CN113072669B - Acrylate swellable rheological modifier with core-shell structure and preparation method thereof - Google Patents
Acrylate swellable rheological modifier with core-shell structure and preparation method thereof Download PDFInfo
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- CN113072669B CN113072669B CN202010005661.9A CN202010005661A CN113072669B CN 113072669 B CN113072669 B CN 113072669B CN 202010005661 A CN202010005661 A CN 202010005661A CN 113072669 B CN113072669 B CN 113072669B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
Abstract
The invention discloses an acrylate swelling type rheology modifier with a core-shell structure and a preparation method thereof, wherein the rheology modifier has a three-layer hierarchical structure, and comprises the following components in parts by weight: 1) the core structure layer is a lightly crosslinked copolymer containing acrylate monomers; 2) the transition layer is a non-crosslinked copolymer containing acrylate monomers; 3) the shell structure layer is a high-crosslinking copolymer containing acrylate monomers; the rheology modifier can reduce the content of free water in a system in the volume swelling process so as to increase the viscosity of the system, and because the external shell structure of the rheology modifier cannot be broken, and an internal alkali swelling hydrophilic substance cannot enter the system, the rheology modifier has small influence on the water resistance and water whitening resistance of a product.
Description
Technical Field
The invention relates to an acrylate swelling type rheology modifier with a core-shell structure and a preparation method thereof, wherein the acrylate swelling type rheology modifier has a three-layer hierarchical structure comprising a core structure layer, a transition layer and a shell structure layer, and can be fully swelled through neutralization in water to form transparent liquid so as to meet the rheological requirements of different aqueous systems. Meanwhile, the invention also relates to a synthetic method and application of the rheological additive.
Background
With the gradual increase of the environmental protection requirements of people and the strict national requirements on environmental protection, the water-based paint system is widely applied at present. The water paint has the advantages of reducing environmental pollution, improving operation and construction environment, saving a large amount of organic solvent, and the like.
The water paint comprises four processes from preparation to film forming, such as manufacturing, storage, construction, leveling and film forming. The viscosity requirements of the coating system vary in different processes, for example during storage of the coating, the need to maintain a high low shear viscosity for long periods of time to prevent the dispersed particles from settling down due to gravity; moderate viscosity is desired in the construction process, so that smooth coating can be ensured, and a certain film forming thickness can be ensured to improve the covering power; the viscosity should be recovered in a short time after construction to facilitate leveling of the coating film, and the viscosity should be rapidly recovered to be high after leveling to prevent sagging. For aqueous coating systems, the viscosity can be adjusted by adjusting the concentration of other solid substances, but the range of adjustment is very limited, and additives are usually added to adjust the viscosity and rheological properties of the system under different shear conditions, and such additives are usually called rheological additives. In addition to providing the desired viscosity of the system, such adjuvants can sometimes improve the flow properties of the system, the dispersion of the pigments and fillers in the system, the adhesion of the coating system, and the like.
The traditional rheology modifier is mainly natural or natural extracted and processed products such as cellulose, gelatin, sodium alginate and the like, the products are thickened by pure water phase, and the thickening efficiency can also be improved but generally have certain colors, which are mainly related to impurities contained in the products. Similarly, the vitamin thickening agent is easy to cause bacterial infection due to the polysaccharide structure, so that the paint film grows enzyme, and the appearance effect of the paint film is influenced.
The polyacrylate thickener is widely applied at present because of various structures and abundant varieties and can meet the requirements of various rheological properties. The thickening mechanism of the polyacrylate thickener comprises two thickening mechanisms of neutralization and hydrogen bond combination. The neutralization thickening is to neutralize the acidic polyacrylic acid thickener with alkali, ionize the molecules and generate negative charges along the main chain of the polymer, and promote the molecular chains to straighten and open to form a network structure by means of repulsion among the charges with the same polarity to achieve the thickening effect.
EP0013836 describes copolymers containing the following components: (1) 20-69.5% by weight of acrylic acid and/or methacrylic acid; (2)0.5 to 25% by weight of a compound having the formula CH2＝C(R)-C(O)-O-(CH2CH2O)n-RoWherein R is H or CH3N is at least 2, RoIs C8-C30Alkyl, alkylaryl or polycycloalkyl; (3) at least 30% by weight of at least one acrylic acid C1-C4Alkyl esters and/or methacrylic acid C1-C4Alkyl esters, and (4)0 to 0.1 wt.% of a polyethylenically unsaturated monomer, wherein the total amount of (1) (2), (3) and (4) is 100%.
CN103068865 discloses acrylic based multi-stage core-shell polymers comprising a linear core polymer and at least one subsequently polymerized shell polymer. At least one of the subsequently polymerized shell polymers is crosslinked. The core shell polymer surprisingly provides desirable rheological, clarity, and aesthetic properties in compositions containing the aqueous surfactant, particularly at low pH.
CN 108299608 describes an alkali swelling associative thickener, which is prepared from the following components in percentage by mass: 10 to 15 percent of methacrylic acid, 15 to 20 percent of ethyl acrylate, 0.1 to 5 percent of polyurea crosslinking monomer, 0.1 to 3 percent of hydrophobic association monomer, 0.5 to 2 percent of anionic surfactant, 0.2 to 0.1 percent of nonionic surfactant and 0.1 to 1 percent of initiator. And is prepared by emulsion polymerization. The thickener is not easily affected by the amount of residual solvent, dispersant and other assistants in the water-based system and the ion concentration of the system, and has good stability.
