methyl) vinylformic acid and high fatty alcohol, under an acidic catalyst effect, (methyl) vinylformic acid high fatty alcohol ester is synthesized in direct esterification.Wherein, (methyl) vinylformic acid is meant acrylic or methacrylic acid; High fatty alcohol is meant that carbonatoms is 12 and above Fatty Alcohol(C12-C14 and C12-C18); Stopper is any or their mixture in Resorcinol, hydroquinone monomethyl ether, thiodiphenylamine, neutralized verdigris, copper sulfate, the copper dibutyldithiocarbamate, preferred Resorcinol or copper sulfate or neutralized verdigris, its consumption is 0.1～5.0wt% of reaction-ure mixture, preferred 0.2～2.0wt%; An acidic catalyst is any or their mixture in sulfuric acid, phosphoric acid, hydrochloric acid, tosic acid, methylsulfonic acid, the sulfonic acid type storng-acid cation exchange resin, preferred methylsulfonic acid or tosic acid, its consumption is 0.1～5.0wt% of reaction-ure mixture, preferred 0.5～2.0wt%; Need the adding entrainer will react the water that generates in the reaction process and shift out reaction system, entrainer is any or their mixture in benzene, toluene, hexanaphthene, tetracol phenixin, chloroform, Skellysolve A, the normal hexane, preferred toluene or hexanaphthene, its consumption is 1～60wt% of reaction-ure mixture, preferred 20～40wt%; The mol ratio of (methyl) vinylformic acid and high fatty alcohol is 0.5～5.0, preferred 1.0～2.0; Esterification reaction temperature is 80～150 ℃, preferred 100～135 ℃; Reaction time of esterification is 1～20h, preferred 5～10h.
(2) after esterification finished, reaction product was handled with sodium hydroxide solution earlier under 60～70 ℃ condition, handled to neutral rectification under vacuum then again with pure water.Wherein, concentration of sodium hydroxide solution is 1～20wt%, preferred 5～10wt%; The rectification under vacuum temperature is 35～70 ℃, preferred 40～60 ℃; Vacuum tightness is 5～100kPa, preferred 30～50kPa.
Through preparation method of the present invention, can get purity greater than 98%, acidity less than 0.03% and colourity APHA less than 100 product.
Embodiment
To come content of the present invention is further described with specific embodiment below, but scope of the present invention be confined to embodiment.
Reaction yield is benchmark with alcohol in following examples.
Embodiment 1～5
In having the reactor of water trap, add high fatty alcohol, after 75 ℃ of following fusions, add vinylformic acid, entrainer hexanaphthene, catalyzer tosic acid and stopper neutralized verdigris, the mol ratio of vinylformic acid/high fatty alcohol is 1.2: 1, the hexanaphthene consumption is reaction-ure mixture 30wt%, the tosic acid consumption is the 1.2wt% of reaction-ure mixture, and the neutralized verdigris consumption is the 0.5wt% of reaction-ure mixture.Stir heat temperature raising down, stirring velocity is that 300r/min, temperature of reaction are 115 ℃, behind the reaction 6.5h is that the reaction yield of benchmark the results are shown in Table 1 with alcohol.
The different high fatty alcohols of table 1 are the reaction yield of raw material
| Embodiment | 1 | 2 | 3 | 4 | 5 |
| The Fatty Alcohol(C12-C14 and C12-C18) reaction yield, % | Lauryl alcohol 95.9 | Tetradecyl alcohol 95.0 | Hexadecanol 94.8 | Stearyl alcohol 93.8 | Eicosanol 90.9 |
Embodiment 6～8
With the stearyl alcohol is raw material acrylic acid synthesizing octadecyl ester, and reaction conditions is with embodiment 1, and the reaction result that changes the stopper kind sees Table 2.
Table 2 stopper kind is to the influence of octadecyl acrylate reaction yield
| Embodiment | 4 | 6 | 7 | 8 |
| The stopper reaction yield, % | Neutralized verdigris 93.8 | Copper sulfate 97.3 | Resorcinol 91.2 | Thiodiphenylamine 78.3 |
Embodiment 9～12
Raw material and reaction conditions are with embodiment 6, and the reaction result that changes the stopper consumption sees Table 3.
Table 3 stopper consumption is to the influence of octadecyl acrylate reaction yield
| Embodiment | 6 | 9 | 10 | 11 | 12 |
| The stopper consumption, wt% reaction yield, % | 0.5 97.3 | 0.2 95.2 | 0.7 96.8 | 1.0 95.8 | 2.0 93.6 |
Embodiment 13～16
Raw material and reaction conditions are with embodiment 6, and the reaction result that changes catalyst levels sees Table 4.
