CN1511859A - Lissapol N(methyl) propenoic acid ester and its preparation and use - Google Patents
Lissapol N(methyl) propenoic acid ester and its preparation and use Download PDFInfo
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Abstract
The present invention relates to the preparation and use of alkylphenol ethoxylate (methyl) acrylic ester. The preparation is preferably a ester exchange reaction process including azeotropic dewatering of the mixture of alkylphenol ethoxylate and acrylic ester or methyl acrylic ester in the presence of azeotropic solvent and polymerization inhibitor, ester exchange reaction in the presence of catalyst, separating and recovering azeotropic solvent and acrylic ester or methyl acrylic ester to obtain alkylphenol ethoxylate (methyl) acrylic ester. The technological process is simple and has no polymerization of the material in the reactor and separating tower, good product appearance and alkylphenol ethoxylate converting rate up to 80-95 %.
Description
Technical field
The present invention relates to a kind of ester product and preparation technology and purposes, particularly alkylphenol polyoxyethylene (methyl) acrylate and preparation and purposes.
Background technology
As everyone knows, alkylphenol polyoxyethylene is a kind of tensio-active agent, it not only has lipophilic group (alkyl phenolic group) and hydrophilic radical (polyoxyethylene group), and molecular polarity is along with ethylene oxide group number increase and decrease in the molecule, the HLB value can be adjusted as required, is purposes nonionic surface active agent the most widely in the world at present.But the molecular weight of alkylphenol polyoxyethylene is less, and water-soluble better, this has also determined its use occasion to be subjected to certain restriction.As when being used for material such as fiber surperficial, surface bonding power is poor, can be because of former thereby loss of performance such as washing, frictions.
The alkylphenol polyoxyethylene molecule has terminal hydroxy group, can carry out a lot of chemical reactions, utilizes this point to carry out chemical modification to it.Be that raw material can synthesize alkylphenol polyoxyethylene acrylate or alkylphenol polyoxyethylene methacrylic ester by esterification or transesterification reaction with alkylphenol polyoxyethylene and (methyl) vinylformic acid or (methyl) acrylate for example, both are collectively referred to as alkylphenol polyoxyethylene (methyl) acrylate.Alkylphenol polyoxyethylene (methyl) acrylate is a kind of important monomer, make the polymeric surface active agent that raw material can synthesize excellent property with it, as static inhibitor, jelling agent, thickening material, flow improver, flocculation agent, emulsifying agent, emulsion splitter and oil-displacing agent etc., can have been widely used at aspects such as chemical fibre industry, fabric treating, crude production, transportation and sewage disposals.
By literature search, still do not find the relevant report of alkylphenol polyoxyethylene (methyl) acrylate.
Summary of the invention
The present invention has obtained alkylphenol polyoxyethylene (methyl) acrylate product, high reaction conversion ratio, reaction conditions gentleness is provided, has been easy to the preparation method and use of industrialized alkylphenol polyoxyethylene (methyl) acrylate.
Alkylphenol polyoxyethylene of the present invention (methyl) acrylate product structure formula is
In the formula: R1 represent H or-CH3; R3 represents the alkyl of carbon atom number from 0 to 15; The n value gets 1～150, and n is the number of ethylene oxide repeating unit in the molecule.
The infrared spectrum of alkylphenol polyoxyethylene of the present invention (methyl) acrylate is seen Figure of description 2.
Alkylphenol polyoxyethylene of the present invention (methyl) acrylate can adopt esterification synthetic, is raw material with alkylphenol polyoxyethylene and acrylic or methacrylic acid promptly, preparation in the presence of catalyzer and stopper, and reaction equation is as follows:
In the formula: R1 represent H or-CH3; R3 represents the alkyl of carbon atom number from 0 to 15; The n value gets 1～150, and n is the number of ethylene oxide repeating unit in the molecule,
But for the ease of operation, the present invention also can adopt ester exchange process, its following steps:
A, in the presence of azeotropic solvent and stopper, the mixture azeotropic dehydration of alkylphenol polyoxyethylene and (methyl) acrylate.
