CN110982023B - Preparation method of salt ion-resistant block copolymer latex - Google Patents
Preparation method of salt ion-resistant block copolymer latex Download PDFInfo
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- CN110982023B CN110982023B CN201911119209.9A CN201911119209A CN110982023B CN 110982023 B CN110982023 B CN 110982023B CN 201911119209 A CN201911119209 A CN 201911119209A CN 110982023 B CN110982023 B CN 110982023B
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- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
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Abstract
The invention provides a preparation method of salt ion resistant block copolymer latex, which is to use an amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent containing a nonionic hydrophilic polyoxyethylene group and an ionizable carboxyl group as an emulsifier for emulsion polymerization to carry out copolymerization of vinyl monomers such as styrene, acrylic ester, methacrylic ester and the like. The method uses the amphiphilic RAFT reagent of which the hydrophilic chain segment is the nonionic hydrophilic monomer containing the ionic hydrophilic monomer and the salt-resistant ion as the emulsifier for emulsion polymerization to finally prepare the segmented copolymer, the molecular weight of the segmented copolymer is controllable, the molecular weight distribution is narrow, the salt-resistant ion stability of the product latex is good, and the product latex cannot be destabilized and demulsified due to the existence of the salt ion in the subsequent application and blending process. The method has the advantages of simple flow equipment, short reaction time, high conversion rate and good latex stability, can be applied to the fields of water-based paint, modified concrete and the like which need to be added with inorganic filler, and has good industrial application prospect.
Description
Technical Field
The present invention relates to emulsion polymerization, and more particularly, to a method for preparing salt ion-resistant block copolymer latex by emulsion polymerization using reversible addition fragmentation chain transfer.
Background
Reversible addition-fragmentation chain transfer living emulsion polymerization, also called RAFT emulsion polymerization technique for short, and its amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent is obtained by polymerizing small molecular reversible addition-fragmentation chain transfer reagent with hydrophilic monomer and lipophilic monomer, and said macromolecular reversible addition-fragmentation chain transfer not only can be used as chain transfer reagent, but also can be used as emulsifying agent, and can be used for reaction for preparing block copolymer by emulsion polymerization1. Compared with other traditional polymerization methods, the method can control molecular weight and distribution without an additional emulsifier, and has the advantages of high heat transfer efficiency, low viscosity, environmental friendliness and the like of emulsion polymerization by using water as a dispersion medium; the reversible addition chain scission chain transfer reagent has wide monomer application range and can be used for producing various types of productsBlock polymer product2,3. Chinese patent of invention4A process for preparing high-molecular-weight and block polymer by reversible addition-fragmentation chain transfer emulsion polymerization features that the used RAFT reagent is the amphiphilic macro-molecule with styrene as lipophilic segment and acrylic acid as hydrophilic segment, and the alkaline liquid is added to ionize the carboxyl group of hydrophilic segment of said amphiphilic macro-molecule reversible addition-fragmentation chain transfer reagent to increase the charges carried by it and greatly increase the stability of emulsion<2.5, polymer emulsion with high colloidal stability. In summary, the amphiphilic RAFT agent used in the conventional RAFT emulsion polymerization is mainly an ionic emulsifier containing carboxylate groups, and the negative charges generated by neutralizing carboxyl groups in the hydrophilic segment of the amphiphilic RAFT agent stabilize emulsion particles, so that destabilization demulsification of the product is easy to occur in a system containing electrolytes such as inorganic salts.
The polymer latex is widely applied to the fields of coatings, concrete modification and the like, in the applications, the latex must have proper electrolyte resistance, and the latex prepared by the conventional RAFT emulsion polymerization cannot be directly applied to the latex mixed with inorganic filler due to the limitation. Electrolyte-resistant polymer latexes are typically prepared using a process in which a non-ionic emulsifier is complexed with an ionic emulsifier. The non-ionic emulsifier stabilizes the latex by forming a hydrophilic protective layer on the surface of the latex and providing steric hindrance, so that the latex is not easily affected by the existence of electrolyte and has strong salt resistance. However, the nonionic emulsifier has a limited ability to stabilize emulsion particles, and the dosage of the nonionic emulsifier is usually large, so that the performance of the product is affected.