CN 103204968 describes a high-performance alkali swelling thickener, which is characterized by comprising the following components in parts by weight: mixing 1000-1010 parts of acrylate monomer, 5-60 parts of emulsifier, 1-50 parts of initiator, 10-150 parts of protective colloid and 1600-1900 parts of deionized water; the mixed acrylate monomer is a mixture of a soft monomer, a hard monomer and a crosslinking functional monomer. The high-performance alkali swelling thickener disclosed by the invention has the advantages of high swelling, high viscosity and high light transmittance, can resist high temperature and low temperature, and is not only suitable for daily cosmetics, household care products and adhesives, but also suitable for the field of oil field drilling.
In addition, U.S. Pat. No. 5,6441 discloses the use of low molecular weight addition polymers A having a molecular weight of less than 100,000 Dalton as dispersing assistants in free-radically initiated aqueous emulsion or suspension polymerization, from 0.1 to 40% by weight of at least one C3-C30Olefin, 40% to 99.9% by weight of at least one ethylenically unsaturated C3-C6Monocarboxylic acid, 0 to 50 wt.% of at least one ethylenically unsaturated C4-C12The dicarboxylic acid and/or the ethylenically unsaturated monoalkyl dicarboxylate or dicarboxylic anhydride obtainable from the carboxylic acid, from 0% to 30% by weight of at least one other ethylenically unsaturated compound copolymerizable with the aforementioned monomers, are composed in copolymerized form.
The above patents are all methods of synthesizing thickeners, but they are all methods in which the whole particles undergo swelling and stretching, so that they are used in aqueous formulations, resulting in poor water resistance or water-whitening resistance of the paint film.
Disclosure of Invention
The invention aims to provide an acrylate swelling rheological modifier with a core-shell structure, which can reduce the content of free water in a system in the volume swelling process so as to increase the viscosity of the system, and has small influence on the water and water whitening resistance of a product because an external shell structure of the modifier cannot be broken and an internal alkali swelling hydrophilic substance cannot enter the system.
In order to achieve the purpose, the invention adopts the following technical scheme:
an acrylate swelling rheology modifier with a core-shell structure, wherein the rheology modifier has a three-layer hierarchical structure, and comprises the following components in parts by weight:
1) the core structure layer is a lightly crosslinked copolymer containing acrylate monomers and is obtained by copolymerizing the following monomers:
-a monomer a: at least one carboxylic acid monomer in an amount of 20% to 59.8% based on the total amount of monomers copolymerized to form the core structure layer;
-a monomer b: at least one C1-C5 alkyl ester of acrylic acid or methacrylic acid and/or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid in an amount of 40% to 79.8% based on the total amount of monomers copolymerized to form the core structure layer;
-monomer c: a crosslinking comonomer which is a polyalkenyl polyether containing at least two polymerizable ethylenically unsaturated double bonds and/or a (meth) acrylate containing at least two polymerizable ethylenically unsaturated double bonds, in an amount of 0.2% to 0.8% based on the total amount of monomers copolymerized to form the core structure layer;
2) the transition layer is a non-crosslinked copolymer containing acrylate monomers and is obtained by copolymerizing the following monomers:
-a monomer d: at least one carboxylic acid monomer in an amount of 10% to 25% based on the total amount of monomers copolymerized to form the transition layer;
-monomer e: at least one C1-C5 alkyl ester of acrylic acid or methacrylic acid and/or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid in an amount of 35% to 55% based on the total amount of monomers copolymerized to form the transition layer;
-a monomer f: at least one C6-C18 alkyl ester of acrylic acid or methacrylic acid and/or at least one C6-C18 hydroxyalkyl ester of acrylic acid or methacrylic acid in an amount of 25% to 50% based on the total amount of monomers copolymerized to form the transition layer;
3) the shell structure layer is a high-crosslinking copolymer containing acrylate monomers and is obtained by copolymerizing the following monomers:
-monomer g: at least one carboxylic acid monomer in an amount of 2% to 6% based on the total amount of monomers copolymerized to form the shell structure layer;
-a monomer h: at least one C6-C18 alkyl ester of acrylic acid or methacrylic acid and/or at least one C6-C18 hydroxyalkyl ester of acrylic acid or methacrylic acid in an amount of 89-97% based on the total amount of monomers copolymerized to form the shell structure layer;
-a monomer i: and the crosslinking comonomer is polyalkenyl polyether containing at least two polymerizable ethylenically unsaturated double bonds and/or (methyl) acrylate containing at least two polymerizable ethylenically unsaturated double bonds, and the dosage of the crosslinking comonomer is 1 to 5 percent based on the total amount of monomers copolymerized to form the shell structure layer.
The core-shell structure acrylate swellable rheology modifier has a three-layer hierarchical structure which is a core structure layer, a transition layer and a shell structure layer, wherein the core structure layer is a lightly crosslinked copolymer containing acrylate monomers. The slightly crosslinked copolymer is the 'driving force' for swelling the latex particles, when alkali is added for neutralization, the acrylic acid structure with higher content on the polymer can be neutralized, carboxylic acid ions are swelled due to charge repulsion after neutralization, and the structure of the latex particles on the outer layer is swelled to be larger. When the content of the cross-linking agent is low, the molecular weight of the product is not large enough and the product cannot be fully swelled, and when the content of the cross-linking agent is high, the cross-linking concentration is large, so that the latex particles cannot be swelled, and the particle size, the later thickening efficiency and the suspension property of the product are further influenced.