Table 4 catalyst levels is to the influence of octadecyl acrylate reaction yield
| Embodiment | 6 | 13 | 14 | 15 | 16 |
| Catalyst levels, wt% reaction yield, % | 1.2 97.3 | 0.3 88.0 | 0.8 95.9 | 1.5 97.4 | 2.0 96.8 |
Embodiment 17～20
Raw material and reaction conditions change the mol ratio of vinylformic acid and stearyl alcohol with embodiment 6, the results are shown in Table 5.
Table 5 proportioning raw materials is to the influence of octadecyl acrylate reaction yield
| Embodiment | 6 | 17 | 18 | 19 | 20 |
| Vinylformic acid/stearyl alcohol molar ratio reaction yield, % | 1.2 97.3 | 1.0 92.1 | 1.1 95.7 | 1.5 97.6 | 2.0 97.8 |
Embodiment 21～24
Raw material and reaction conditions are with embodiment 6, and the reaction result that changes the entrainer kind sees Table 6.
Table 6 entrainer kind is to the influence of octadecyl acrylate reaction yield
| Embodiment | 6 | 21 | 22 | 23 | 24 |
| The entrainer reaction yield, % | Hexanaphthene 97.3 | Toluene 95.1 | Tetracol phenixin 88.7 | Normal hexane 90.6 | Benzene 91.8 |
Embodiment 25～28
Raw material and reaction conditions are with embodiment 6, and the reaction result that changes the entrainer consumption sees Table 7.
Table 7 entrainer consumption is to the influence of octadecyl acrylate reaction yield
| Embodiment | 6 | 25 | 26 | 27 | 28 |
| The entrainer consumption, wt% reaction yield, % | 30 97.3 | 10 90.7 | 20 95.3 | 40 97.8 | 50 96.9 |
Embodiment 29～31
Raw material and reaction conditions change temperature of reaction with embodiment 6, and reaction result is as shown in table 8.
Table 8 temperature of reaction is to the influence of octadecyl acrylate reaction yield
| Embodiment | 6 | 29 | 30 | 31 |
| Temperature of reaction, ℃ reaction yield, % | 115 97.3 | 105 93.9 | 130 95.8 | 150 94.2 |
Embodiment 32～36
Raw material and reaction conditions are with embodiment 6.The crude product that reaction obtains neutralizes with sodium hydroxide solution under 60 ℃, washes with water to water to be neutral again; Remaining hexanaphthene and water are removed in underpressure distillation under 50 ℃ of temperature, vacuum tightness 30kPa then, obtain vinylformic acid stearyl alcohol ester product.Every index of the finished product sees Table 9.
Table 9 aftertreatment is to the influence of the every index of the finished product
| Embodiment | 32 | 33 | 34 | 35 | 36 |
| Naoh concentration, wt% final product total recovery, % final product purity, % acidity (% is in vinylformic acid) colourity (APHA) | 4.0 91.4.0 98.0 0.026 is greater than 200 | 6.0 92.6 98.2 0.025 100 | 8.0 93.8 98.6 0.025 less than 100 | 10.0 92.8 98.6 0.025 less than 100 | 15.0 82.9 98.8 0.024 less than 100 |
Embodiment 37
In having the reactor of water trap, add stearyl alcohol, after 75 ℃ of following fusions, add methacrylic acid, hexanaphthene, tosic acid and stopper, the mol ratio of methacrylic acid/stearyl alcohol is 1.3, entrainer hexanaphthene consumption is the 40wt% of reaction-ure mixture, catalyzer tosic acid consumption is the 1.2wt% of reaction-ure mixture, and stopper copper sulfate consumption is the 0.5wt% of reaction-ure mixture.Stir heat temperature raising down, the control stirring velocity is that 300r/min, temperature of reaction are 120 ℃, stopped reaction behind the reaction 8.0h, and reaction yield is 95.2%.Reacting coarse product uses the alkali lye of 8wt% to neutralize down at 70 ℃, washes with water to water to be neutral again; Be 60 ℃ in temperature then, vacuum tightness is that remaining hexanaphthene and water are removed in underpressure distillation under the 30kPa condition, obtains methacrylic acid stearyl alcohol ester product.The yield of the finished product is 92.6%, and purity is 98.3%, and acidity (in methacrylic acid) is 0.028%, and colourity is less than 100.