The invention uses the amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent containing both nonionic hydrophilic polyoxyethylene groups and ionizable carboxyl groups as the emulsifier for emulsion polymerization to prepare the salt ion-resistant latex product with low emulsifier consumption and high colloid stability. However, there is no amphiphilic macro-molecule RAFT agent containing both non-ionic hydrophilic groups and ionic hydrophilic groups, such as polystyrene polyethylene, that can achieve effective reversible addition-fragmentation chain transfer emulsion polymerization of vinyl monomersReversible addition chain scission chain transfer reagent of alkenyl phenyl triethyl ammonium chloride diblock5Monoblock reversible addition and chain scission chain transfer reagent of poly diethyl methacrylic acid ethylamine6Two-block reversible addition-fragmentation chain transfer reagent of polyethylene oxide poly-diethyl-methyl-acrylic-ethylamine7And the like.
Reference to the literature
(1)Xiaoguang Wang,Yingwu Luo,Bogeng Li and Shiping Zhu.Macromolecules，2009，42，6414—6421.
(2)Yingwu Luo,Xiaoguang Wang,Yue Zhu,Bo-Geng Li and Shiping Zhu.Macromolecules,2010,43,7472-7481.
(3)Yingwu Luo,Xiaoguang Wang,Bo-Geng Li and Shiping Zhu.Macromolecules,2011,44,221-229.
(4) Light of king dawn; a process for preparing high-molecular-weight block polymer by emulsion polymerization of reversible addition-fragmentation chain transfer includes CN 200910099918.5P 2009-12-02.
(5)Save,M.；Manguian,M.；Chassenieux,C.；Charleux,B.Macromolecules 2005,38,280-289.
(6)Manguian,M.；Save,M.；Charleux,B.Macromol.Rapid.Commun.2006,27,399-404.
(7)Dos Santos,A.M.；Pohn,J.；Lansalot,M.；D’Agosto,F.Macromol.Rapid.Commun.2007,28,1325-1332.
Disclosure of Invention
The invention aims to disclose an amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent containing a nonionic hydrophilic polyoxyethylene group and an ionizable carboxyl group simultaneously as a reactive emulsifier for emulsion polymerization, and a method for controllably preparing salt ion-resistant block copolymer latex by RAFT emulsion polymerization.
The preparation method of the salt ion resistant block copolymer latex by using reversible addition-fragmentation chain transfer emulsion polymerization comprises the following steps: adding 20-40 parts by weight of water, 0.01-1.5 parts by weight of amphiphilic macromolecular reversible addition and fragmentation chain transfer reagent and 1-200 parts by weight of first-stage monomer into a reactor, stirring and mixing, introducing nitrogen to completely replace air, heating to 50-80 ℃, adding 0.002-0.04 part by weight of water-soluble initiator, adding 0.01-2 parts by weight of aqueous solution of alkali when initiating polymerization for 10-60 minutes, wherein the concentration of the aqueous solution of the alkali is determined according to the carboxyl needed to be neutralized by the amphiphilic macromolecular reversible addition and fragmentation chain transfer reagent in the reaction, and the ratio of the amount of the general alkali to the amount of the carboxyl in the amphiphilic macromolecular reversible addition and fragmentation chain transfer reagent is more than 0.5; after the time interval of 0-2 hours, sequentially adding a second section of monomer, a third section of monomer … … to an Nth section of monomer, wherein the adding amount of each section of monomer is 1-200 parts by weight, and each section of monomer is polymerized for 0.5-3 hours until the Nth section of monomer is polymerized to obtain salt ion-resistant block copolymer latex; n is the number of blocks.
