CN101338005B - Process for synthesizing acrylic ester copolymer of ultra-high molecular mass - Google Patents
Process for synthesizing acrylic ester copolymer of ultra-high molecular mass Download PDFInfo
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Abstract
The invention relates to a synthesis method of acrylic ester copolymer with ultra-high molecular weight (more than 6 million). The technical problem to be solved by the invention is to provide a method with multistage reaction and higher efficiency. The method comprises the following steps: (1) preparation of a seed emulsion: adding a portion weight of water and two or more unsaturated monomers with olefinic bonds, wherein the weight ratio of water to the monomers is 1:0.6 to 1; adding an emulsifying agent and a pH buffer, and adding a portion weight of or the total weight of one or two oxidants and one or two reducers to carry out reaction completely, wherein the weight ratio of the oxidant to the reducer is 1:0.7 to 1.5; and (2) multistage polymerization reaction: adding unsaturated monomers with olefinic bonds in balancing amount in multiple stages after rising the temperature, keeping the temperature at 45 to 65 DEG C, adding the balancing amount of water in multiple stages, rising the temperature to 80 to 85 DEG C, and adding the balancing amount of the oxidant and the reducer.
Description
Technical field
The present invention relates to the macromolecular compound field, specifically is the synthetic method of a kind of ultra-high molecular weight (more than 6,000,000) acrylate copolymer.
Background technology
200510105276.7 of Chinese patent literatures are called " polyvinyl chloride processing plasticizing modifier, preparation method and application thereof " and disclose plasticizing modifier---the method for polymerization macromolecule amount (high viscosity) acrylate.This method is not enough to some extent, and when disposable the feeding intake of the actual batch process of big industry, because of exothermic heat of reaction is rapid, uncontrollable temperature of reaction causes " quick-fried still gel " phenomenon, and temperature is crossed the low production efficiency that also reduced in addition.
Summary of the invention
The technical issues that need to address of the present invention are, overcome the existing deficiency of prior art, provide a kind of multistage reaction, the acrylic ester copolymer of ultra-high molecular mass synthetic method that efficient is higher.
Acrylic ester copolymer of ultra-high molecular mass synthetic method of the present invention is characterized in that:
1) preparation seed emulsion: two or more ethylene linkage unsaturated monomers of water and 15～40% (being preferably 25～40%) weight of input 25～40% weight, and water earlier and monomeric weight ratio are 1: 0.6～1 (being preferably 1: 1); Drop into emulsifying agent and pH value buffer reagent, drop into one or both oxygenants of 60～90% weight again, one or both reductive agents that reach 60～100% weight fully react, and the weight ratio of Oxidizing and Reducing Agents is 1: 0.7～1.5;
Above-mentioned ethylene linkage unsaturated monomer is 100 weight parts, water is 100～160 weight parts, emulsifying agent is 1.5～3% of an ethylene linkage unsaturated monomer weight, the pH buffer reagent is 0.3～0.5% of an ethylene linkage unsaturated monomer weight, oxygenant is 0.2～0.5% of an ethylene linkage unsaturated monomer weight, and reductive agent is 0.14～0.75% of an ethylene linkage unsaturated monomer weight;
2) stage feeding polymerization reaction: after reaction heats up, divide multistage to drop into the ethylene linkage unsaturated monomer of residuals weight, make temperature remain on 45～65 ℃; The water that divides multistage to drop into residuals weight again, and allow temperature be raised to 80～85 ℃, drop into the Oxidizing and Reducing Agents of residuals weight at last;
Described ethylene linkage unsaturated monomer is selected from acrylate, methacrylic ester, and vinylbenzene, propylene is fine;
Described emulsifying agent is ionic or nonionic emulsifier, as alkyl sulfonate or alkyl-sulphate, and preferably from hexadecyl benzene semi-annular jade pendant acid sodium, dodecylbenzene semi-annular jade pendant acid sodium, Sodium palmityl sulfate;
Described pH value buffer reagent is selected from sodium hydroxide, sodium bicarbonate, potassium hydroxide;
Described oxygenant can be water-soluble persulphate or oil soluble organic hydroperoxide, preferably from Potassium Persulphate, and ammonium persulphate, hydrogen peroxide, tertbutyl peroxide;
Described reductive agent can be a hydrosulphite, pyrosulphate or divalent metal salt, and preferably from sodium bisulfite, SODIUM HYDROSULPHITE hydrogen sodium, sodium pyrosulfate, ferrous sulfate, copper sulfate.
The present invention prepares seed emulsion earlier, stage feeding polymerization reaction on the seed emulsion basis then, and the may command temperature of reaction prevents that gel phenomenon from taking place like this.It is one of innovative point of the present invention.
