CN111019281B - Acrylate epoxy resin hybrid emulsion, preparation method and application thereof, and artificial colored sand using acrylate epoxy resin hybrid emulsion - Google Patents
Acrylate epoxy resin hybrid emulsion, preparation method and application thereof, and artificial colored sand using acrylate epoxy resin hybrid emulsion Download PDFInfo
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
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- 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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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
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Abstract
The invention provides an acrylate epoxy resin hybrid emulsion, a preparation method and application thereof and artificial colored sand using the same. The acrylate epoxy resin hybrid emulsion comprises acrylic resin, epoxy resin and an emulsifier, wherein the epoxy resin is dispersed in a network of the acrylic resin; the acrylic resin is a polymerization product of acrylate monomers, and the acrylate monomers consist of 64-70 wt% of methyl methacrylate, 29-35 wt% of butyl acrylate and 1-3 wt% of modified acrylate; the mass ratio of the acrylate monomer to the epoxy resin is (60-80) to (20-40). When the acrylate epoxy resin hybrid emulsion provided by the invention is cured, the strength is quickly established, the final strength, the bonding force and the wear resistance are higher, and the acrylate epoxy resin hybrid emulsion is yellowing-resistant, ageing-resistant and low in cost. The artificial colored sand prepared based on the hybrid emulsion has the characteristics of high wear resistance and good aging resistance.
Description
Technical Field
The invention belongs to the technical field of building coatings, and particularly relates to an acrylate epoxy resin hybrid emulsion, a preparation method and application thereof, and artificial colored sand using the acrylate epoxy resin hybrid emulsion.
Background
With the rapid development of the building industry, personalized paint veneers become the mainstream of the current exterior decoration of building paints, such as texture paints, brick-like paints, stone-like paints, multicolor paints and the like. The natural granite particles are used as coloring materials of the stone-like paint, so that the stone-like paint has excellent weather resistance, can protect the beauty of buildings for a long time, can be constructed on building curved surfaces in any shapes, can be sprayed into a multicolor marble effect, fully shows the unique shape and rich texture of natural stones, and is deeply loved by people. With the increase of the proportion of high-rise buildings, the demand of the stone-like paint is larger and larger.
As a decorative material, the colored sand is always an important aggregate of building coating, and plays an important role in building materials with the advantages of bright color, stable performance, rich texture, no toxicity, environmental protection and the like. At present, the raw material colored sand for producing the stone-like paint is natural colored sand, and along with the strict requirements of environmental protection policies on mineral sources, the supply of the natural colored sand is more and more limited. Meanwhile, most of natural colored sand is chaotic in color and luster, poor in strength and easy to pulverize due to direct crushing from nature. The natural colored sand with bright color is less in quantity, expensive and large in limitation. The artificial colored sand is formed by coloring quartz sand, has various and rich colors, bright colors, consistent colors, uniform granularity, high hardness and good durability, and gradually becomes a preferred material for producing modern real stone paint.
At present, there are two kinds of domestic artificial color sand making processes. One is high temperature sintering process, which includes mixing inorganic pigment, low melting point matter and quartz sand, sintering at 1350 deg.c, crushing and sieving to obtain color sand product. However, the method has the disadvantages of high energy consumption, complex process and difficult color control. Meanwhile, a method for preparing artificial colored sand by adopting a ceramic colored glaze sintering principle is adopted, but the process has high requirements on a base material, is difficult to control color, and often needs secondary coating, so that the production cost is greatly increased.
The other method is a dyeing method for coating the pigment with an organic adhesive, wherein the pigment is adhered to quartz sand through organic resins such as acrylic resin, organic silicon resin and the like. For example, CN 102464460a discloses a color sand and a preparation method thereof, namely, acrylic resin is used as an adhesive of artificial color sand. The acrylic resin has the advantages of yellowing resistance, aging resistance and low cost, but the strength is poor, the daily color matching requirement of the real stone paint is difficult to guarantee due to the wear resistance, and the artificial color sand prepared from the acrylic resin is easy to fade due to long-time friction, so that the use risk of the artificial color sand is increased undoubtedly.
With the continuous development of the organic resin industry, more and more resins with excellent performance enter the artificial color sand industry to be used as color sand color-mixing adhesives.