The chemical structural general formula of the amphiphilic macromolecular reversible addition and chain scission chain transfer reagent simultaneously containing the nonionic hydrophilic polyoxyethylene group and the ionizable carboxyl group is as follows:
n and m in the structural formula1And m2Respectively the number of lipophilic monomers, ionic hydrophilic monomers and nonionic hydrophilic monomers, m1+m2The ratio to n is 3: 1 to 7:1, m1And m2The ratio of (A) to (B) is 3: 1 to 1: 6. Wherein the Z group is selected from: phenyl, benzyl, methyl, ethyl, propyl, isopropyl, butyl and isomers thereof, pentyl and isomers thereof, ethoxy, methoxythiol, ethylmercapto, isopropylmercapto, butylmercapto, C12A mercapto group; the R group is selected from: 1-methylbenzyl, 1-dimethylbenzyl, isopropyl, 2-diisobutyl, 2-isobutyronitrile, nitrilopentanyl, 3-benzoic acid.
Further, the lipophilic monomer is styrene, acrylate and methacrylate, the hydrophilic segment monomer section consists of ionic hydrophilic monomer and non-ionic monomer, wherein the ionic monomer is acrylic acid or methacrylic acid, and the non-ionic hydrophilic monomer is acrylic polyether ester macromonomer (CH) with polyethylene oxide as a side chain2＝CH-COO-(-CH2CH2O-)k-CH3) Or a methacrylic acid polyether ester macromonomer (CH)2＝C(CH3)-COO-(-CH2CH2O-)k-CH3) The number k of ethoxy units is from 2 to 8.
Furthermore, the molecular weight of the amphiphilic macromolecule reversible addition-fragmentation chain transfer reagent is 1000-10000. The first stage monomer, the second stage monomer and the Nth stage monomer are all formed by mixing one or more of styrene, methacrylate or acrylate according to any proportion. The water-soluble initiator is persulfate or hydrogen peroxide and derivatives thereof, and the persulfate is potassium persulfate or ammonium persulfate. The alkali is sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate.
The invention utilizes the amphiphilic macromolecular emulsifier simultaneously containing nonionic hydrophilic polyoxyethylene groups and ionizable carboxyl groups and combines the reversible addition chain scission chain transfer active free radical polymerization technology, and can prepare the salt ion-resistant block polymer latex with controllable molecular weight, molecular weight distribution of less than 2.5 and high colloid stability without the traditional emulsifier. The great innovation of the patent is that the amphiphilic macromolecules of the reversible addition and chain scission chain transfer reagent simultaneously contain an ionic hydrophilic section and a non-ionic hydrophilic section, so that the stability of salt-tolerant ions of the emulsion is improved while the higher emulsifying capacity is kept. When an amphiphilic macromolecular reversible addition and fragmentation chain transfer reagent is synthesized and used for emulsion polymerization before reaction, the length of a hydrophilic and lipophilic chain segment is adjusted, so that the reversible addition and fragmentation chain transfer reagent can be directly dissolved in water during dissolution and polymerization without using alkali such as sodium hydroxide, ammonia water and the like for neutralization, and the pH of a formed aqueous phase solution is less than or equal to 4.0; the product latex can be directly blended with inorganic particles such as calcium carbonate and the like to be used as a coating without demulsification. The method has the following advantages: (1) the reaction inhibition period is short, the reaction speed is high, the final conversion rate is high, the reaction time is saved, and the production efficiency is improved; (2) the method can realize intermittent polymerization, and the monomers, the water and the reversible addition chain scission chain transfer reagent are all added into the water before the reaction without being continuously added in the reaction process, thereby simplifying the flow equipment; (3) water is used as a dispersing medium, so that the heat transfer effect is good, and the environment is protected; (4) the stability of the emulsion can be improved by the technique of adding alkali later; (5) block copolymers can be synthesized. (6) After the obtained latex is blended with inorganic filler, the nonionic hydrophilic section plays a stabilizing role to avoid demulsification, so that the segmented copolymer latex can be applied to the fields of coating and concrete modification. The invention is not only the combination of the advantages of the reversible addition-fragmentation chain transfer living emulsion polymerization technology and the nonionic emulsifier and the ionic emulsifier, but also the expansion of the latex product of the reversible addition-fragmentation chain transfer living polymerization technology in the fields of water paint, modified concrete and the like which need to be added with inorganic filler.