Wherein the transition layer is a non-crosslinked copolymer containing acrylate monomers. The transition layer has low polymer content, mainly plays the role of transition of the core layer and the shell layer, has large monomer polarity difference between the core layer and the shell layer, needs a middle transition part, ensures that the whole latex particle has uniform cladding in the growth process, ensures that the whole latex particle forms regular spherical shape in later alkali and swelling process, and improves the performance and the effective utilization rate of the rheological modifier.
The shell structure layer is a high-crosslinking copolymer containing acrylate monomers, and is composed of monomers with a lower glass transition temperature, so that the shell structure can be effectively swelled without cracking in the core structure during swelling, the water-soluble core structure is wrapped inside, and the water-whitening resistance of the product is not affected when the water-based system is applied.
In one embodiment of the present invention, the mass ratio of the total amount of monomers copolymerized to form the core structure layer, the total amount of monomers copolymerized to form the transition layer, and the total amount of monomers copolymerized to form the shell structure layer may be (3-6): 1: (3-6), for example, the mass ratio of the total amount of monomers copolymerized to form the core structure layer to the total amount of monomers copolymerized to form the transition layer may be 3.2:1, 4:1, 4.8:1, or 5:1, and the mass ratio of the total amount of monomers copolymerized to form the shell structure layer to the total amount of monomers copolymerized to form the transition layer may be 3.5:1, 4.2:1, or 5.5: 1; through the cooperation of the three-layer structure, the excellent swelling effect is favorably realized.
In one embodiment of the present invention, the amount of the monomer a used in the core structure layer is 25% to 49.7%, such as 27%, 30%, 35%, 45% or 48%; the amount of monomer b is 50% to 74.7%, such as 52%, 60%, 65%, 70% or 72%; the amount of monomer c is 0.3% to 0.6%, such as 0.4%, 0.5% or 0.6%; based on the total amount of monomers copolymerized to form the core structure layer.
In one embodiment of the invention, the monomer d is used in an amount of 15% to 20%, such as 16%, 18% or 19%, in the transition layer; the amount of monomer e is 45% to 50%, such as 46%, 48% or 49%; the amount of monomer f is 30% to 40%, such as 32%, 35%, 38% or 39%; based on the total amount of monomers copolymerized to form the transition layer.
In one embodiment of the present invention, the amount of the monomer g in the shell structure layer is 3% to 5%, such as 3.2%, 3.5%, 4%, 4.5% or 4.8%; the amount of monomer h is 91% to 95%, such as 92%, 93% or 94%; the amount of monomer i is 2% to 4%, such as 2.2%, 2.5%, 3%, 3.5% or 3.8%; based on the total amount of monomers copolymerized to form the shell structure layer.
In the present invention, the monomers a, d and g may be the same or different carboxylic acid monomers, and for example, may be one or more of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and maleic acid, respectively.
In the present invention, the monomers b, e may be the same or different at least one C1-C5 alkyl acrylate or methacrylate and/or at least one C1-C5 hydroxyalkyl acrylate or methacrylate, such as one or more of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, respectively.
In the present invention, the monomers f, h may be the same or different at least one C6-C18 alkyl ester of acrylic acid or methacrylic acid and/or at least one C6-C18 hydroxyalkyl ester of acrylic acid or methacrylic acid, such as at least one C8-C18 alkyl ester of acrylic acid or methacrylic acid and/or at least one C8-C18 hydroxyalkyl ester of acrylic acid or methacrylic acid, which may be, for example, one or more of n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, dodecyl (meth) acrylate and stearyl (meth) acrylate, respectively.
In the present invention, the monomers c, i may be the same or different c) crosslinking comonomer selected from polyalkenyl polyethers or (meth) acrylates containing at least two polymerizable ethylenically unsaturated double bonds, or combinations thereof, the selected crosslinking agent being a monomer having at least two polymerizable ethylenically unsaturated double bonds, which may be selected from polyalkenyl polyethers selected from the group consisting of etherification products of allyl alcohol with linear or branched polyols having 2 to 15 carbon atoms or (meth) acrylate compounds of linear or branched polyols having 2 to 20 carbon atoms, wherein the polyols are selected from one or more of sucrose, pentaerythritol, dipentaerythritol, trimethylolpropane and dimers thereof. In the present invention, the crosslinking comonomer may be a (meth) acrylate-based compound, such as ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, and tetramethylolmethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like; in the present invention, the crosslinking comonomer may also be polyallyl ethers having a functionality of 2 to 4 per molecule, such as pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether and the like. It is understood by those skilled in the art that other types of crosslinking agents such as silicon crosslinking agents, zinc oxide crosslinking agents, divinyl benzene, methylene bisacrylamide, and the like are also within the scope of the present invention.
The term "(meth) acrylic acid" as used herein is meant to include both acrylic acid and methacrylic acid. Similarly, the term "alkyl (meth) acrylate" as used herein is meant to include alkyl acrylates and alkyl methacrylates, for the same reason.