The epoxy resin contains hydroxyl with very high polarity and difficult hydrolysis, has very strong adhesive force after being cured into a film, is very excellent in chemical resistance, has good high and low temperature resistance and higher mechanical strength, and has been widely researched and applied in the field of epoxy floor coatings. Therefore, researchers can directly use the epoxy resin for the epoxy floor coating in the artificial colored sand adhesive. For example, CN 1986479a discloses an aqueous epoxy color sand mortar, a preparation method and a construction method thereof, namely, an adhesive using an aqueous epoxy resin for artificial color sand. Although the epoxy resin has enough mechanical strength after being cured, the problems of easy yellowing, no aging resistance and complex curing process are very prominent, and the cost is high.
The polyurethane is an organic resin with excellent ageing resistance and mechanical property, and is suitable for being used as an adhesive of artificial colored sand. The polyurethane industry at present develops very rapidly, but the price of raw materials does not fluctuate greatly, the cost is too high, and therefore, the application is greatly limited.
Other synthetic resins are also used as artificial colored sand adhesives, for example, the benzene-acrylic emulsion colored sand coating is manufactured and used, and benzene-acrylic copolymer emulsion is used as the adhesive to prepare artificial colored sand, but the artificial colored sand coating has the defects of poor resin adhesion, hardness, acid and alkali resistance and weather resistance.
The existing numerical values for the artificial colored sand adhesive have respective defects, so that the organic resin for the artificial colored sand adhesive, which is simple in curing process, high in strength and wear resistance after curing, yellowing-resistant, aging-resistant and low in cost, is expected to be obtained in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an acrylate epoxy resin hybrid emulsion, a preparation method and application thereof and artificial colored sand using the acrylate epoxy resin hybrid emulsion. When the acrylate epoxy resin hybrid emulsion provided by the invention is cured, the strength is quickly established, the final strength, the bonding force and the wear resistance are higher, and the acrylate epoxy resin hybrid emulsion is yellowing-resistant, ageing-resistant and low in cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an acrylate epoxy hybrid emulsion comprising:
acrylic resin, epoxy resin and an emulsifier, wherein the epoxy resin is dispersed in a network of the acrylic resin;
the acrylic resin is a polymerization product of acrylate monomers, and the acrylate monomers consist of 64-70 wt% of methyl methacrylate, 29-35 wt% of butyl acrylate and 1-3 wt% of modified acrylate;
the mass ratio of the acrylate monomer to the epoxy resin is (60-80) to (20-40).
In the invention, the content of methyl methacrylate in the acrylate monomer is 64-70 wt%; for example, it may be 64 wt%, 65 wt%, 66 wt%, 67 wt%, 68 wt%, 69 wt%, 70 wt%, or the like.
The content of butyl acrylate in the acrylate monomer is 29-35 wt%; for example, it may be 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, or the like.
The content of the modified acrylate in the acrylate monomer is 1-3 wt%; for example, it may be 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, 2 wt%, 2.2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, or the like.
The mass ratio of the acrylate monomer to the epoxy resin is (60-80) to (20-40); for example, 60:40, 62:38, 65:35, 68:32, 70:30, 72:28, 75:25, 78:22, or 80:20, etc.
The invention utilizes different acrylate compounds to synthesize the acrylic resin with good hardness and toughness; the epoxy resin is inserted into the network of the acrylic resin molecular chain, and forms an interpenetrating network after crosslinking and curing, so that the epoxy resin has high binding power, strength and wear resistance.
In the present invention, since the acrylic resin is cured quickly, the strength of the hybrid emulsion is established quickly when cured, and the initial strength is determined by the acrylic resin, but the final strength is determined by the epoxy resin. The mass ratio of the acrylate monomer to the epoxy resin is (60-80): 20-40), and when the proportion of the epoxy resin is too large, the mechanical strength of the emulsion after curing is reduced because the acrylate monomer and the epoxy resin are incompatible; too small a proportion of epoxy resin also results in a lower final mechanical strength.
Compared with epoxy resin emulsion, the acrylic resin in the hybrid emulsion provided by the invention replaces part of epoxy resin, so that the hybrid emulsion has better yellowing resistance and aging resistance and lower cost.
As a preferable technical scheme of the invention, the epoxy value of the epoxy resin is 0.4-0.5; for example, it may be 0.4, 0.41, 0.42, 0.43, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, or 0.5, etc.
Preferably, the modified acrylate is a silicone modified acrylate and/or an organofluorine modified acrylate.
In the present invention, the silicone-modified acrylate is preferably an acrylate modified with a silicone active monomer having a carbon-carbon double bond. Illustratively, the organosilicon reactive monomer containing a carbon-carbon double bond may be methylvinylchlorosilane, vinyltrichlorosilane, or the like.