B, in the presence of catalyzer, alkylphenol polyoxyethylene is carried out transesterification reaction with (methyl) acrylate in a mixture in solvent, generates the reaction mixture of alkylphenol polyoxyethylene (methyl) acrylate and alkylphenol polyoxyethylene and (methyl) acrylate.
C, from the product described in the b Separation and Recovery solvent, (methyl) acrylate.
It is as follows to adopt transesterification reaction to prepare the reaction equation of alkylphenol polyoxyethylene (methyl) acrylate among the present invention:
In the formula: R1 represent H or-CH3;
R2 represents the alkyl of carbon atom number from 1 to 8;
R3 represents the alkyl of carbon atom number from 0 to 15;
The n value gets 1～150, n is the number of ethylene oxide repeating unit in the molecule, can the different alkylphenol polyoxyethylene of selective oxidation ethylene repeating unit number prepare needed alkylphenol polyoxyethylene (methyl) acrylate as raw material according to the different of performance and purposes.In general, the n value is big more, and the polarity of product is big more, and wetting ability is good more.
Particularly importantly, in the reaction process of the present invention, selected suitable azeotropic solvent for use, the same water of this azeotropic solvent, pure azeotropic, and not with (methyl) acrylate azeotropic.Azeotropic solvent and water azeotropic before the reaction, moisture content in the system is removed rapidly, add catalyzer then and carry out transesterification reaction, azeotropic solvent and by-product alcohols azeotropic, rapidly the by-product alcohol in the reaction system is deviate from, promote reaction to carry out, also guaranteed higher reaction conversion ratio simultaneously to the positive reaction direction.The existence of azeotropic solvent guarantees that raw material (methyl) acrylate is retained in Polycondensation Reactor and Esterification Reactor participation reaction in the entire reaction course, and can not enter separation column, has prevented the generation of the stifled poly-phenomenon of separation column.
Describe synthetic method of the present invention in detail with transesterification reaction below.
The raw material dehydration:
The used catalyzer of transesterification reaction is very responsive to water sometimes, and minor amount of water can make it be destroyed, thereby loses catalytic activity, and the existence meeting of water simultaneously causes adverse influence to reaction, therefore can dewater to system before the reaction.With alkylphenol polyoxyethylene, (methyl) acrylate, entrainer, stopper have stirring by being metered into, temperature is taken into account in the reactor of separation column, heating, treat that alkylphenol polyoxyethylene melts back (about about 70 ℃) fully, start and stir, continue heating, make the mixed reaction solution azeotropic, divide water, up to the distillate clarification, tower top temperature reaches the boiling point of entrainer.
Temperature is 80～150 ℃ at the bottom of the still of control azeotropic dehydration, more preferably 100～140 ℃, the azeotropic solvent consumption is 50%～150% of (methyl) acrylate consumption, the stopper consumption is 0.1～0.5% of a reaction mixture total amount, and stopper is selected 2,6 di t butyl phenol (being stopper 264) for use, phenothiazine, Resorcinol, or arsenic pyridine alcohol phosphoric acid ester stopper (as Z-705, Z-701) in one or more.
Transesterification reaction:
After moisture content removed and finishes, cooling added catalyzer in reactor, and temperature reaction is from the azeotrope that the by-product alcohol and the entrainer of cat head fractionation reaction generation are formed, the composition of sampling analysis azeotrope (with the transformation efficiency of assaying reaction).Catalyst system therefor comprises the mixture that the alcoholate, tin of alkaline earth metal oxide or its esters, basic metal or alkaline-earth metal or plumbous oxide compound or organic compound, titanic acid ester or above-mentioned two or more materials are formed.