In the present invention, the rheology modifier is white emulsion with initial particle size of about 200-300nm, and in one embodiment, when neutralization is carried out by adding neutralizing agent such as sodium hydroxide, potassium hydroxide, triethanolamine, AMP-95, etc. into the system, the product size can be swelled from 200-300nm to 1-1.5 μm, and the outer shell structure maintains spherical structure. During volume swelling, free water enters the interior of the rheology modifier due to osmotic pressure, and the lightly crosslinked polyacrylate compound with the core structure forms a hydrated structure, so that the content of free water in the system is reduced, and the viscosity of the system is increased.
The invention also provides a preparation method of the rheology modifier, which comprises the following steps:
(1) adding an anionic emulsifier and water into a first reaction kettle, uniformly mixing, and introducing nitrogen for replacement;
(2) configuration of monomers used for the core structure layer: adding an anionic emulsifier and water into a second reaction kettle, stirring and dissolving, and then adding monomers a, b and c to prepare a pre-emulsion 1;
(3) configuration of monomers used for the transition layer: adding an anionic emulsifier and water into a third reaction kettle, stirring and dissolving, and then adding monomers d, e and f to prepare a pre-emulsion 2;
(4) configuration of monomers used for the shell structure layer: adding anions and water into a fourth reaction kettle, stirring and dissolving, and then adding monomers g, h and i to prepare a pre-emulsion 3;
(5) preparing an initiator solution: dissolving an initiator into water, and uniformly mixing to obtain an initiator solution;
(6) heating the first reaction kettle to 80-90 ℃, gradually adding the pre-emulsion 1 and part of the initiator solution for emulsion polymerization, and carrying out heat preservation reaction after the addition is finished;
(7) further gradually adding the pre-emulsion 2 and part of the initiator into the first reaction kettle, and carrying out heat preservation reaction after the addition is finished;
(8) further gradually adding the pre-emulsion 3 and an initiator solution into the first reaction kettle, and carrying out heat preservation reaction after the addition is finished; and after the reaction is finished, cooling and discharging to obtain the acrylate swellable rheology modifier with the core-shell structure.
In one embodiment, the preparation method comprises the steps of:
(1) adding 1 part by weight of anionic emulsifier and 240 parts by weight of water, such as 250 parts by weight, into a first reaction kettle, uniformly mixing, and introducing nitrogen for replacement;
(2) configuration of monomers used for the core structure layer: adding 3-6.5 parts by weight, such as 4.4 parts by weight of anionic emulsifier and 65-120 parts by weight, such as 85, 100 or 110 parts by weight of water into a second reaction kettle, stirring and dissolving, then adding a total of 150 parts by weight, such as 160, 200 or 295 parts by weight of monomers a, b and c, and preparing into a pre-emulsion 1;
(3) configuration of monomers used for the transition layer: adding 0.5-1 part by weight, such as 0.6 or 0.9 part by weight of anionic emulsifier and 15-20 parts by weight, such as 16, 18 or 20 parts by weight of water into a third reaction kettle, stirring and dissolving, then adding 45-55 parts by weight, such as 45, 50 or 55 parts by weight of monomers d, e and f in total to prepare a pre-emulsion 2;
(4) configuration of monomers used for the shell structure layer: adding 1-3 parts by weight, such as 1.5, 2, 2.5 and 3 parts by weight of anionic emulsifier and 35-75 parts by weight, such as 40, 50 or 65 parts by weight of water into a fourth reaction kettle, stirring and dissolving, and adding 150 parts by weight, such as 150, 200 or 250 parts by weight of monomer g, h and i in total to prepare a pre-emulsion 3;
(5) preparing an initiator solution: dissolving 0.8-1.5 parts by weight, such as 1 or 1.2 parts by weight of initiator into 70-80 parts by weight, such as 72, 75 or 78 parts by weight of water, and uniformly mixing to obtain an initiator solution;
(6) heating the first reaction kettle to 80-90 ℃, gradually adding the pre-emulsion 1 and part of the initiator solution for emulsion polymerization, and carrying out heat preservation reaction after the addition is finished;
(7) further gradually adding the pre-emulsion 2 and part of the initiator into the first reaction kettle, and carrying out heat preservation reaction after the addition is finished;
(8) further gradually adding the pre-emulsion 3 and an initiator solution into the first reaction kettle, and carrying out heat preservation reaction after the addition is finished; and after the reaction is finished, cooling and discharging to obtain the acrylate swellable rheology modifier with the core-shell structure.
In the invention, the anionic emulsifier can be one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, alcohol ether sulfosuccinate, alkyl alcohol ether sulfate and alkyl alcohol ether phosphate; the initiator is one or more of organic peroxide compounds, azo compounds, inorganic persulfate compounds and hydrogen peroxide, such as azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate and hydrogen peroxide.
The core-shell structure acrylate swelling type rheology modifier has three hierarchical structures, namely a core structure layer, an excess layer and a shell structure layer, and in the volume swelling process, free water can enter the interior of the rheology modifier due to osmotic pressure and form a hydration structure with a lightly crosslinked polyacrylate compound of the core structure, so that the content of the free water of the system is reduced, and the viscosity of the system is increased. And because the external shell structure of the invention can not be broken, the internal alkali swelling hydrophilic substance can not enter the system, and the influence on the water and water whitening resistance of the product is small. Because the shell structure and the resin have good compatibility, the hydrophilic core structure can be deeply buried in the paint film after film formation, and the water-white resistance of the paint film can be effectively improved. The water-based system has excellent performances such as high thickening efficiency, good system compatibility, storage stability and the like.