In a preferred embodiment of the present invention, the emulsifier accounts for 7 to 11% by mass of the acrylate monomer, and may be, for example, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, or the like.
Preferably, the emulsifier is a composite emulsifier of alkylphenol polyoxyethylene and sodium dodecyl benzene sulfonate.
Preferably, the mass ratio of the alkylphenol polyoxyethylene to the sodium dodecyl benzene sulfonate is 6: 1.
The composite emulsifier of alkylphenol ethoxylates and sodium dodecyl benzene sulfonate is adopted, which is beneficial to controlling the particle size and the polymerization degree of micelles in the emulsion, so that the hybrid emulsion has good comprehensive performance.
On the other hand, the invention provides a preparation method of the acrylate epoxy resin hybrid emulsion, which comprises the following steps:
(1) dispersing 70-90% (such as 70%, 72%, 74%, 75%, 76%, 78%, 80%, 82%, 84%, 85%, 86%, 88%, or 90%, etc.) of the formula amount of acrylate monomer in an aqueous solution of an emulsifier, and adjusting the pH to 7-8 to obtain an acrylate emulsion;
(2) carrying out emulsion polymerization on the acrylate emulsion under the action of an initiator to obtain an acrylic resin emulsion;
(3) and dissolving epoxy resin by using the residual acrylate monomer, adding the epoxy resin into the acrylic resin emulsion, and heating for reaction to obtain the acrylate epoxy resin hybrid emulsion.
The solid content of the obtained acrylate epoxy resin hybrid emulsion can be controlled by the using amount of water in the emulsifier aqueous solution in the step (1), and when the hybrid emulsion is used for artificial colored sand, the solid content is preferably more than or equal to 10 wt%. In step (2), it is ensured that sufficient acrylate monomer is converted to acrylic resin to form an acrylic resin network, so that the amount of acrylate monomer used to dissolve the epoxy resin in step (3) cannot exceed 30% of the formula amount. The temperature rise reaction in the step (3) helps the epoxy resin to enter the acrylic resin network more quickly.
In the present invention, the timing of the addition of the epoxy resin has a large influence on the performance of the hybrid emulsion, and the timing of the addition can not be before the polymerization reaction nor after all the acrylate monomers are converted into the acrylic resin. If the epoxy resin is mixed with the acrylate monomer firstly and then emulsion polymerization is carried out, the reaction system is easy to be unstable, and the performance of the hybrid emulsion is influenced; if the epoxy resin is added after all of the acrylate monomer is converted to the acrylic resin, the epoxy resin has difficulty entering the network of the acrylic resin. If the acrylate epoxy resin hybrid emulsion is prepared by a method of grafting the epoxy resin with the acrylic resin, the initial strength of the resin component is easily high, the viscosity of the emulsion is too high, and the emulsion is difficult to apply to artificial colored sand.
As a preferable technical scheme of the invention, the initiator accounts for 0.1-1% of the total mass of the acrylate monomer in the step (2); for example, it may be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.
Preferably, the initiator is ammonium persulfate or peroxide.
As a preferred embodiment of the present invention, the emulsion polymerization method in the step (2) is:
taking 10-20% (such as 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% and the like) of the acrylate emulsion, adding 30-50% (such as 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50% and the like) of a formula amount of an initiator, reacting until an emulsion system turns blue, and dropwise adding the rest of the acrylate emulsion and the initiator while reacting until the dropwise adding is finished to obtain the acrylic resin emulsion.
Preferably, the temperature of the reaction in step (2) is 75-85 ℃; for example, the temperature may be 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃ or 85 ℃.
Preferably, the remaining acrylate emulsion and the initiator are added dropwise over 3 h.
Preferably, the reaction temperature in step (3) is 80-90 ℃, for example, 80 ℃, 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ or 90 ℃ and the like; the time is 1 to 3 hours, and may be, for example, 1 hour, 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours, 2.8 hours, 3 hours, or the like.
Preferably, after the reaction in step (3) is finished, the following operations are also performed: adjusting the pH value of the emulsion system to 7-8.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) dispersing 70-90% of acrylate monomer with formula amount in an aqueous solution of an emulsifier, and adjusting the pH to 7-8 to obtain acrylate emulsion;
(2) taking 10-20% of the acrylate emulsion, adding 30-50% of initiator according to the formula amount, reacting at 75 ℃ until the emulsion system turns blue, dropwise adding the rest acrylate emulsion and initiator while reacting, and completing dropwise adding within 3h to obtain acrylic resin emulsion;
(3) and dissolving epoxy resin by using the residual acrylate monomer, adding the epoxy resin into the acrylic resin emulsion, heating to 85 ℃, reacting for 1h, and adjusting the pH value of an emulsion system to 7-8 to obtain the acrylate epoxy resin hybrid emulsion.
