CN104151485A - Long-chain unsaturated fatty acid-modified acrylate emulsion and preparation method thereof - Google Patents

Long-chain unsaturated fatty acid-modified acrylate emulsion and preparation method thereof Download PDF

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Publication number
CN104151485A
CN104151485A CN201410342796.9A CN201410342796A CN104151485A CN 104151485 A CN104151485 A CN 104151485A CN 201410342796 A CN201410342796 A CN 201410342796A CN 104151485 A CN104151485 A CN 104151485A
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emulsion
long
fatty acid
unsaturated fatty
chain unsaturated
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周铭
杨建红
沈琴
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SONGTEN JIANGSU NEW MSTAR TECHNOLOGY Ltd
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SONGTEN JIANGSU NEW MSTAR TECHNOLOGY Ltd
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Abstract

The invention relates to a long-chain unsaturated fatty acid-modified acrylate emulsion and a preparation method thereof. The acrylate emulsion is prepared from raw materials such as acrylate soft monomers, acrylate hard monomers, long-chain unsaturated fatty acid, an initiator, an emulsifier, sodium bicarbonate and water by virtue of emulsion polymerization. The emulsion prepared by the preparation method takes the long-chain unsaturated fatty acid as a functional monomer which is introduced into an acrylate emulsion system and accounts for 0.5%-5% of the total amount of the monomers; the film performance is improved by virtue of further self-crosslinking reaction of unsaturated double bonds of the functional monomer during a film drying process to solve problems of poor water resistance, lower hardness, and the like of an existing acrylate emulsion film, and use of an artificially synthesized modifier which is relatively high in price and causes environmental pollution further can be avoided. By introducing the long-chain unsaturated fatty acid, not only can the film performance be effectively improved, but also the acrylate emulsion can be developed in a green direction to satisfy environmental protection requirements well.

Description

Acrylic ester emulsion of a kind of long-chain unsaturated fatty acid modification and preparation method thereof
Technical field
The present invention relates to a kind of acrylic ester emulsion and preparation method thereof and be particularly related to acrylic ester emulsion of a kind of long-chain unsaturated fatty acid modification and preparation method thereof.
Background technology
Acrylic ester emulsion because of its over-all properties comparatively excellent, price is also occupied certain advantage and is widely used in the field such as coating, sizing agent, but self also has certain limitation, as water tolerance is not good, hardness is lower etc.Investigator in the past for these deficiencies the synthetic method to acrylic ester emulsion, processing parameter, improved performance and application study, and the main method that adopts modification improves its performance at present, comprise organic-silicon-modified, nanometer particle-modified, cross-linking modified, polyurethane-modifiedly etc., and all obtained certain achievement.Publication number CN 102649835 A disclose a kind of organic inorganic hybridization high silicon content acrylic ester emulsion and preparation method thereof.The hydrophilic monomer of the alkaline silica sol through silane coupler modified and hydroxyl is carried out coupling by the method, combine as emulsification system using reactive emulsifier, anionic emulsifier, nonionic emulsifier again, carry out in-situ polymerization with acrylate monomer, make the sizing agent that emulsion appearance is good, stability in storage is high, surface energy is low, water-intake rate is low.But its preparation technology is comparatively complicated, silane coupling agent cost is relatively high, and, through the acrylic ester emulsion of other modifier modification problems such as also existence and stability, consistency be not good, so find the Focal point and difficult point that properties-correcting agent relatively inexpensive, excellent performance is research.