As preferably, the multistage in the described stage feeding polymerization reaction is 5～30 sections, every section be spaced apart 3～10 minutes, every section charging capacity equates.
Reaction early stage is because the polymkeric substance transformation efficiency is low, and second-order transition temperature is also corresponding low, and as preferably, preparation seed emulsion phase temperature is controlled at 20～40 ℃, and stage feeding polymerization step of reaction temperature is controlled at≤and 90 ℃.
In stage feeding polymerization reaction rear half stage, because the raising of molecular weight, make the emulsion thickness that becomes, easy gel breakdown of emulsion, preferably add concentration again and be 10% emulsifier aqueous solution, add-on is 5～10% of an ethylene linkage unsaturated monomer weight, to reach stabilization of polymer emulsion purpose.
During the seeded emulsion polymerization before the stage feeding polymerization step of reaction, for improving speed of reaction, reduce inductive phase, the preferred complexing of metal ion agent of adding ethylene linkage unsaturated monomer weight 3/1000000ths～5, to remove the stopper in the monomer, described complexing of metal ion agent is selected from copper sulfate, ferrous sulfate.
The present invention has characteristics such as kick off temperature is low, and reaction relaxes and is easy to control, and the reaction times is short.The final molecular weight of described multipolymer is more than 6,000,000, and transformation efficiency reaches more than 99%.
Embodiment
Monomer content when present method can effectively improve reaction, and then make polymerization that competent monomer source be arranged, and the increase of system viscosity, it is a lot of to make that also chain termination reaction descends, and has guaranteed increasing of polymerizable molecular amount.In the time of molecular weight will being improved in other patent and the document, all be to reduce temperature of reaction and reduce initiator amount, but can make polymerization process very slow like this that reduce production efficiency greatly, the also corresponding raising of cost is a lot.And use present method, and can not reduce fully under the situation of efficiency, reach the effect that improves molecular weight.
Embodiment
Following example is used to illustrate the present invention, but the present invention should not be subjected to the restriction of these examples.
Weight-average molecular weight (Mw) is measured with gel permeation chromatography, and also available characteristic viscosity characterizes;
Example one
1) preparation seed emulsion: be reflected in one cube of reactor and carry out, in reactor, add deionized water 200kg (total amount 500kg,), add ethylene linkage unsaturated monomer---methymethacrylate 150kg (total amount 500kg), all Butyl acrylate 30kg and all Ethyl acrylate 20kg, add emulsifying agent hexadecyl benzene semi-annular jade pendant acid sodium 6kg, oxygenant Potassium Persulphate 0.144kg (total amount 0.16kg), Restore All agent sulfurous acid oxygen sodium 0.10kg, pH value buffer reagent sodium hydroxide 0.03kg, complexing of metal ion agent copper sulfate 0.000002kg and ferrous sulfate 0.000004kg stir under nitrogen protection and are warmed up to 25 ℃;
2) stage feeding polymerization reaction: observing response is emitted heat, when equitemperature is raised to 50 ℃, with remaining 350kg methymethacrylate, divide 10 sections (every spacer segments 10 minutes, every section charging capacity equates) put in the reactor, at this moment the unusual thickness of observing response system, temperature rise clearly when equitemperature is raised to 62 ℃, should be implemented whole covers that adds and cool off, and divide 15 sections (every spacer segments 3 minutes, every section charging capacity equates) add remaining 300kg deionized water, temperature can be elevated to 80 ℃ always, at this moment adds remaining Potassium Persulphate 0.016kg again, temperature can be raised to 86 ℃, cool to 30 ℃ then, measure transformation efficiency 99.2%, emulsion is emitted, record weight-average molecular weight 1,000 ten thousand, limiting viscosity is 13.1.
Example two
1) preparation seed emulsion: be reflected in one cube of reactor and carry out, in reactor, add deionized water 200kg (total amount 500kg), add ethylene linkage unsaturated monomer---methymethacrylate 150kg (total amount 500kg), all Butyl acrylate 30kg and all Ethyl acrylate 20kg, add emulsifier sodium lauryl sulfate 6kg, oxygenant ammonium persulphate 0.144kg (total amount 0.16kg), Restore All agent V-Brite B 0.10kg, whole pH value buffer reagent sodium hydroxide 0.03kg, add complexing of metal ion agent copper sulfate 0.000002kg (all) and ferrous sulfate 0.000004kg (all), under nitrogen protection, stir and be warmed up to 25 ℃;
2) stage feeding polymerization reaction: observing response is emitted heat, when equitemperature is raised to 50 ℃, with residual monomers 350kg, divide 5～30 sections (every spacer segments 10 minutes, every section charging capacity equates) put in the reactor, at this moment the unusual thickness of observing response system, temperature rise clearly when equitemperature is raised to 62 ℃, should be implemented whole add the cover cooling to add concentration be 10% emulsifying agent (water: 1kg emulsifying agent=90: 10), and divide 5～20 sections (every spacer segments 3 minutes, every section charging capacity equates) add remaining 300kg deionized water, temperature can be elevated to 86 ℃ always, at this moment adds remaining oxygenant 0.016kg again, temperature can be raised to 90 ℃, cool to 30 ℃ then, measure transformation efficiency 99.4%, emulsion is emitted, record weight-average molecular weight 600～1,130 ten thousand, limiting viscosity is 6.9～15.2.