In a third aspect, the invention provides an application of the acrylate epoxy resin hybrid emulsion in an artificial colored sand adhesive.
In a fourth aspect, the invention provides artificial colored sand, which is prepared from the following raw materials:
in the present invention, the inorganic toner may be 10 parts by mass, 12 parts by mass, 14 parts by mass, 15 parts by mass, 16 parts by mass, 18 parts by mass, 20 parts by mass, 22 parts by mass, 24 parts by mass, 25 parts by mass, 26 parts by mass, 28 parts by mass, 30 parts by mass, or the like.
The acrylate epoxy hybrid emulsion may be 20 parts by mass, 22 parts by mass, 25 parts by mass, 28 parts by mass, 30 parts by mass, 32 parts by mass, 35 parts by mass, 38 parts by mass, 40 parts by mass, 42 parts by mass, 45 parts by mass, 48 parts by mass, 50 parts by mass, 52 parts by mass, 55 parts by mass, 58 parts by mass, 60 parts by mass, or the like.
The curing agent may be 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass, 13 parts by mass, 14 parts by mass, 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass, or the like.
Preferably, the curing agent is an aliphatic polyamine and/or an aromatic polyamine.
In a fifth aspect, the invention provides a preparation method of the artificial colored sand, which comprises the following steps:
firstly, mixing quartz sand, inorganic toner, acrylate epoxy resin hybrid emulsion and a curing agent according to the formula ratio at a stirring speed of 100-200r/min (such as 100r/min, 120r/min, 140r/min, 150r/min, 160r/min, 180r/min or 200 r/min) for 3-5min (such as 3min, 3.2min, 3.5min, 3.8min, 4min, 4.2min, 4.5min, 4.8min or 5 min) and drying by hot air at the temperature of 120-150 ℃; and then dehydrating and curing in an environment of 100-200 ℃ (such as 100 ℃, 120 ℃, 140 ℃, 150 ℃, 160 ℃, 180 ℃ or 200 ℃ and the like), or curing at normal temperature for at least 3 days to obtain the artificial colored sand.
Compared with the prior art, the invention has the following beneficial effects:
the invention utilizes different acrylate compounds to synthesize the acrylic resin with good hardness and toughness; the epoxy resin is inserted into the network of the acrylic resin molecular chain, and forms an interpenetrating network after crosslinking and curing, so that the epoxy resin has high binding power, strength and wear resistance. The acrylate epoxy resin hybrid emulsion provided by the invention is used for preparing artificial colored sand, and is used for carrying out adhesion and wear resistance tests (stirring at a high speed of 1000r/min in a water phase), wherein the color-losing time is more than or equal to 20 min.
The acrylate epoxy resin hybrid emulsion provided by the invention is dried quickly, the surface drying time of a coating film (with the thickness of 200 mu m) is less than or equal to 1h at normal temperature, and the actual drying time is less than or equal to 2 h; the strength is quickly established during curing, and the final mechanical strength can be achieved after curing for 3 days at normal temperature.
The acrylate epoxy resin hybrid emulsion provided by the invention has a long pot life, and after the curing agent is added, the acrylate epoxy resin hybrid emulsion is placed for 10 hours at normal temperature, and the viscosity is increased by less than or equal to 20%.
In addition, the acrylate epoxy resin hybrid emulsion provided by the invention has lower cost than epoxy resin, and better yellowing resistance and aging resistance.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
An acrylate epoxy resin hybrid emulsion (solid content is 20 wt%) is prepared from the following raw materials in parts by mass:
60 parts of an acrylate monomer, 40 parts of an epoxy resin E44 (Hunan Balling petrochemical, epoxy value 0.44), 5.4 parts of an emulsifier and 0.6 part of ammonium persulfate;
wherein the acrylate monomer consists of 64 wt% of methyl methacrylate, 35 wt% of butyl acrylate and 1 wt% of methyl vinyl chlorosilane modified methyl methacrylate;
the emulsifier is composed of 4.8 parts of alkylphenol polyoxyethylene ether and 0.8 part of sodium dodecyl benzene sulfonate.