Because environmental problem becomes increasingly conspicuous; a lot of scholars find trim point in social development and environment protection between the two; in constantly improving the various performances of polymkeric substance, research and development tool recyclability, degradation property, the polymkeric substance of environmental protection more, improve the utilization ratio of Biological resources.Natural vegetables oil, as a kind of renewable resources of wide material sources, is a kind of for improving the ideal material of polymer performance, and existing Patents discloses in the middle of the preparation that different types of vegetables oil is applied to Synolac, urethane resin etc.As publication number CN 102796228 A disclose a kind of preparation method of acrylic modified waterborne tall oil alkyd resin emulsion.Its main process comprises the preparation of urethane intermediate, after it is reacted with vegetable fatty acids, polyvalent alcohol, polyprotonic acid, add a certain amount of deionized water to prepare Synolac water dispersion; Finally it is reacted with acrylic ester monomer, make acrylate modified aqueous alkide resin.Product does not contain emulsifying agent, viscosity is low, stability in storage good, and its dried coating film is fast, hardness is high, has good mechanical property and Corrosion Protection.And for example publication number CN 102234371 A disclose polymeric system, emulsion and synthetic method thereof and the application based on crude vegetal, this invention adopts the oligopolymer of reactive monomer or reactive monomer to carry out modification to poly-crude vegetal and makes polymeric system, wherein reactive monomer is one or more of acrylic ester monomer, silicone based monomer, fluorine carbon monomer and self-emulsifying monomer, the oligopolymer of reactive monomer is polyurethanes oligopolymer, then be main raw material synthetic emulsion with this polymeric acceptor, and relate to its synthetic method and application.This invention has great importance to search for oil substitute, dependence and the environmental protection of minimizing to petroleum resources.Also have patent utilization vegetables oil to carry out modified acrylate emulsion, publication number CN 102010477 A disclose unsaturated long-chain fatty acid ester modified acrylate emulsion of a kind of low water absorption and preparation method thereof, the method adopts unsaturated longer chain fatty acid alcohol ester and the synthetic acrylic ester emulsion with low water absorption of (methyl) acrylate reactions, and the usage quantity of unsaturated longer chain fatty acid alcohol ester is 9%-60%.This synthetic method do not use price relatively high containing fluoroalkane ester and organosilicon, do not use solia particle yet, can reduce energy consumption and the pollution to environment, but the usage quantity of unsaturated longer chain fatty acid alcohol ester is more, affect the stability of product.
Summary of the invention
The object of the invention is: the water tolerance, hardness, the not good defect of sticking power that exist for existing acrylic ester emulsion, propose acrylic ester emulsion of a kind of long-chain unsaturated fatty acid modification and preparation method thereof.
The technical scheme that realizes the object of the invention is: a kind of acrylic ester emulsion of long-chain unsaturated fatty acid modification, there is following component, and each constituent mass umber proportioning is as follows:
Esters of acrylic acid soft monomer: 38-65; Preferably 38,40,44,55,60
Esters of acrylic acid hard monomer: 15-42; Preferably 20,25,36,40,42
Long-chain unsaturated fatty acid: 0.4-4.8; Preferably 0.8,1.2,1.6
Initiator: 0.16-0.48; Preferably 0.24,0.4
Emulsifying agent: 0.8-4; Preferably 2.4
Sodium bicarbonate: 0.16-0.48; Preferably 0.4
Water: 115-125.Preferably 120
The acrylic ester emulsion of above-mentioned long-chain unsaturated fatty acid modification, preferred each constituent mass umber proportioning is as follows:
Esters of acrylic acid soft monomer: 40;
Esters of acrylic acid hard monomer: 40;
Long-chain unsaturated fatty acid: 0.8;
Initiator: 0.4;
Emulsifying agent: 2.4;
Sodium bicarbonate: 0.4;
Water: 120.
In this formula situation, reaction conversion ratio is the highest, the water-intake rate minimum of acrylic ester emulsion film, and hardness and sticking power are the most excellent.
The fill a prescription usage quantity of the long-chain unsaturated fatty acid that uses of the present invention is few, because the membership that adds of long-chain unsaturated fatty acid increases emulsion viscosity, the diffusion hindered of monomer and free radical, emulsion transformation efficiency is declined, final emulsion and the film performance thereof of affecting, in actual preparation, the usage quantity of long-chain unsaturated fatty acid can not be excessive.