Detailed Description
The present invention will be further described with reference to the following examples for better carrying out the invention, but the examples are not intended to limit the invention. The products sold on the market, alkali swelling thickener B1 and alkali swelling thickener product B2, were selected as controls and compared in different paint formulations with the products made in the examples below.
Wherein the alkali swelling thickener B1 is of DOW chemistry
ASE-60, B1 are products with high market acceptance, and the main parameters are as follows:
wherein the alkali swelling thickener B2 is Gaotai
730, B2 is widely applied in the market, and the main parameters are as follows:
| appearance of the product | Milk white liquid |
| Chemical type | Anion(s) |
| Density of | 1.06g/cm3 |
| pH value | 3 |
| Non-volatile matter | 30％ |
| Solvent(s) | Water (W) |
The raw materials listed in the following table were used in the examples of the present invention.
Example 1
The core-shell structure acrylate swelling type rheology modifier has the following synthetic formula composition shown in the table 1:
TABLE 1
The acrylate swelling rheological modifier with a core-shell structure synthesized by adopting the formula comprises the following steps:
1) adding 1g of SDS and 250g of water into a four-neck flask, connecting a condenser tube, starting stirring, uniformly mixing, and introducing nitrogen to remove oxygen in a reactor;
2) configuration of core layer monomer: adding 4.51g of SDS and 87.9g of water into a flask 1, stirring to fully dissolve the SDS, and sequentially adding 151.81g of BA, 1.19g of cross-linking monomer TMPDE and 52g of MAA to prepare a pre-emulsion 1;
3) configuration of transition layer monomer: adding 0.6g of SDS and 15g of water into a flask 2, stirring to fully dissolve the SDS, and sequentially adding 21g of BA, 17g of EHA and 7g of MAA to prepare a pre-emulsion 2;
4) and (3) configuring shell monomers: adding 2.5g of SDS and 62.5g of water into a flask 3, stirring to fully dissolve the SDS, and sequentially adding 237.5g of EHA, 5g of crosslinking monomer APE and 7.5g of MAA to prepare a pre-emulsion 3;
5) preparing an initiator solution: dissolving 1g of APS initiator into 75g of water, and uniformly mixing;
6) heating in a water bath, heating to 85 ℃, and beginning to dropwise add the pre-emulsion 1 and the initiator solution for emulsion polymerization, wherein the dropwise adding time of the pre-emulsion 1 is 1.5 hours, and the dropwise adding time of the initiator solution is 4 hours;
7) stopping dripping the initiator solution when the pre-emulsion 1 is completely dripped, and keeping the temperature at 85 ℃ for 0.5 h;
8) beginning to drip the pre-emulsion 2 and the initiator, wherein the dripping time of the pre-emulsion 2 is 0.5h, stopping dripping the initiator solution after dripping the complete pre-emulsion 2, and keeping the temperature at 85 ℃ for 0.5 h;
9) beginning to dropwise add the pre-emulsion 3 and the initiator solution, wherein the dropwise adding time of the pre-emulsion 3 is 2 hours, and simultaneously dropwise adding the initiator solution, and keeping the temperature at 85 ℃ for 2 hours;
10) cooling to room temperature, discharging and packaging to obtain the product A1.
Example 2
The core-shell structure acrylate swelling type rheology modifier has the following synthetic formula composition shown in the table 2:
TABLE 2
The synthesis process of example 2 is the same as that of example 1, and details are not repeated here, and the product A2 is obtained according to the formula.
Example 3
The core-shell structure acrylate swelling type rheology modifier has the following synthetic formula composition shown in the following table 3:
TABLE 3
The synthesis process of example 3 is the same as that of example 1, and details are not repeated here, and the product A3 is obtained according to the formula.
Example 4
The core-shell structure acrylate swelling rheology modifier has the following synthetic formula composition shown in the table 4:
TABLE 4
The synthesis process of example 4 is the same as that of example 1, and details are not repeated here, and the product A4 is obtained according to the formula.
Example 5
The core-shell structure acrylate swelling rheology modifier has the following synthetic formula composition shown in the table 5:
TABLE 5
The synthesis process of example 5 is the same as that of example 1, and details are not repeated here, so that the product A5 is obtained according to the formula.
Comparative example 1
Comparative example 1-1 differs from example 1 in that the intermediate transition layer structure is eliminated, only the core structure and the shell structure, and the composition of the synthetic formulation is shown in table 6:
table 6:
the synthesis process of comparative example 1-1 is the same as that of example 1, and details are omitted, and product A1-1 is obtained according to the formula.