Detailed Description
The reversible addition and chain scission chain transfer reagent used in the invention is dithioester or trithioester, and the chemical structural general formulas are respectively as follows:
the amphiphilic macromolecular reversible addition and fragmentation chain transfer reagent with different chain segment lengths can be prepared by the reaction of the reversible addition and fragmentation chain transfer reagent with a certain monomer and an initiator. The R group of the amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent comprises an oleophilic chain segment with the structural unit number of n as a first block and a structural unit number of m ═ m1+m2As a second block. Wherein the first block is formed by homopolymerization of an oil-soluble vinyl monomer or copolymerization of a plurality of oil-soluble monomers, and the oil-soluble monomers are styrene, acrylic ester and methacrylate; the hydrophilic segment of the second block is composed of m1An ionic hydrophilic monomer and m2The non-ionic hydrophilic monomer is formed by random copolymerization of acrylic acid or methacrylic acid as an ionic monomer and acrylic polyether ester macromonomer (CH) with polyethylene oxide side chain as a non-ionic monomer2＝CH-COO-(-CH2CH2O-)k-CH3The number k of ethoxy units being from 2 to 8) or a methacrylic acid polyether ester macromonomer (C)H2＝C-(CH3)-COO-(-CH2CH2O-)k-CH3The number k of ethoxy units is from 2 to 8).
The chemical structure of the amphiphilic macromolecular reversible addition and chain scission chain transfer reagent used in the embodiment of the invention is simple and mainly comprises the following 5 types:
the amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent (1) is obtained by copolymerizing styrene, acrylic acid and polyethylene oxide methyl acrylate into dodecyl-2-isopropyl thioester (firstly, the acrylic acid, the polyethylene oxide methyl acrylate and the dodecyl-2-isopropyl thioester are dissolved in dioxane and react for 2 hours at 80 ℃, and then styrene is supplemented to continue to react for 12 hours at 80 ℃), wherein the first block is 5 styrene homopolymerizations, and the second block is 21 acrylic acids and 7 polyethylene oxide methyl acrylates (the number of ethoxy units is 8) which are randomly copolymerized.
The amphiphilic macromolecular reversible addition and chain scission chain transfer reagent (2) is obtained by copolymerizing styrene, acrylic acid and polyethylene oxide methyl acrylate into dodecyl-2-isopropyl thioester (firstly, dissolving the acrylic acid, the polyethylene oxide methyl acrylate and the dodecyl-2-isopropyl thioester in dioxane, reacting for 2 hours at 80 ℃, and then supplementing styrene to continue reacting for 12 hours at 80 ℃), wherein the first block is 4 styrene homopolymerizations, and the second block is 6 acrylic acid and 12 polyethylene oxide methyl acrylates (the number of ethoxy units is 4) random copolymerization.
The amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent (3) is obtained by copolymerizing styrene, acrylic acid and polyethylene oxide methyl acrylate into dodecyl-2-isopropyl thioester (firstly, the acrylic acid, the polyethylene oxide methyl acrylate and the dodecyl-2-isopropyl thioester are dissolved in dioxane and react for 2 hours at 80 ℃, and then styrene is supplemented to continue to react for 12 hours at 80 ℃), wherein the first block is 5 styrene homopolymerizations, and the second block is a random copolymerization of 10 acrylic acids and 20 polyethylene oxide methyl acrylates (the number of ethoxy units is 4).
The amphiphilic macromolecular reversible addition and chain scission chain transfer reagent (4) is obtained by copolymerizing styrene, acrylic acid and polyethylene oxide methyl acrylate into dodecyl-2-isopropyl thioester (firstly, the acrylic acid, the polyethylene oxide methyl acrylate and the dodecyl-2-isopropyl thioester are dissolved in dioxane and react for 2 hours at 80 ℃, and then styrene is supplemented to continue to react for 12 hours at 80 ℃), wherein the first block is 5 styrene homopolymerizations, and the second block is a random copolymerization of 10 acrylic acids and 30 polyethylene oxide methyl acrylates (the number of ethoxy units is 4).