The acrylic ester emulsion of above-mentioned long-chain unsaturated fatty acid modification, described esters of acrylic acid soft monomer is at least one in butyl acrylate, ethyl propenoate; Described esters of acrylic acid hard monomer is at least one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate.
The acrylic ester emulsion of above-mentioned long-chain unsaturated fatty acid modification, described long-chain unsaturated fatty acid is at least one in eleostearic acid, ricinolic acid, oleum lini, soybean oil, Semen Maydis oil.
The acrylic ester emulsion of above-mentioned long-chain unsaturated fatty acid modification, described emulsifying agent is the Compositional type emulsifying agent of anionic and non-ionic type, wherein anionic emulsifier is at least one in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium oleate, and nonionic emulsifier is at least one in polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, oleic acid.
The acrylic ester emulsion of above-mentioned long-chain unsaturated fatty acid modification, described initiator is at least one in Potassium Persulphate, ammonium persulphate.
The preparation method of the acrylic ester emulsion of above-mentioned long-chain unsaturated fatty acid modification, comprises the steps:
A takes the initiator of water, charging capacity 1/3rd of the esters of acrylic acid soft monomer of charging capacity 1/5th and esters of acrylic acid hard monomer, charging capacity 1/2nd and emulsifying agent, whole sodium bicarbonate in proportion, said mixture material is carried out to emulsification and make pre-emulsion;
B stirs 0.5-1.0h by above-mentioned pre-emulsion under 78-85 DEG C of condition, obtains light blue emulsion;
C takes the initiator of water, residue 2/3rds of residue 4/5ths esters of acrylic acid soft monomer and esters of acrylic acid hard monomer, residue 1/2nd and emulsifying agent, whole long-chain unsaturated fatty acid, said mixture material is carried out to emulsification and make pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 2-3h;
E dropwises rear continuation isothermal reaction, has reacted rear intensification 3-5 DEG C insulation, then cooling, and discharging, adjusting pH obtain final product.
Wherein, e step is specially and dropwises rear continuation isothermal reaction 2h, has reacted rear intensification 3-5 DEG C of insulation 1h, takes cooling measure, and after temperature is down to 45 DEG C of left and right, discharging, adds ammoniacal liquor to adjust pH, obtains the acrylic ester emulsion of long-chain unsaturated fatty acid modification.
Present method substep feeds intake and makes a, two pre-emulsions of c, adopts and can make in this way that stability of emulsion is better, narrow diameter distribution, reaction be easy to control.
The present invention has positive effect:
1. the present invention is using long-chain unsaturated fatty acid as functional monomer, be introduced in acrylic ester emulsion system, its consumption accounts for the 0.5%-5% of monomer total amount, utilize its unsaturated double-bond having that self-crosslinking reaction occurs further in film drying process and improve film properties, with solve acrylic ester emulsion film existing not good, the problem such as hardness is lower of water tolerance, also can avoid using the synthetic properties-correcting agent that price is relatively high, cause environmental pollution.The introducing of long-chain unsaturated fatty acid not only can effectively improve film properties, also makes acrylic ester emulsion towards greenization future development, more meets the requirement of environment protection.The synthetic acrylic ester emulsion stability of the present invention is better, and hardness, the sticking power of film are more excellent, and water-intake rate is less, and contact angle is larger, and the less over-all properties that just can effectively improve emulsion and film of long-chain unsaturated fatty acid consumption, and application prospect is comparatively wide.
2. compared with the performance of improving emulsion and film with properties-correcting agent such as utilizing organosilicon, the present invention adopts long-chain unsaturated fatty acid to carry out modification to acrylic ester emulsion, stability of emulsion is better, gel content is few, and water-resistance property of coating, sticking power, hardness are better, and the impact of environment is reduced to some extent.
3. come compared with modified acrylate emulsion with utilizing a large amount of vegetables oil or long-chain unsaturated fatty acid alcohol ester, the usage quantity of long-chain unsaturated fatty acid of the present invention is less, and product property is better.