The preparation method of the acrylate epoxy resin hybrid emulsion comprises the following steps:
(1) dispersing 42 parts of acrylate monomer in an aqueous solution of an emulsifier, and adjusting the pH to 7.4 to obtain acrylate emulsion;
(2) taking 10% of the acrylic ester emulsion, adding 0.18 part of initiator, reacting at 75 ℃ until the emulsion system turns blue, dropwise adding the rest acrylic ester emulsion and the initiator while reacting, and obtaining acrylic resin emulsion after dropwise adding within 3 h;
(3) and (3) dissolving epoxy resin E44 by using the residual acrylate monomer, adding the dissolved epoxy resin E44 into the acrylic resin emulsion, heating to 85 ℃, reacting for 1h, and adjusting the pH value of the emulsion system to 7.4 to obtain the acrylic ester epoxy resin hybrid emulsion.
The artificial colored sand prepared by using the acrylate epoxy resin hybrid emulsion comprises the following raw materials in parts by weight:
the preparation method of the artificial colored sand comprises the following steps:
firstly, mixing quartz sand, inorganic toner, acrylate epoxy resin hybrid emulsion and curing agent according to the formula ratio at a stirring speed of 100r/min for 3min, and drying by hot air at 150 ℃; and curing for 7 days at normal temperature to obtain the artificial colored sand.
Example 2
An acrylate epoxy resin hybrid emulsion (solid content is 20 wt%) is prepared from the following raw materials in parts by mass:
65 parts of an acrylate monomer, 35 parts of an epoxy resin E44 (Hunan Balling petrochemical, epoxy value 0.44), 4.55 parts of an emulsifier and 0.52 part of ammonium persulfate;
wherein the acrylate monomer consists of 65 wt% of methyl methacrylate, 33 wt% of butyl acrylate and 2 wt% of methyl vinyl chlorosilane modified methyl methacrylate;
the emulsifier is composed of 3.9 parts of alkylphenol polyoxyethylene ether and 0.65 part of sodium dodecyl benzene sulfonate.
The preparation method of the acrylate epoxy resin hybrid emulsion comprises the following steps:
(1) dispersing 52 parts of acrylate monomer into an aqueous solution of an emulsifier, and adjusting the pH to 7.4 to obtain an acrylate emulsion;
(2) taking 15% of the acrylic ester emulsion, adding 0.21 part of initiator, reacting at 80 ℃ until the emulsion system turns blue, dropwise adding the rest acrylic ester emulsion and the initiator while reacting, and obtaining acrylic resin emulsion after dropwise adding within 3 h;
(3) and (3) dissolving epoxy resin E44 by using the residual acrylate monomer, adding the dissolved epoxy resin E44 into the acrylic resin emulsion, heating to 80 ℃, reacting for 3 hours, and adjusting the pH value of an emulsion system to 7.4 to obtain the acrylic ester epoxy resin hybrid emulsion.
The artificial colored sand prepared by using the acrylate epoxy resin hybrid emulsion comprises the following raw materials in parts by weight:
the preparation method of the artificial colored sand comprises the following steps:
firstly, mixing quartz sand, inorganic toner, acrylate epoxy resin hybrid emulsion and curing agent according to the formula ratio at a stirring speed of 150r/min for 4min, and drying by hot air at 150 ℃; and curing for 7 days at normal temperature to obtain the artificial colored sand.
Example 3
An acrylate epoxy resin hybrid emulsion (solid content is 20 wt%) is prepared from the following raw materials in parts by mass:
70 parts of an acrylate monomer, 30 parts of an epoxy resin E44 (Hunan Balling petrochemical, epoxy value 0.44), 5.6 parts of an emulsifier and 0.42 part of ammonium persulfate;
wherein the acrylate monomer consists of 66 wt% of methyl methacrylate, 31 wt% of butyl acrylate and 3 wt% of methyl vinyl chlorosilane modified methyl methacrylate;
the emulsifier is composed of 4.8 parts of alkylphenol polyoxyethylene ether and 0.8 part of sodium dodecyl benzene sulfonate.