Control reaction temperature is 80～180 ℃, more preferably 100～170 ℃, and the content of by-product alcohol in the detection azeotrope, when pure content is low to azeotrope, stopped reaction.Remove unreacted (methyl) acrylate and solvent then, obtain target product alkylphenol polyoxyethylene (methyl) acrylate.Used catalyzer comprises the mixture of two or more compositions in organic compound, titanic acid ester or the above-claimed cpd of metals such as the alcoholate, tin lead of part metals oxide compound and its esters, alkalies and alkaline earth.
The distillation of product is refining:
Reaction finishes, cooling moves into reaction solution in another reactor of band stirring, adds a certain amount of 10% sulfuric acid, distilled water respectively, stir, the distillation that heats up removes excessive starting ester, when treating that temperature reaches 100 ℃, reduces rate of heating, open vacuum system, underpressure distillation keeps temperature in the kettle about 100 ℃, steams until no longer including liquid.
The present invention adopts azeotropic dehydration dealcoholysis technology, has removed by-product alcohol quickly and effectively, and reaction can be carried out smoothly; Make (methyl) acrylate that has a large amount of two keys be retained in Polycondensation Reactor and Esterification Reactor simultaneously, prevented the generation of polymerism in reactor and the knockout tower.The azeotrope that reaction generates can carry out effective Separation and Recovery, (methyl) acrylate that last handling process obtains also can be recycled, waste material is few, reaction process is simple, and product purity is higher, the transformation efficiency of raw material alkylphenol polyoxyethylene can reach 80%～95%, and whole technology simple and feasible has prevented the generation of raw material polymerism in reactor and knockout tower effectively.
Alkylphenol polyoxyethylene of the present invention (methyl) acrylate can be used as a kind of monomer, be used for the synthetic macromolecule tensio-active agent, as static inhibitor, jelling agent, thickening material, flow improver, flocculation agent, emulsifying agent, emulsion splitter and oil-displacing agent etc., especially for synthetic a kind of acrylic fibers durable antistatic agent.
The invention will be further described below by embodiment and comparative example, but the present invention is not limited only to these examples.Also can fully understand essence of the present invention and invention scope by these embodiment, further understand relative merits of the present invention.
The drawing explanation
Figure of description 1 is the infrared spectrum of alkylphenol polyoxyethylene, and Figure of description 2 is the infrared spectrum of alkylphenol polyoxyethylene acrylate, and wherein arrow marks and partly is the characteristic peak of ester.
Embodiment
Embodiment 1
Stirring is housed, temperature is taken into account in the 500ml four-hole boiling flask of separation column, add polyoxyethylene octylphenol ether (OP-10) 80g, methyl methacrylate 80g, normal hexane 70g, stopper Z-701 0.3g, heating, start and stir, keep the still temperature about 105 ℃, make the mixed reaction solution azeotropic, divide water, up to the distillate clarification, tower top temperature reaches 68.5 ℃.
In reactor, add tetraethyl titanate 2.0g then, insulation reaction, methanol content in the sampling analysis cat head azeotrope, when methanol content is lower than 0.1% in the cat head azeotrope, stopped reaction.
Reaction obtains azeotrope 55.0g altogether, and its methanol content of sampling analysis is 6.7%, and the transformation efficiency of polyoxyethylene octylphenol ether is 93.05%.
In above-mentioned reaction solution, add the sulfuric acid of 20g 10%, mix and stirred 20 minutes, add 80g distilled water then, light constituent is removed in elder generation's air distillation, underpressure distillation then, last vacuum pressure reaches-0.097MPa, can obtain polyoxyethylene octylphenol ether methacrylic ester product.
Embodiment 2
Stirring is housed, temperature is taken into account in the 500ml four-hole boiling flask of separation column, add polyoxyethylene octylphenol ether (OP-10) 80g, ethyl propenoate 80g, normal hexane 70g, stopper Z-701 0.3g, heating, start and stir, keep the still temperature about 105 ℃, make the mixed reaction solution azeotropic, divide water, up to the distillate clarification, tower top temperature reaches 68.5 ℃.
In reactor, add metatitanic acid orthocarbonate 2.0g then, insulation reaction, ethanol content in the sampling analysis cat head azeotrope, when ethanol content is lower than 0.1% in the cat head azeotrope, stopped reaction.