4. the emulsion polymerization technique process control that preparation method of the present invention selects is comparatively simple, and adopt substep to feed intake and prepare that pre-emulsion makes that stability of emulsion is better, narrow diameter distribution, reaction be easy to control.
Embodiment
(embodiment 1)
The mass fraction proportioning of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification of the present embodiment is as follows:
Butyl acrylate 40; Methyl methacrylate 40; Eleostearic acid 0.8; Potassium Persulphate 0.4; Sodium lauryl sulphate 0.6; Polyoxyethylene nonylphenol ether 1.8; Sodium bicarbonate 0.4; Water 120.
Preparation method is as follows:
A takes the butyl acrylate of charging capacity 1/5th and methyl methacrylate, the water of charging capacity 1/2nd, Potassium Persulphate, sodium lauryl sulphate and the polyoxyethylene nonylphenol ether of charging capacity 1/3rd, whole sodium bicarbonates in proportion, appeal mixture is carried out to emulsification and make pre-emulsion;
B will appeal pre-emulsion and stir 0.5h under 83 DEG C of conditions, obtain light blue emulsion;
C takes residue 4/5ths butyl acrylate and methyl methacrylate, the water of residue 1/2nd, Potassium Persulphate, sodium lauryl sulphate and the polyoxyethylene nonylphenol ether of residue 2/3rds, whole eleostearic acids, carries out emulsification by appeal mixture and makes pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 3h;
E dropwises rear continuation isothermal reaction 2h;
F has reacted 3 DEG C of insulation 1h of rear intensification;
G takes cooling measure, treats that temperature is down to 45 DEG C of left and right, add ammoniacal liquor to stir after discharging, obtain the acrylic ester emulsion of long-chain unsaturated fatty acid modification.
(embodiment 2)
The mass fraction proportioning of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment is as follows:
Butyl acrylate 40; Methyl methacrylate 40; Eleostearic acid 1.2; Potassium Persulphate 0.4; Sodium lauryl sulphate 0.6; Polyoxyethylene nonylphenol ether 1.8; Sodium bicarbonate 0.4; Water 116.
The preparation of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment comprises the steps:
A takes the butyl acrylate of charging capacity 1/5th and methyl methacrylate, the water of charging capacity 1/2nd, Potassium Persulphate, sodium lauryl sulphate and the polyoxyethylene nonylphenol ether of charging capacity 1/3rd, whole sodium bicarbonates in proportion, appeal mixture is carried out to emulsification and make pre-emulsion;
B will appeal pre-emulsion and stir 0.6h under 85 DEG C of conditions, obtain light blue emulsion;
C takes residue 4/5ths butyl acrylate and methyl methacrylate, the water of residue 1/2nd, Potassium Persulphate, sodium lauryl sulphate and the polyoxyethylene nonylphenol ether of residue 2/3rds, whole eleostearic acids, carries out emulsification by appeal mixture and makes pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 2h;
E dropwises rear continuation isothermal reaction 2h;
F has reacted 3 DEG C of insulation 1h of rear intensification;
G takes cooling measure, treats that temperature is down to 45 DEG C of left and right, add ammoniacal liquor to stir after discharging, obtain the acrylic ester emulsion of long-chain unsaturated fatty acid modification.
(embodiment 3)
The mass fraction proportioning of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment is as follows:
Butyl acrylate 38; β-dimethyl-aminoethylmethacrylate 42; Soybean oil 0.8; Potassium Persulphate 0.4; Sodium dodecylbenzene sulfonate 0.4; Polyoxyethylene nonylphenol ether 1.2; Sodium bicarbonate 0.4; Water 120.