Example three
1) preparation seed emulsion: be reflected in one cube of reactor and carry out, in reactor, add deionized water 200kg (total amount 500kg), add ethylene linkage unsaturated monomer---methymethacrylate 150kg (total amount 500kg), all Butyl acrylate 15kg and all Ethyl acrylate 20kg, whole vinylbenzene 10KG, vinylformic acid 5KG, add emulsifier sodium lauryl sulfate 6kg, oxygenant ammonium persulphate 0.144kg (total amount 0.16kg), Restore All agent V-Brite B 0.10kg, whole pH value buffer reagent sodium hydroxide 0.03kg, add complexing of metal ion agent copper sulfate 0.000002kg (all) and ferrous sulfate 0.000004kg (all), under nitrogen protection, stir and be warmed up to 25 ℃;
2) stage feeding polymerization reaction: observing response is emitted heat, when equitemperature is raised to 50 ℃, with residual monomers 350kg, divide 5～30 sections (every spacer segments 10 minutes, every section charging capacity equates) put in the reactor, at this moment the unusual thickness of observing response system, temperature rise clearly when equitemperature is raised to 62 ℃, should be implemented whole add the cover cooling to add concentration be 10% emulsifying agent (water: 1kg emulsifying agent=90: 10), and divide 5～20 sections (every spacer segments 3 minutes, every section charging capacity equates) add remaining 300kg deionized water, temperature can be elevated to 86 ℃ always, at this moment adds remaining oxygenant 0.016kg again, temperature can be raised to 90 ℃, cool to 30 ℃ then, measure transformation efficiency 99.4%, emulsion is emitted, record weight-average molecular weight 690～1,230 ten thousand, limiting viscosity is 8.3～17.2.
Example four
According to example one, the monomer segmentation added change into 6 times, other is constant, obtains weight-average molecular weight and be 1,200 ten thousand polymkeric substance, and limiting viscosity is 16.8.
Example five
According to example one, change the monomer add-on into 20 addings.Other is constant, obtains weight-average molecular weight and be 8,900,000 polymkeric substance, and limiting viscosity is 11.3.
Example six
According to example one, change the monomer add-on into 30 addings, other is constant, obtains weight-average molecular weight and be 8,100,000 polymkeric substance, and limiting viscosity is 10.1.
Example seven
According to example one.Change the deionized water add-on into 5 addings, other is constant, obtains weight-average molecular weight and be 6,400,000 polymkeric substance, and limiting viscosity is 7.5.
Example eight
According to example one, change the deionized water add-on into 10 addings, other is constant, obtains weight-average molecular weight and be 7,300,000 polymkeric substance, and limiting viscosity is 8.9.
Example nine
According to example one, change the deionized water add-on into 20 addings, other is constant, obtains weight-average molecular weight and be 1,030 ten thousand polymkeric substance.Limiting viscosity is 13.4.
The polymkeric substance that above-mentioned example obtains is used for the PVC processing of plastic, can effectively improve the degree of plasticification of PVC, and can reduce add-on, and its plasticizing effect is a times of common process ACR.