Reaction obtains azeotrope 57.0g altogether, and its ethanol content of sampling analysis is 9.7%, and the transformation efficiency of polyoxyethylene octylphenol ether is 94.55%.
In above-mentioned reaction solution, add the sulfuric acid of 20g 10%, mix and stirred 20 minutes, add 80g distilled water then, light constituent is removed in elder generation's air distillation, underpressure distillation then, last vacuum pressure reaches-0.097MPa, can obtain polyoxyethylene octylphenol ether acrylate product.
Embodiment 3
Stirring is housed, temperature is taken into account in the 500ml four-hole boiling flask of separation column, add polyoxyethylene octylphenol ether (OP-10) 80g, butyl acrylate 80g, toluene 80g, stopper Z-705 0.3g, heating, start and stir, keep the still temperature about 135 ℃, make the mixed reaction solution azeotropic, divide water, up to the distillate clarification, tower top temperature reaches 109.5 ℃.
In reactor, add tetraethyl titanate 2.0g then, insulation reaction, butanol content in the sampling analysis cat head azeotrope, when butanol content is lower than 0.1% in the cat head azeotrope, stopped reaction.
Reaction obtains azeotrope 63.0g altogether, and the sampling analysis butanol content is 13.7%, and the transformation efficiency of polyoxyethylene octylphenol ether is 94.22%.
In above-mentioned reaction solution, add the sulfuric acid of 20g 10%, mix and stirred 20 minutes, add 80g distilled water then, light constituent is removed in elder generation's air distillation, underpressure distillation then, last vacuum pressure reaches-0.097MPa, can obtain polyoxyethylene octylphenol ether acrylate product.
Embodiment 4
Stirring is housed, temperature is taken into account in the 500ml four-hole boiling flask of separation column, add polyoxyethylene nonylphenol ether (NP-30) 80g, methyl methacrylate 80g, hexanaphthene 70g, stopper Z-701 0.3g, heating, start and stir, keep the still temperature about 105 ℃, make the mixed reaction solution azeotropic, divide water, up to the distillate clarification, tower top temperature reaches 80.5 ℃.
In reactor, add plumbous oxide 2.0g then, insulation reaction, methanol content in the sampling analysis cat head azeotrope, when methanol content is lower than 0.1% in the cat head azeotrope, stopped reaction.
Reaction obtains azeotrope 57.0g altogether, and its methanol content of sampling analysis is 2.7%, and the transformation efficiency of polyoxyethylene nonylphenol ether is 90.53%.
In above-mentioned reaction solution, add the sulfuric acid of 20g 10%, mix and stirred 20 minutes, add 80g distilled water then, light constituent is removed in elder generation's air distillation, underpressure distillation then, last vacuum pressure reaches-0.097MPa, can obtain polyoxyethylene octylphenol ether methacrylic ester product.
Embodiment 5
Stirring is housed, temperature is taken into account in the 500ml four-hole boiling flask of separation column, add polyoxyethylene nonylphenol ether (NP-40) 80g, butyl methacrylate 80g, dimethylbenzene 70g, stopper Z-701 0.3g, heating, start and stir, keep the still temperature about 145 ℃, make the mixed reaction solution azeotropic, divide water, up to the distillate clarification, tower top temperature reaches 136.0 ℃.
In reactor, add sodium methylate 2.0g then, insulation reaction, butanol content in the sampling analysis cat head azeotrope, when butanol content is lower than 0.1% in the cat head azeotrope, stopped reaction.
Reaction obtains azeotrope 65.0g altogether, and its butanol content of sampling analysis is 5.0%, and the transformation efficiency of polyoxyethylene nonylphenol ether is 96.05%.
In above-mentioned reaction solution, add the sulfuric acid of 20g 10%, mix and stirred 20 minutes, add 80g distilled water then, light constituent is removed in elder generation's air distillation, underpressure distillation then, last vacuum pressure reaches-0.097MPa, can obtain polyoxyethylene nonylphenol ether methacrylic ester product.