The preparation of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment comprises the steps:
A takes the butyl acrylate of charging capacity 1/5th and β-dimethyl-aminoethylmethacrylate, the water of charging capacity 1/2nd, Potassium Persulphate, Sodium dodecylbenzene sulfonate and the polyoxyethylene nonylphenol ether of charging capacity 1/3rd, whole sodium bicarbonates in proportion, appeal mixture is carried out to emulsification and make pre-emulsion;
B will appeal pre-emulsion and stir 1.0h under 83 DEG C of conditions, obtain light blue emulsion;
C takes residue 4/5ths butyl acrylate and β-dimethyl-aminoethylmethacrylate, the water of residue 1/2nd, Potassium Persulphate, Sodium dodecylbenzene sulfonate and the polyoxyethylene nonylphenol ether of residue 2/3rds, whole soybean oil, carries out emulsification by appeal mixture and makes pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 2.5h;
E dropwises rear continuation isothermal reaction 2h;
F has reacted 3 DEG C of insulation 1h of rear intensification;
G takes cooling measure, treats that temperature is down to 45 DEG C of left and right, add ammoniacal liquor to stir after discharging, obtain the acrylic ester emulsion of long-chain unsaturated fatty acid modification.
(embodiment 4)
The mass fraction proportioning of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment is as follows:
Ethyl propenoate 60; Methyl methacrylate 20; Eleostearic acid 1.8; Potassium Persulphate 0.48; Sodium lauryl sulphate 0.6; Polyoxyethylene octylphenol ether 1.8; Sodium bicarbonate 0.4; Water 120.
The preparation of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment comprises the steps:
A takes the ethyl propenoate of charging capacity 1/5th and methyl methacrylate, the water of charging capacity 1/2nd, Potassium Persulphate, sodium lauryl sulphate and the polyoxyethylene octylphenol ether of charging capacity 1/3rd, whole sodium bicarbonates in proportion, appeal mixture is carried out to emulsification and make pre-emulsion;
B will appeal pre-emulsion and stir 0.9h under 80 DEG C of conditions, obtain light blue emulsion;
C takes residue 4/5ths ethyl propenoate and methyl methacrylate, the water of residue 1/2nd, Potassium Persulphate, sodium lauryl sulphate and the polyoxyethylene octylphenol ether of residue 2/3rds, whole eleostearic acids, carries out emulsification by appeal mixture and makes pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 2.8h;
E dropwises rear continuation isothermal reaction 2h;
F has reacted 3 DEG C of insulation 1h of rear intensification;
G takes cooling measure, treats that temperature is down to 45 DEG C of left and right, add ammoniacal liquor to stir after discharging, obtain the acrylic ester emulsion of long-chain unsaturated fatty acid modification.
(embodiment 5)
The mass fraction proportioning of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment is as follows:
Ethyl propenoate 55; β-dimethyl-aminoethylmethacrylate 25; Semen Maydis oil 0.4; Ammonium persulphate 0.24; Sodium dodecylbenzene sulfonate 0.6; Oleic acid 1.8; Sodium bicarbonate 0.4; Water 120.
The preparation of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment comprises the steps:
A takes the ethyl propenoate of charging capacity 1/5th and β-dimethyl-aminoethylmethacrylate, the water of charging capacity 1/2nd, ammonium persulphate, Sodium dodecylbenzene sulfonate and the oleic acid of charging capacity 1/3rd, whole sodium bicarbonates in proportion, appeal mixture is carried out to emulsification and make pre-emulsion;
B will appeal pre-emulsion and stir 1.0h under 85 DEG C of conditions, obtain light blue emulsion;
C takes residue 4/5ths ethyl propenoate and β-dimethyl-aminoethylmethacrylate, the water of residue 1/2nd, ammonium persulphate, Sodium dodecylbenzene sulfonate and the oleic acid of residue 2/3rds, whole Semen Maydis oil, carries out emulsification by appeal mixture and makes pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 3h;
E dropwises rear continuation isothermal reaction 2h;
F has reacted 4 DEG C of insulation 1h of rear intensification;
G takes cooling measure, treats that temperature is down to 45 DEG C of left and right, add ammoniacal liquor to stir after discharging, obtain the acrylic ester emulsion of long-chain unsaturated fatty acid modification.