Claims (10)
1. acrylic ester copolymer of ultra-high molecular mass synthetic method is characterized in that:
1) preparation seed emulsion: the ethylene linkage unsaturated monomer is 100 weight parts, water is 100～160 weight parts, emulsifying agent is 1.5～3% of an ethylene linkage unsaturated monomer weight, pH value buffer reagent is 0.3～0.5% of an ethylene linkage unsaturated monomer weight, oxygenant is 0.2～0.5% of an ethylene linkage unsaturated monomer weight, and reductive agent is 0.14～0.75% of an ethylene linkage unsaturated monomer weight;
Drop into earlier the water of 25～40% weight and the multiple ethylene linkage unsaturated monomer of 15～40% weight, and water and monomeric weight ratio are 1: 0.6～1; Drop into emulsifying agent and pH value buffer reagent, drop into one or both oxygenants of 60～90% weight again, one or both reductive agents that reach 60～100% weight fully react, and the weight ratio of Oxidizing and Reducing Agents is 1: 0.7～1.5;
2) stage feeding polymerization reaction: after reaction heats up, divide multistage to drop into the ethylene linkage unsaturated monomer of residuals weight, make temperature remain on 45～65 ℃; The water that divides multistage to drop into residuals weight again, and allow temperature be raised to 80～85 ℃, drop into the Oxidizing and Reducing Agents of residuals weight at last;
Described ethylene linkage unsaturated monomer is selected from acrylate, methacrylic ester, vinylbenzene, vinyl cyanide;
Described emulsifying agent is selected from hexadecyl benzene sulfonic acid sodium salt, Sodium dodecylbenzene sulfonate, Sodium palmityl sulfate;
Described pH value buffer reagent is selected from sodium hydroxide, sodium bicarbonate, potassium hydroxide;
Described oxygenant is selected from Potassium Persulphate, ammonium persulphate, hydrogen peroxide, tertbutyl peroxide;
Described reductive agent is selected from sodium bisulfite, SODIUM HYDROSULPHITE hydrogen sodium, sodium pyrosulfate, ferrous sulfate.
2. acrylic ester copolymer of ultra-high molecular mass synthetic method according to claim 1 is characterized in that: the described multiple ethylene linkage unsaturated monomer that drops into earlier 25～40% weight, and water and monomeric weight ratio are 1: 1.
3. acrylic ester copolymer of ultra-high molecular mass synthetic method according to claim 1 and 2 is characterized in that: the multistage in the reaction of described stage feeding polymerization is 5～30 sections, every section be spaced apart 3～10 minutes, every section charging capacity equates.
4. acrylic ester copolymer of ultra-high molecular mass synthetic method according to claim 3 is characterized in that: preparation seed emulsion phase temperature is controlled at 20～40 ℃, and stage feeding polymerization step of reaction temperature is controlled at≤and 90 ℃.
5. acrylic ester copolymer of ultra-high molecular mass synthetic method according to claim 1 and 2 is characterized in that: adding concentration again in the stage feeding polymerization step of reaction is 10% emulsifier aqueous solution, and dosage is 5～10% of an ethylene linkage unsaturated monomer weight again.
6. acrylic ester copolymer of ultra-high molecular mass synthetic method according to claim 3 is characterized in that: adding concentration again in the stage feeding polymerization step of reaction is 10% emulsifier aqueous solution, and dosage is 5～10% of an ethylene linkage unsaturated monomer weight again.
7. acrylic ester copolymer of ultra-high molecular mass synthetic method according to claim 1 and 2, it is characterized in that: before the stage feeding polymerization step of reaction during the seeded emulsion polymerization, add 3/1000000ths～5 complexing of metal ion agent of ethylene linkage unsaturated monomer weight, described complexing of metal ion agent is selected from copper sulfate, ferrous sulfate.
8. acrylic ester copolymer of ultra-high molecular mass synthetic method according to claim 3, it is characterized in that: 3/1000000ths～5 of interpolation ethylene linkage unsaturated monomer weight complexing of metal ion agent during the seeded emulsion polymerization before the stage feeding polymerization step of reaction, described complexing of metal ion agent is selected from copper sulfate, ferrous sulfate.
9. acrylic ester copolymer of ultra-high molecular mass synthetic method according to claim 4, it is characterized in that: 3/1000000ths～5 of interpolation ethylene linkage unsaturated monomer weight complexing of metal ion agent during the seeded emulsion polymerization before the stage feeding polymerization step of reaction, described complexing of metal ion agent is selected from copper sulfate, ferrous sulfate.
10. acrylic ester copolymer of ultra-high molecular mass synthetic method according to claim 5, it is characterized in that: 3/1000000ths～5 of interpolation ethylene linkage unsaturated monomer weight complexing of metal ion agent during the seeded emulsion polymerization before the stage feeding polymerization step of reaction, described complexing of metal ion agent is selected from copper sulfate, ferrous sulfate.
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| CN101693753B (en) * | 2009-10-15 | 2011-04-13 | 晋江市南星印染材料有限公司 | Preparation method of acrylic ester emulsion |
| CN103980409B (en) * | 2014-04-30 | 2015-09-16 | 中国科学院化学研究所 | Poly-(methyl) acrylate powder of a kind of ultra-high molecular weight for 3D printing and preparation method thereof |
| CN103980411B (en) * | 2014-04-30 | 2016-02-24 | 中国科学院化学研究所 | A kind of poly-(methyl) acrylate powder of ultra-high molecular weight that can be used for 3D printing and preparation method thereof |
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