The following examples 6-9 are application examples in which the items and methods to be tested are as follows:
1) adding the same amount of thickener into the system, and inspecting the KU viscosity of the system;
2) water-white test: brushing a base coat on a 150x70mm CCA plate by using a soft brush, and maintaining for 24 hours in a standard environment; roller coating the primary colored paint for one time, drying for 6 hours in a standard environment, roller coating the primary colored paint for one time, and drying overnight in the standard environment; uniformly spraying the colorful paint by a colorful paint spray gun, wherein the spraying amount is 0.45-0.53 g/plate; and (3) drying the sample plate for 24 hours in a standard environment, soaking the sample plate in water for 24 hours, observing the whitening degree of the sample plate, and grading the whitening degree from 1 to 5, wherein 1 is the worst, and 5 is the best. The standard environment presented here is an environment with a temperature of 23 ± 2 ℃ and a humidity of 50%.
3) The storage stability is that the prepared finished paint is put into a 50 ℃ oven and is placed for 14 days, and the performance of the finished paint is inspected; and (3) judging standard: the storage stability was good at 5 points, not good at 1 point;
4) and (3) testing water resistance: preparing a film with the thickness of 20 microns on a polished tinplate with the humidity of 50% at the room temperature of 25 ℃, putting the tinplate containing a paint film into water for 7 days, and observing the foaming condition of the foamed paint film; and (3) judging standard: the water resistance is good for 5 minutes, and the water resistance is poor for 1 minute;
5) scrub resistance test: and (3) manufacturing a plate according to the national standard GB/T9266-aid 2009, and testing by adopting a BGD 526 architectural coating scrub resistance instrument.
6) And (3) low-temperature film forming property test: the film was scraped off on a clean glass plate using a 400 μm wet film maker and immediately after completion was dried in a constant temperature and humidity cabinet at 3 ℃. Drying in a constant temperature and humidity cabinet for 4.5-5.5 hours until the paint film is dried.
7) And (3) testing the contrast ratio: and (4) manufacturing a board according to the national standard GB/T23981-2009, and testing by using a C84-III reflectivity instrument.
8) And (3) transparency test: the sample was placed in a sample dish and measured using a DC420 spectrophotometer.
9) Testing the suspension property: the sample and the suspended standard spheres were placed in a 50 ℃ oven and their settling rate was observed.
10) And (3) observing particle morphology: the particle shape is graded from 1 to 5, wherein 1 is the worst, 5 is the best, the particles of 1 are easy to be pasty, and the particles of 5 are not sticky and are easy to be granular.
Example 6
The building coating is a branch of the largest amount of the water-based coating market, the maturity is high, and the application types of the thickening agent are more. This application example demonstrates the use of the combination rheology modifiers of the invention in architectural coatings and comparison to commercially available products.
Building interior wall formula: 44% PVC
TABLE 7
In this formulation, comparative examples synthesized core-shell acrylate swelling rheology modifiers A1-A5 and A1-1 and commercial products B1, B2, with the following Table results:
TABLE 8
As can be seen from Table 8, the core-shell structured acrylate swelling rheology modifiers of the present invention have good thickening efficiency in PVC 44% architectural interior wall formulations without negatively impacting scrub resistance, water-white resistance, storage stability and contrast ratio.
Example 7
The core-shell structure acrylate swelling rheology modifier of the invention also has better performance in the field of personal care. This application example demonstrates the use of core-shell structured acrylate swelling rheology modifiers of the present invention in personal care shampoo formulations and comparison to commercially available products.
TABLE 9
In this formulation, comparative examples combined rheology modifiers A1-A5 and A1-1 and commercial products B1, B2 were synthesized with the following Table results:
watch 10
As can be seen from table 10, the core-shell structured acrylate swelling rheology modifiers of the present invention have better thickening efficiency in personal care shampoo formulations without negatively impacting the storage stability, clarity and suspensibility of the formulations.
Example 8
The core-shell structure acrylate swelling type rheological modifier also has better performance in the field of colorful paint of building coating. This application example demonstrates the use of core-shell structured acrylate swelling rheology modifiers of the present invention in personal care shampoo formulations and comparison to commercially available products.
The formulation of the dispersed phase consisted of:
TABLE 11
The steps of the dispersed phase prepared by adopting the formula are as follows:
1) mixing part of deionized water, a defoaming agent, cellulose or a polymer of the patent, a pH regulator, a dispersing agent, a mildew inhibitor, a bactericide and an antifreezing agent, and stirring to be in a uniform state;
2) then slowly adding pigment and filler, and dispersing at high speed until the fineness is less than or equal to 50 mu m;
3) adding the anionic emulsion, the rest deionized water, the film forming auxiliary agent and the protective glue solution, and uniformly mixing;
4) adding the color paste, and uniformly mixing to obtain the dispersion phase.
For the above 6 samples, the viscosity of the dispersed phase prepared by the stormer viscometer model STM-iv was measured, and the data obtained were as follows:
TABLE 12
| Sample numbering | B1 | B2 | A1 | A2 | A3 | A4 | A5 | A1-1 |
| Medium shear viscosity/KU | 94 | 92 | 100 | 103 | 104 | 107 | 110 | 96 |
Preparing multi-color paint and carrying out comprehensive evaluation on performance.
The water-based multicolor paint comprises a dispersed phase, a protective glue solution and a continuous phase, wherein the mass ratio of the dispersed phase to the protective glue solution is as follows: 30:30:40.
1. Preparation of protective colloid solution
7 parts of S482 are added to 93 parts of deionized water and dispersed with high-speed stirring until completely dissolved to give a colorless transparent solution for further use.