(embodiment 6)
The mass fraction proportioning of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment is as follows:
Butyl acrylate 44; Methyl methacrylate 36; Ricinolic acid 0.8; Potassium Persulphate 0.20; Sodium lauryl sulphate 0.6; Polyoxyethylene nonylphenol ether 1.8; Sodium bicarbonate 0.4; Water 120.
The preparation of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment comprises the steps:
A takes the butyl acrylate of charging capacity 1/5th and methyl methacrylate, the water of charging capacity 1/2nd, Potassium Persulphate, sodium lauryl sulphate and the polyoxyethylene nonylphenol ether of charging capacity 1/3rd, whole sodium bicarbonates in proportion, appeal mixture is carried out to emulsification and make pre-emulsion;
B will appeal pre-emulsion and stir 0.5h under 81 DEG C of conditions, obtain light blue emulsion;
C takes residue 4/5ths butyl acrylate and methyl methacrylate, the water of residue 1/2nd, Potassium Persulphate, sodium lauryl sulphate and the polyoxyethylene nonylphenol ether of residue 2/3rds, whole ricinolic acids, carries out emulsification by appeal mixture and makes pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 2h;
E dropwises rear continuation isothermal reaction 2h;
F has reacted 4 DEG C of insulation 1h of rear intensification;
G takes cooling measure, treats that temperature is down to 45 DEG C of left and right, add ammoniacal liquor to stir after discharging, obtain the acrylic ester emulsion of long-chain unsaturated fatty acid modification.
(embodiment 7)
The mass fraction proportioning of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment is as follows:
Butyl acrylate 39; Methyl methacrylate 40; Oleum lini 0.8; Potassium Persulphate 0.4; Sodium oleate 0.4; Polyoxyethylene nonylphenol ether 2.2; Sodium bicarbonate 0.32; Water 122.
The preparation of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment comprises the steps:
A takes the butyl acrylate of charging capacity 1/5th and methyl methacrylate, the water of charging capacity 1/2nd, Potassium Persulphate, sodium oleate and the polyoxyethylene nonylphenol ether of charging capacity 1/3rd, whole sodium bicarbonates in proportion, appeal mixture is carried out to emulsification and make pre-emulsion;
B will appeal pre-emulsion and stir 0.5h under 80 DEG C of conditions, obtain light blue emulsion;
C takes residue 4/5ths butyl acrylate and methyl methacrylate, the water of residue 1/2nd, Potassium Persulphate, sodium oleate and the polyoxyethylene nonylphenol ether of residue 2/3rds, whole oleum lini, carries out emulsification by appeal mixture and makes pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 2h;
E dropwises rear continuation isothermal reaction 2h;
F has reacted 3 DEG C of insulation 1h of rear intensification;
G takes cooling measure, treats that temperature is down to 45 DEG C of left and right, add ammoniacal liquor to stir after discharging, obtain the acrylic ester emulsion of long-chain unsaturated fatty acid modification.
(embodiment 8)
The mass fraction proportioning of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment is as follows:
Butyl acrylate 44; Methyl methacrylate 36; Oleum lini 1.6; Ammonium persulphate 0.4; Sodium lauryl sulphate 2.6; Polyoxyethylene nonylphenol ether 1.4; Sodium bicarbonate 0.16; Water 120.
The preparation of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment comprises the steps:
A takes the butyl acrylate of charging capacity 1/5th and methyl methacrylate, the water of charging capacity 1/2nd, ammonium persulphate, sodium lauryl sulphate and the polyoxyethylene nonylphenol ether of charging capacity 1/3rd, whole sodium bicarbonates in proportion, appeal mixture is carried out to emulsification and make pre-emulsion;
B will appeal pre-emulsion and stir 0.8h under 83 DEG C of conditions, obtain light blue emulsion;
C takes residue 4/5ths butyl acrylate and methyl methacrylate, the water of residue 1/2nd, ammonium persulphate, sodium lauryl sulphate and the polyoxyethylene nonylphenol ether of residue 2/3rds, whole oleum lini, carries out emulsification by appeal mixture and makes pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 2.5h;
E dropwises rear continuation isothermal reaction 2h;
F has reacted 3 DEG C of insulation 1h of rear intensification;
G takes cooling measure, treats that temperature is down to 45 DEG C of left and right, add ammoniacal liquor to stir after discharging, obtain the acrylic ester emulsion of long-chain unsaturated fatty acid modification.