The amphiphilic macromolecular reversible addition and chain scission chain transfer reagent (5) is obtained by copolymerizing styrene, acrylic acid and polyethylene oxide methyl acrylate into dodecyl-2-isopropyl thioester (firstly, the acrylic acid, the polyethylene oxide methyl acrylate and the dodecyl-2-isopropyl thioester are dissolved in dioxane and react for 2 hours at 80 ℃, and then styrene is supplemented to continue to react for 12 hours at 80 ℃), wherein the first block is 5 styrene homopolymerizations, and the second block is a random copolymerization of 10 acrylic acids and 30 polyethylene oxide methyl acrylates (the number of ethoxy units is 8).
Example 1:
adding 40 g of water, 0.7 g of amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent (1) and 1 g of styrene into a reactor, stirring and mixing, stirring, introducing nitrogen for 30 minutes, heating to 70 ℃, adding 0.01 g of potassium persulfate to initiate polymerization, adding an aqueous solution containing 0.2 g of sodium hydroxide when the reaction time is 10 minutes, adding 20g of butyl acrylate when the reaction time is 60 minutes, and continuing to polymerize for 2 hours to obtain the salt ion-resistant block copolymer latex.
Example 2:
adding 40 g of water, 0.7 g of amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent (2) and 1 g of styrene into a reactor, stirring and mixing, stirring, introducing nitrogen for 30 minutes, heating to 70 ℃, adding 0.01 g of potassium persulfate to initiate polymerization, adding an aqueous solution containing 0.2 g of sodium hydroxide when the reaction time is 10 minutes, adding 20g of butyl acrylate when the reaction time is 30 minutes, and continuing to polymerize for 2 hours to obtain the salt ion-resistant block copolymer latex.
Example 3:
adding 40 g of water, 0.4 g of amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent (3) and 20g of styrene into a reactor, stirring and mixing, stirring, introducing nitrogen for 30 minutes, heating to 70 ℃, adding 0.006 g of potassium persulfate to initiate polymerization, adding an aqueous solution containing 0.1 g of sodium hydroxide when the reaction time is 30 minutes, adding 1 g of butyl acrylate when the reaction time is 120 minutes, and continuing to polymerize for 30 minutes to obtain the salt ion-resistant block copolymer latex.
Example 4:
adding 40 g of water, 0.7 g of amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent (3) and 5 g of styrene into a reactor, stirring and mixing, stirring, introducing nitrogen for 30 minutes, heating to 70 ℃, adding 0.01 g of potassium persulfate to initiate polymerization, adding an aqueous solution containing 0.1 g of sodium hydroxide when reacting for 50 minutes, adding 10 g of butyl acrylate, reacting for 180 minutes, adding 5 g of styrene, and continuing to polymerize for 90 minutes to obtain the salt ion-resistant block copolymer latex.
Example 5:
adding 40 g of water, 0.4 g of amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent (3) and 4 g of styrene into a reactor, stirring and mixing, stirring, introducing nitrogen for 30 minutes, heating to 70 ℃, adding 0.006 g of potassium persulfate to initiate polymerization, adding an aqueous solution containing 0.1 g of sodium hydroxide when reacting for 60 minutes, adding 12 g of butyl acrylate, reacting for 120 minutes, adding 4 g of styrene, and continuing to polymerize for 120 minutes to obtain the salt ion-resistant block copolymer latex.
Example 6:
adding 40 g of water, 0.7 g of amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent (4) and 5 g of styrene into a reactor, stirring and mixing, stirring, introducing nitrogen for 30 minutes, heating to 70 ℃, adding 0.01 g of potassium persulfate to initiate polymerization, adding an aqueous solution containing 0.1 g of sodium hydroxide when reacting for 50 minutes, adding 10 g of butyl acrylate, reacting for 90 minutes, adding 5 g of styrene, and continuing to polymerize for 60 minutes to obtain the salt ion-resistant block copolymer latex.