2. Preparation of the dispersed phase
The dispersion phase prepared in application example 1 was taken, and at the last step of the preparation, color paste was slowly added, adjusted to a pre-designed color, mixed to a uniform state, and kept for future use.
3. Preparation of the continuous phase
Watch 13
| Raw materials | Mass/g |
| Deionized water | 18.56 |
| Archsol○R8087 | 72 |
| Texanol | 4.32 |
| NXZ | 0.51 |
| DF-19 | 0.52 |
| LX150 | 0.56 |
| Propylene glycol | 3.53 |
The continuous phase is prepared according to the following steps: mixing the deionized water, the emulsion, the film-forming assistant, the defoaming agent, the bactericide, the mildew preventive and the antifreezing agent, and stirring at a medium speed to be in a uniform state for later use.
4. Granulating
And mixing 30 parts of the dispersed phase after color mixing with 30 parts of the protective glue solution, and adding the mixture into granulation equipment to obtain a mixture with dispersed phase color dots suspended in the protective glue solution for later use.
5. Adding the continuous phase
40 parts of the continuous phase are added to the granulation mixture and, with stirring at low speed, 0.57 parts of thickener (Vesmody. RTM. RA401) are added to complete the preparation of the multicolor paint.
For the above 6 samples, the viscosity of the prepared dispersed phase was measured by a stormer viscometer, and the state of the dispersed phase particles was observed, and the data were as follows:
TABLE 14
The core-shell acrylate swelling rheology modifier prepared by the method shows excellent performances such as high thickening efficiency, water-white resistance, good system compatibility, storage stability and the like in water-based multicolor paint.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, simplifications, substitutions and equivalents which do not depart from the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (11)
1. The core-shell structure acrylate swelling type rheology modifier is characterized by having a three-layer hierarchical structure, and comprising the following components in percentage by weight:
1) the core structure layer is a lightly crosslinked copolymer containing acrylate monomers and is obtained by copolymerizing the following monomers:
-a monomer a: at least one carboxylic acid monomer in an amount of 20% to 59.8% based on the total amount of monomers copolymerized to form the core structure layer;
-a monomer b: at least one C1-C5 alkyl ester of acrylic acid or methacrylic acid and/or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid in an amount of 40% to 79.8% based on the total amount of monomers copolymerized to form the core structure layer;
-monomer c: a crosslinking comonomer which is a polyalkenyl polyether containing at least two polymerizable ethylenically unsaturated double bonds and/or a (meth) acrylate containing at least two polymerizable ethylenically unsaturated double bonds, in an amount of 0.2% to 0.8% based on the total amount of monomers copolymerized to form the core structure layer;
2) the transition layer is a non-crosslinked copolymer containing acrylate monomers and is obtained by copolymerizing the following monomers:
-a monomer d: at least one carboxylic acid monomer in an amount of 10% to 25% based on the total amount of monomers copolymerized to form the transition layer;
-monomer e: at least one C1-C5 alkyl ester of acrylic acid or methacrylic acid and/or at least one C1-C5 hydroxyalkyl ester of acrylic acid or methacrylic acid in an amount of 35% to 55% based on the total amount of monomers copolymerized to form the transition layer;
-a monomer f: at least one C6-C18 alkyl ester of acrylic acid or methacrylic acid and/or at least one C6-C18 hydroxyalkyl ester of acrylic acid or methacrylic acid in an amount of 25% to 50% based on the total amount of monomers copolymerized to form the transition layer;
3) the shell structure layer is a high-crosslinking copolymer containing acrylate monomers and is obtained by copolymerizing the following monomers:
-monomer g: at least one carboxylic acid monomer in an amount of 2% to 6% based on the total amount of monomers copolymerized to form the shell structure layer;
-a monomer h: at least one C6-C18 alkyl ester of acrylic acid or methacrylic acid and/or at least one C6-C18 hydroxyalkyl ester of acrylic acid or methacrylic acid in an amount of 89-97% based on the total amount of monomers copolymerized to form the shell structure layer;
-a monomer i: and the crosslinking comonomer is polyalkenyl polyether containing at least two polymerizable ethylenically unsaturated double bonds and/or (methyl) acrylate containing at least two polymerizable ethylenically unsaturated double bonds, and the dosage of the crosslinking comonomer is 1 to 5 percent based on the total amount of monomers copolymerized to form the shell structure layer.
2. The swellable rheology modifier of core-shell structure acrylates of claim 1, wherein,
the mass ratio of the total amount of the monomers for forming the core structure layer by copolymerization, the total amount of the monomers for forming the transition layer by copolymerization and the total amount of the monomers for forming the shell structure layer by copolymerization is (3-6): 1: (3-6).
3. The swellable rheology modifier of core-shell structure acrylates of claim 1, wherein,
in the core structure layer, the dosage of the monomer a is 25-49.7%, the dosage of the monomer b is 50-74.7%, and the dosage of the monomer c is 0.3-0.6% based on the total amount of the monomers copolymerized to form the core structure layer;
in the transition layer, the using amount of the monomer d is 15-20%, the using amount of the monomer e is 45-50%, and the using amount of the monomer f is 30-40% based on the total amount of the monomers copolymerized to form the transition layer;
the shell structure layer comprises 3-5% of monomer g, 91-95% of monomer h and 2-4% of monomer i by total amount of monomers copolymerized to form the shell structure layer.