Claims (4)
1, the preparation method of a kind of (methyl) vinylformic acid high fatty alcohol ester, it is characterized in that be raw material with (methyl) vinylformic acid and carbonatoms greater than 12 high fatty alcohol, in the presence of at least a stopper and entrainer, under the effect of an acidic catalyst, (methyl) vinylformic acid high fatty alcohol ester is synthesized in direct esterification; Esterification reaction product is through aftertreatment, and entrainer and water are removed in underpressure distillation again, can get purity greater than 98%, acidity less than 0.03% and colourity APHA less than 100 product;
Stopper is Resorcinol or copper sulfate or neutralized verdigris, and entrainer is toluene or hexanaphthene, and catalyzer is methylsulfonic acid or tosic acid;
The stopper consumption is 0.1～5.0 weight % of reaction-ure mixture; The entrainer consumption is 1～60 weight % of reaction-ure mixture, and catalyst levels is 0.1～5.0 weight % of reaction-ure mixture;
The mol ratio of (methyl) vinylformic acid and high fatty alcohol is 0.5～5.0: 1, and esterification reaction temperature is 80～150 ℃, and the acetify reaction times is 1～20h;
Aftertreatment is under the condition of 60 ℃-70 ℃ of temperature, is the sodium hydroxide solution processing of 1～20 weight % with concentration, handles to neutral with pure water again, carries out underpressure distillation then under 35～70 ℃ of temperature and vacuum tightness 5～100kPa.
2, method according to claim 1 is characterized in that, the mol ratio of (methyl) vinylformic acid and high fatty alcohol is 1.0～2.0: 1, and esterification reaction temperature is 100～135 ℃, and reaction time of esterification is 5～10h.
3, method according to claim 1 is characterized in that the stopper consumption is 0.2～2.0 weight % of reaction-ure mixture, and the entrainer consumption is 20～40 weight % of reaction-ure mixture, and catalyst levels is 0.5～2.0 weight % of reaction-ure mixture.
4, method according to claim 1 is characterized in that concentration of sodium hydroxide solution is 5～10 weight %, and it is 30～50kPa with vacuum tightness that vacuum distillation temperature is 40～60 ℃.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146035A (en) * | 2010-11-24 | 2011-08-10 | 天津市天骄辐射固化材料有限公司 | Method for preparing lauryl methacrylate |
| CN102229529B (en) * | 2011-05-11 | 2013-12-04 | 华诺森（武汉）生物医药技术有限公司 | Preparation method of (methyl) crylic acid phenylethanol ester compounds |
| CN102633633B (en) * | 2012-03-31 | 2014-05-14 | 江苏利田科技股份有限公司 | Pollution-free production method of lauryl alcohol acrylate, hexadecanol acrylate or stearyl alcohol acrylate |
| CN103642469B (en) * | 2013-12-12 | 2016-03-30 | 中国石油集团渤海钻探工程有限公司 | The drilling fluid preparation method of low-freezing lubricant |
| CN104710560B (en) * | 2013-12-13 | 2017-06-06 | 中国石油天然气集团公司 | A kind of dicyclopentadiene and Long Chain Alkyl Acrylate polymer pour point depressant for crude oil |
| CN104557539A (en) * | 2014-12-23 | 2015-04-29 | 安徽助成信息科技有限公司 | Method for separating methyl acrylate (MA) from methyl propionate (MP) |
| CN108821968A (en) * | 2018-06-28 | 2018-11-16 | 西北大学 | Acid resin in situ catalyzes and synthesizes the preparation method of acrylic acid high-carbon-alkyl |
| CN109912411A (en) * | 2019-01-17 | 2019-06-21 | 克拉玛依市正诚有限公司 | Octadecyl alcolol methylpropionate and preparation method thereof, water-soluble thickener and preparation method thereof |
| CN109608332A (en) * | 2019-01-18 | 2019-04-12 | 西安优耐特容器制造有限公司 | The method for being catalyzed continuous 14 ester of acrylic acid synthesizing using microwave-microreactor |
| CN109678717A (en) * | 2019-01-18 | 2019-04-26 | 西安优耐特容器制造有限公司 | A method of utilizing microchannel consersion unit acrylic acid synthesizing high-carbon ester |
| CN112608248A (en) * | 2020-12-16 | 2021-04-06 | 无锡海特圣大光电材料科技有限公司 | Method for synthesizing N, N-dimethylaminopropyl acrylamide by decarboxylation |
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| JPS61176555A (en) * | 1985-01-30 | 1986-08-08 | Nippon Oil & Fats Co Ltd | Production of acrylic ester or methacrylic ester |
| CN1060297A (en) * | 1991-08-15 | 1992-04-15 | 中国石油天然气总公司胜利设计院 | The preparation method of waxy crude oil pour point depressant |
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