Example 7:
adding 40 g of water, 0.7 g of amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent (5) and 5 g of styrene into a reactor, stirring and mixing, stirring, introducing nitrogen for 30 minutes, heating to 70 ℃, adding 0.01 g of potassium persulfate to initiate polymerization, adding an aqueous solution containing 0.1 g of sodium hydroxide when reacting for 30 minutes, adding 10 g of butyl acrylate, reacting for 120 minutes, adding 5 g of styrene, and continuing to polymerize for 30 minutes to obtain the salt ion-resistant block copolymer latex.
The emulsion reaction rates and final conversion for examples 1-7 are shown in Table 1:
table 1: emulsion reaction rate and final conversion
| Examples | Reaction time (including inhibition period)/min | Inhibition period/min | Final conversion rate |
| 1 | 180 | 10 | 96％ |
| 2 | 150 | 10 | 98％ |
| 3 | 180 | 10 | 99％ |
| 4 | 320 | 10 | 90％ |
| 5 | 300 | 10 | 96％ |
| 6 | 200 | 10 | 90％ |
| 7 | 145 | 10 | 99％ |
Wherein, the reaction time, the polymerization inhibition period and the final conversion rate in the table 1 are measured by a mass method, and as can be seen from the table 1, the reaction polymerization inhibition period of the segmented copolymer latex of salt-tolerant ions prepared by the method of the invention is short, the reaction speed is high, the final conversion rate is high, which is beneficial to saving the reaction time and improving the production efficiency.
The criteria for the stability test of the emulsions prepared in examples 1 to 7 were the storage stability: GB6753.3-86 shows that the emulsion keeps a good dispersion state and has no coagulation after being stored for half a year, which indicates that the emulsion has good stability. The test results for each example are shown in table 2:
table 2: emulsion stability chart
| Examples | Emulsion stability |
| 1 | Good taste |
| 2 | Good taste |
| 3 | Good taste |
| 4 | Good taste |
| 5 | Good taste |
| 6 | Good taste |
| 7 | Good taste |
The molecular weight control properties of the emulsions of examples 1-7 are shown in Table 3.
Table 3: molecular weight control performance table of emulsion
| Examples | Design value of molecular weight | Molecular weight test value | Molecular weight distribution |
| 1 | 90000 | 87400 | 1.45 |
| 2 | 84000 | 82600 | 1.96 |
| 3 | 167000 | 156510 | 2.38 |
| 4 | 72000 | 71000 | 1.67 |
| 5 | 151500 | 160200 | 2.05 |
| 6 | 76000 | 71531 | 1.86 |
| 7 | 41500 | 42700 | 1.54 |
Wherein the molecular weight is designed to be within the range of
Formula calculation, where Mn,theoRefers to the molecular weight design value, M, of the polymer in the emulsion after the reaction is finishedn,RAFTRefers to an amphiphilic macromolecular reversible addition-fragmentation chain transfer reagent, M, that has not undergone polymerizationn,monomerRefers to the molecular weight of the monomer styrene, x refers to the conversion of the emulsion polymerization reaction, [ M ]]And [ RAFT ]]Respectively representing the molar concentrations of the monomer and the reversible addition-fragmentation chain transfer reagent. Molecular weight test values and molecular weight distribution PDI were determined by gel permeation chromatography Waters 1525-2414-. As can be seen from Table 3, the molecular weights measured experimentally are close to the design values, indicating that the molecular weight of the method of the invention is controllable and the molecular weight distribution is narrow.
In addition, the latex prepared by the method is tested for stability against salt ions.
Example 8:
20g of calcium carbonate particles were added to 100g of the emulsion obtained in example (1), and the mixture was stirred and mixed to prepare a latex.
Example 9:
20g of calcium carbonate particles were added to 100g of the emulsion obtained in example (2), and the mixture was stirred and mixed to prepare a latex.
Example 10:
20g of calcium carbonate particles were added to 100g of the emulsion obtained in example (3), and the mixture was stirred and mixed to prepare a latex.
Example 11:
20g of calcium carbonate particles were added to 100g of the emulsion obtained in example (4), and the mixture was stirred and mixed to prepare a latex.
Example 12:
20g of calcium carbonate particles were added to 100g of the emulsion obtained in example (5), and the mixture was stirred and mixed to prepare a latex.