(embodiment 9)
The mass fraction proportioning of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment is as follows:
Butyl acrylate 60; Methyl methacrylate 40; Oleum lini 3.6; Ammonium persulphate 0.4; Sodium lauryl sulphate 2.4; Polyoxyethylene nonylphenol ether 1.6; Sodium bicarbonate 0.16; Water 125.
The preparation of the acrylic ester emulsion of the long-chain unsaturated fatty acid modification described in the present embodiment comprises the steps:
A takes the butyl acrylate of charging capacity 1/5th and methyl methacrylate, the water of charging capacity 1/2nd, ammonium persulphate, sodium lauryl sulphate and the polyoxyethylene nonylphenol ether of charging capacity 1/3rd, whole sodium bicarbonates in proportion, appeal mixture is carried out to emulsification and make pre-emulsion;
B will appeal pre-emulsion and stir 0.8h under 83 DEG C of conditions, obtain light blue emulsion;
C takes residue 4/5ths butyl acrylate and methyl methacrylate, the water of residue 1/2nd, ammonium persulphate, sodium lauryl sulphate and the polyoxyethylene nonylphenol ether of residue 2/3rds, whole oleum lini, carries out emulsification by appeal mixture and makes pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 2.5h;
E dropwises rear continuation isothermal reaction 2h;
F has reacted 3 DEG C of insulation 1h of rear intensification;
G takes cooling measure, treats that temperature is down to 45 DEG C of left and right, add ammoniacal liquor to stir after discharging, obtain the acrylic ester emulsion of long-chain unsaturated fatty acid modification.
Embodiment emulsion property
Embodiment emulsion film performance
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment of making, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (7)

1. an acrylic ester emulsion for long-chain unsaturated fatty acid modification, is characterized in that: have following component, each constituent mass umber proportioning is as follows:
Esters of acrylic acid soft monomer: 38-65;
Esters of acrylic acid hard monomer: 15-42;
Long-chain unsaturated fatty acid: 0.4-4.8;
Initiator: 0.16-0.48;
Emulsifying agent: 0.8-4;
Sodium bicarbonate: 0.16-0.48;
Water: 115-125.
2. the acrylic ester emulsion of long-chain unsaturated fatty acid modification according to claim 1, is characterized in that: each constituent mass umber proportioning is as follows:
Esters of acrylic acid soft monomer: 40;
Esters of acrylic acid hard monomer: 40;
Long-chain unsaturated fatty acid: 0.8;
Initiator: 0.4;
Emulsifying agent: 2.4;
Sodium bicarbonate: 0.4;
Water: 120.
3. the acrylic ester emulsion of long-chain unsaturated fatty acid modification according to claim 1 and 2, is characterized in that: described esters of acrylic acid soft monomer is at least one in butyl acrylate, ethyl propenoate; Described esters of acrylic acid hard monomer is at least one in methyl methacrylate, β-dimethyl-aminoethylmethacrylate.
4. the acrylic ester emulsion of long-chain unsaturated fatty acid modification according to claim 1 and 2, is characterized in that: described long-chain unsaturated fatty acid is at least one in eleostearic acid, ricinolic acid, oleum lini, soybean oil, Semen Maydis oil.
5. the acrylic ester emulsion of long-chain unsaturated fatty acid modification according to claim 1 and 2, it is characterized in that: described emulsifying agent is the Compositional type emulsifying agent of anionic and non-ionic type, wherein anionic emulsifier is at least one in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, sodium oleate, and nonionic emulsifier is at least one in polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether, oleic acid.