4. The swellable rheology modifier with core-shell structure of acrylate, according to claim 1, characterized in that the monomers a, d, g are the same or different and are one or more of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and maleic acid respectively.
5. The swellable rheology modifier of core-shell structure acrylates of claim 1, wherein the monomers b and e are the same or different and are one or more of methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.
6. The swellable rheology modifier with core-shell structure of acrylate, according to claim 1, wherein the monomers c and i are the same or different and are ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, trimethylolpropane tetra (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, and/or a-acrylate, and/or a copolymer, One or more of pentaerythritol tetra (meth) acrylate, pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropane diallyl ether, and trimethylolpropane triallyl ether.
7. The swellable rheology modifier with core-shell structure of acrylate, according to claim 1, characterized in that the monomers f and h are the same or different and are respectively one or more of n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, dodecyl (meth) acrylate and octadecyl (meth) acrylate.
8. The swellable rheology modifier with core-shell structure of acrylate, according to claim 1, characterized in that the particle size of the rheology modifier is 200nm-300 nm.
9. The swellable rheology modifier with core-shell structure of acrylate, according to claim 8, characterized in that the particle size of the swollen rheology modifier is 1 μm to 1.5 μm.
10. Process for the preparation of swellable rheology modifiers of the acrylate type with core-shell structure according to any of claims 1 to 9, characterized in that it comprises the following steps:
(1) adding an anionic emulsifier and water into a first reaction kettle, uniformly mixing, and introducing nitrogen for replacement;
(2) configuration of monomers used for the core structure layer: adding an anionic emulsifier and water into a second reaction kettle, stirring and dissolving, and then adding monomers a, b and c to prepare a pre-emulsion 1;
(3) configuration of monomers used for the transition layer: adding an anionic emulsifier and water into a third reaction kettle, stirring and dissolving, and then adding monomers d, e and f to prepare a pre-emulsion 2;
(4) configuration of monomers used for the shell structure layer: adding an anionic emulsifier and water into a fourth reaction kettle, stirring and dissolving, and then adding monomers g, h and i to prepare a pre-emulsion 3;
(5) preparing an initiator solution: dissolving an initiator into water, and uniformly mixing to obtain an initiator solution;
(6) heating the first reaction kettle to 80-90 ℃, gradually adding the pre-emulsion 1 and part of the initiator solution for emulsion polymerization, and carrying out heat preservation reaction after the addition is finished;
(7) further gradually adding the pre-emulsion 2 and part of the initiator into the first reaction kettle, and carrying out heat preservation reaction after the addition is finished;
(8) further gradually adding the pre-emulsion 3 and an initiator solution into the first reaction kettle, and carrying out heat preservation reaction after the addition is finished; and after the reaction is finished, cooling and discharging to obtain the acrylate swellable rheology modifier with the core-shell structure.
11. The preparation method according to claim 10, wherein the anionic emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, alcohol ether sulfosuccinate, alkyl alcohol ether sulfate and alkyl alcohol ether phosphate;
the initiator is one or more of organic peroxide compounds, azo compounds, inorganic persulfate compounds and hydrogen peroxide.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311261A (en) * | 2000-03-02 | 2001-09-05 | 山东省昌乐县合力塑料改性剂厂 | Nuclear-shell graft copolymer chemical bond connected between nuclear and shell and its preparing method |
| CN1410495A (en) * | 2002-11-20 | 2003-04-16 | 广州擎天新材料研究开发有限公司 | Preparation method of covering emulsion used in water printing ink |
| CN1845883A (en) * | 2003-09-04 | 2006-10-11 | 默克专利股份有限公司 | Use of core-shell particles |
| CN109957062A (en) * | 2017-12-22 | 2019-07-02 | 万华化学（宁波）有限公司 | High cross-linked acrylic acid lipin polymer and preparation method thereof and purposes as thickener |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004075943A1 (en) * | 2003-02-28 | 2004-09-10 | Biointeractions Ltd. | Polymeric network system for medical devices and methods of use |
-
2020
- 2020-01-03 CN CN202010005661.9A patent/CN113072669B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311261A (en) * | 2000-03-02 | 2001-09-05 | 山东省昌乐县合力塑料改性剂厂 | Nuclear-shell graft copolymer chemical bond connected between nuclear and shell and its preparing method |
| CN1410495A (en) * | 2002-11-20 | 2003-04-16 | 广州擎天新材料研究开发有限公司 | Preparation method of covering emulsion used in water printing ink |
| CN1845883A (en) * | 2003-09-04 | 2006-10-11 | 默克专利股份有限公司 | Use of core-shell particles |
| CN109957062A (en) * | 2017-12-22 | 2019-07-02 | 万华化学（宁波）有限公司 | High cross-linked acrylic acid lipin polymer and preparation method thereof and purposes as thickener |
Non-Patent Citations (2)
| Title |
|---|
| A Rheological Model for Polymer Blends based on the Concentric Multilayer Approach. 1. Homogeneous Polymer Blends;Line-Hwa Chu;《Polymer International》;19941231;95- 103 * |
| 丙烯酸酯类抗冲改性剂的合成与应用性能;张宁;《中国优秀博硕士学位论文全文数据库（硕士）工程科技I辑》;20120515(第5期);B016-260 * |
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