Claims (12)
1. alkylphenol polyoxyethylene acrylate or alkylphenol polyoxyethylene methacrylic ester, its structural formula is:
In the formula: R1 represent H or-CH3; R3 represents the alkyl of carbon atom number from 0 to 15; The n value gets 1～150, and n is the number of ethylene oxide repeating unit in the molecule.
2. the preparation method of described alkylphenol polyoxyethylene acrylate of claim 1 or alkylphenol polyoxyethylene methacrylic ester may further comprise the steps:
A, in the presence of azeotropic solvent and stopper, the mixture of alkylphenol polyoxyethylene and acrylate or methacrylic ester is carried out azeotropic dehydration.
B, in the presence of catalyzer, alkylphenol polyoxyethylene through step a dehydration is carried out transesterification reaction with acrylate or methacrylic ester in azeotropic solvent, generate alkylphenol polyoxyethylene acrylate or alkylphenol polyoxyethylene methacrylic ester.
C, from the product mixtures of step b Separation and Recovery azeotropic solvent, acrylate or methacrylic ester.
3. method according to claim 2 is characterized in that described acrylate or methacrylic ester comprise methyl acrylate, methyl methacrylate, ethyl propenoate, butyl acrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, butyl methacrylate, Octyl methacrylate or Octyl acrylate.
4. method according to claim 2 is characterized in that described azeotropic dehydration temperature is 80～150 ℃,
5. method according to claim 2 is characterized in that described transesterification reaction temperature is 80～180 ℃.
6. method according to claim 2 is characterized in that described catalyzer comprises the mixture that the alcoholate, tin of alkaline earth metal oxide or its esters, basic metal or alkaline-earth metal or plumbous oxide compound or organic compound, titanic acid ester or above-mentioned two or more materials are formed.
7. method according to claim 2 is characterized in that described catalyst levels is 0.5～4.0% of a reaction mixture total amount.
8. method according to claim 2 is characterized in that being selected from hexanaphthene, normal hexane, toluene, dimethylbenzene or N-BUTYL ACETATE at described azeotropic solvent.
9. method according to claim 2 is characterized in that described azeotropic solvent consumption is 50%～150% of raw material propylene acid esters or a methacrylic ester weight.
10. method according to claim 2 is characterized in that described stopper is selected from 2,6 di t butyl phenol, phenothiazine, Resorcinol, or in the arsenic pyridine alcohol phosphoric acid ester stopper one or more.
11. method according to claim 2 is characterized in that described stopper consumption is 0.1～0.5% of a reaction mixture gross weight.
12. described alkylphenol polyoxyethylene acrylate of claim 1 or the alkylphenol polyoxyethylene methacrylic ester purposes in preparation static inhibitor, jelling agent, thickening material, flow improver, flocculation agent, emulsifying agent, emulsion splitter or oil-displacing agent.
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| CN02151545.XA CN1245433C (en) | 2002-12-31 | 2002-12-31 | Lissapol N(methyl) propenoic acid ester and its preparation and use |
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| CN114316781B (en) * | 2020-09-30 | 2022-06-28 | 上海飞凯材料科技股份有限公司 | Curable composition, cured coating, coating product and preparation method |
| CN114316251B (en) * | 2020-09-30 | 2023-08-22 | 上海飞凯材料科技股份有限公司 | Treatment method, oligomer, coating raw material, coating and preparation method of alkylphenol polyoxyethylene (methyl) acrylate |
| CN114316249B (en) * | 2020-09-30 | 2023-08-22 | 上海飞凯材料科技股份有限公司 | Alkylphenol polyoxyethylene (methyl) acrylate, treatment method thereof and coating |
| CN115069199A (en) * | 2022-07-14 | 2022-09-20 | 山东大明精细化工有限公司 | Preparation process of sodium alkyl polyoxyethylene ether sulfonate |
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