6. the acrylic ester emulsion of long-chain unsaturated fatty acid modification according to claim 1 and 2, is characterized in that: described initiator is at least one in Potassium Persulphate, ammonium persulphate.
7. according to the preparation method of the acrylic ester emulsion of the arbitrary described long-chain unsaturated fatty acid modification of claim 1~6, it is characterized in that comprising the steps:
A takes the initiator of water, charging capacity 1/3rd of the esters of acrylic acid soft monomer of charging capacity 1/5th and esters of acrylic acid hard monomer, charging capacity 1/2nd and emulsifying agent, whole sodium bicarbonate in proportion, said mixture material is carried out to emulsification and make pre-emulsion;
B stirs 0.5-1.0h by above-mentioned pre-emulsion under 78-85 DEG C of condition, obtains light blue emulsion;
C takes the initiator of water, residue 2/3rds of residue 4/5ths esters of acrylic acid soft monomer and esters of acrylic acid hard monomer, residue 1/2nd and emulsifying agent, whole long-chain unsaturated fatty acid, said mixture material is carried out to emulsification and make pre-emulsion;
D evenly drips the pre-emulsion making in operation c in light blue emulsion, drips 2-3h;
E dropwises rear continuation isothermal reaction, has reacted rear intensification 3-5 DEG C insulation, then cooling, and discharging, adjusting pH obtain final product.
CN201410342796.9A 2014-07-17 2014-07-17 Long-chain unsaturated fatty acid-modified acrylate emulsion and preparation method thereof Pending CN104151485A (en)

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CN105885512A (en) * 2016-06-18 2016-08-24 宁波南海化学有限公司 Powder coating leveling agent and preparation method and application thereof
WO2018027890A1 (en) * 2016-08-12 2018-02-15 Dow Global Technologies Llc Water-based pressure sensitive adhesive compositions and methods of making same
CN109135459A (en) * 2018-08-07 2019-01-04 嘉兴市嘉盛绝缘材料有限公司 A kind of insulated paint eleostearic acid modifying cinepazid emulsion and preparation method thereof
CN109294716A (en) * 2018-11-13 2019-02-01 贵州石博士科技有限公司 A kind of preparation method and application of new concrete release agent
RU2748660C2 (en) * 2016-08-12 2021-05-28 Дау Глоубл Текнолоджиз Ллк Pressure sensitive water-based adhesive compositions and methods for their production

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105885512A (en) * 2016-06-18 2016-08-24 宁波南海化学有限公司 Powder coating leveling agent and preparation method and application thereof
CN105885512B (en) * 2016-06-18 2021-05-11 宁波南海化学有限公司 Powder coating leveling agent and preparation method and application thereof
WO2018027890A1 (en) * 2016-08-12 2018-02-15 Dow Global Technologies Llc Water-based pressure sensitive adhesive compositions and methods of making same
CN109790428A (en) * 2016-08-12 2019-05-21 陶氏环球技术有限责任公司 Water based pressure sensitive adhesion agent composition and preparation method thereof
RU2741435C2 (en) * 2016-08-12 2021-01-26 Дау Глоубл Текнолоджиз Ллк Pressure-sensitive water-based adhesive compositions and methods for production thereof
RU2748660C2 (en) * 2016-08-12 2021-05-28 Дау Глоубл Текнолоджиз Ллк Pressure sensitive water-based adhesive compositions and methods for their production
CN109135459A (en) * 2018-08-07 2019-01-04 嘉兴市嘉盛绝缘材料有限公司 A kind of insulated paint eleostearic acid modifying cinepazid emulsion and preparation method thereof
CN109294716A (en) * 2018-11-13 2019-02-01 贵州石博士科技有限公司 A kind of preparation method and application of new concrete release agent
CN109294716B (en) * 2018-11-13 2021-08-20 贵州石博士科技股份有限公司 Preparation method and application of novel concrete release agent

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