Example 13:
20g of calcium carbonate particles were added to 100g of the emulsion obtained in example (6), and the mixture was stirred and mixed to prepare a latex.
Example 14:
20g of calcium carbonate particles were added to 100g of the emulsion obtained in example (7), and the mixture was stirred and mixed to prepare a latex.
The stability of the latex after mixing with calcium carbonate particles is shown in table 4:
table 4: latex stability chart after mixing with calcium carbonate particles
| Examples | Latex stability |
| 8 | Good taste |
| 9 | Good taste |
| 10 | Good taste |
| 11 | Good taste |
| 12 | Good taste |
| 13 | Good taste |
| 14 | Good taste |
After the latex is stored for half a year, the latex keeps a good dispersion state without coagulation, which indicates that the latex has good stability. In addition, the latex of the invention does not need to add an emulsifier additionally to improve the stability, and the performance of the polymer of the latex is not influenced.
Claims (6)
1. A preparation method of salt ion resistant block copolymer latex is characterized by comprising the following steps:
adding 20-40 parts by weight of water, 0.01-1.5 parts by weight of amphiphilic macromolecular reversible addition fragmentation chain transfer reagent and 1-200 parts by weight of first-stage monomer into a reactor, stirring and mixing, introducing nitrogen until air is completely replaced, heating to 50-80 ℃, adding 0.002-0.04 part by weight of water-soluble initiator, initiating polymerization for 10-60 minutes, and adding 0.01-2 parts by weight of alkali aqueous solution; wherein the ratio of the amount of the alkali substance to the amount of the carboxyl substance in the amphiphilic macromolecule reversible addition fragmentation chain transfer reagent is more than 0.5; after the time interval of 0-2 hours, sequentially adding a second section of monomer, a third section of monomer … … to an Nth section of monomer, wherein the adding amount of each section of monomer is 1-200 parts by weight, and each section of monomer is polymerized for 0.5-3 hours until the Nth section of monomer is polymerized to obtain salt ion-resistant block copolymer latex;
the chemical structural general formula of the amphiphilic macromolecule reversible addition fragmentation chain transfer reagent is as follows:
wherein m is1+m2The ratio of n to n is 3-7: 1, m1And m2The ratio of (A) to (B) is 1-18: 6; the Z group is selected from: phenyl, benzyl, methyl, ethyl, propyl, isopropyl, butyl and its isomers, pentyl and its isomers, ethoxy, ethylmercapto, isopropylmercapto, butylmercapto, C12A mercapto group; the R group is selected from: isopropyl acid group, 2-diisobutyl acid group, 2-isobutyronitrile group, nitrilopentyl acid group, 3-benzoic acid group; the lipophilic monomer comprises styrene, acrylate and methacrylate, the ionic hydrophilic monomer is acrylic acid or methacrylic acid, and the nonionic hydrophilic monomer is acrylic polyether ester macromonomer CH with polyethylene oxide as side chain2＝CH-COO-(-CH2CH2O-)k-CH3Or methacrylic acid polyether ester macromonomer CH2＝C-(CH3)-COO-(-CH2CH2O-)k-CH3The number k of ethoxy units is from 2 to 8.
2. The method for preparing the salt ion-resistant block copolymer latex according to claim 1, wherein the molecular weight of the amphiphilic macromolecular reversible addition fragmentation chain transfer reagent is 1000-10000.
3. The method for preparing the salt ion resistant block copolymer latex according to claim 1, wherein the first-stage monomer, the second-stage monomer and the Nth-stage monomer are all formed by mixing one or more of styrene, methacrylate or acrylate according to any proportion.
4. The method for preparing the salt ion resistant block copolymer latex according to claim 1, wherein the water-soluble initiator is persulfate, or hydrogen peroxide and its derivatives.
5. The method for preparing the salt ion-resistant block copolymer latex according to claim 4, wherein the persulfate is potassium persulfate or ammonium persulfate.
6. The method of claim 1, wherein the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.
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| WO2017035570A1 (en) * | 2015-08-28 | 2017-03-09 | Commonwealth Scientific And Industrial Research Organisation | Amphiphilic raft agent |
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