The preparation method of the acrylate epoxy resin hybrid emulsion comprises the following steps:
(1) dispersing 52.5 parts of acrylate monomer in an aqueous solution of an emulsifier, and adjusting the pH to 7.4 to obtain acrylate emulsion;
(2) taking 20% of the acrylic ester emulsion, adding 0.21 part of initiator, reacting at 85 ℃ until the emulsion system turns blue, dropwise adding the rest acrylic ester emulsion and the initiator while reacting, and obtaining acrylic resin emulsion after dropwise adding within 3 h;
(3) and (3) dissolving epoxy resin E44 by using the residual acrylate monomer, adding the dissolved epoxy resin E44 into the acrylic resin emulsion, heating to 90 ℃, reacting for 2 hours, and adjusting the pH value of an emulsion system to 7.4 to obtain the acrylic ester epoxy resin hybrid emulsion.
The artificial colored sand prepared by using the acrylate epoxy resin hybrid emulsion comprises the following raw materials in parts by weight:
the preparation method of the artificial colored sand comprises the following steps:
firstly, mixing quartz sand, inorganic toner, acrylate epoxy resin hybrid emulsion and curing agent according to the formula ratio at a stirring speed of 200r/min for 3min, and drying by hot air at 150 ℃; and curing for 7 days at normal temperature to obtain the artificial colored sand.
Example 4
An acrylate epoxy resin hybrid emulsion (solid content is 20 wt%) is prepared from the following raw materials in parts by mass:
75 parts of an acrylate monomer, 25 parts of an epoxy resin E44 (Hunan Balling petrochemical, epoxy value 0.44), 7.5 parts of an emulsifier and 0.3 part of ammonium persulfate;
wherein the acrylate monomer consists of 68 wt% of methyl methacrylate, 30 wt% of butyl acrylate and 2 wt% of vinyl trichlorosilane modified methyl methacrylate;
the emulsifier is composed of 6.4 parts of alkylphenol polyoxyethylene ether and 1.1 part of sodium dodecyl benzene sulfonate.
The preparation method of the acrylate epoxy resin hybrid emulsion comprises the following steps:
(1) dispersing 67.5 parts of acrylate monomer in an aqueous solution of an emulsifier, and adjusting the pH to 7.4 to obtain acrylate emulsion;
(2) taking 12% of the acrylic ester emulsion, adding 0.1 part of initiator, reacting at 75 ℃ until the emulsion system turns blue, dropwise adding the rest acrylic ester emulsion and the initiator while reacting, and obtaining acrylic resin emulsion after dropwise adding within 3 h;
(3) and (3) dissolving epoxy resin E44 by using the residual acrylate monomer, adding the dissolved epoxy resin E44 into the acrylic resin emulsion, heating to 85 ℃, reacting for 1h, and adjusting the pH value of the emulsion system to 7.4 to obtain the acrylic ester epoxy resin hybrid emulsion.
The artificial colored sand prepared by using the acrylate epoxy resin hybrid emulsion comprises the following raw materials in parts by weight:
the preparation method of the artificial colored sand comprises the following steps:
firstly, mixing quartz sand, inorganic toner, acrylate epoxy resin hybrid emulsion and curing agent according to the formula ratio at a stirring speed of 120r/min for 5min, and drying by hot air at 150 ℃; and curing for 7 days at normal temperature to obtain the artificial colored sand.
Example 5
An acrylate epoxy resin hybrid emulsion (solid content is 20 wt%) is prepared from the following raw materials in parts by mass:
80 parts of acrylate monomer, 20 parts of epoxy resin E44 (Hunan Ba Ling petrochemical, epoxy value 0.44), 8.8 parts of emulsifier and 0.4 part of ammonium persulfate;
wherein the acrylate monomer consists of 70 wt% of methyl methacrylate, 29 wt% of butyl acrylate and 1 wt% of vinyl trichlorosilane modified methyl methacrylate;
the emulsifier is composed of 7.5 parts of alkylphenol polyoxyethylene ether and 1.3 parts of sodium dodecyl benzene sulfonate.
The preparation method of the acrylate epoxy resin hybrid emulsion comprises the following steps:
(1) dispersing 68 parts of acrylate monomer in an aqueous solution of an emulsifier, and adjusting the pH to 7.4 to obtain acrylate emulsion;
(2) taking 18% of the acrylic ester emulsion, adding 0.2 part of initiator, reacting at 75 ℃ until the emulsion system turns blue, dropwise adding the rest acrylic ester emulsion and the initiator while reacting, and obtaining acrylic resin emulsion after dropwise adding within 3 h;
(3) and (3) dissolving epoxy resin E44 by using the residual acrylate monomer, adding the dissolved epoxy resin E44 into the acrylic resin emulsion, heating to 85 ℃, reacting for 1h, and adjusting the pH value of the emulsion system to 7.4 to obtain the acrylic ester epoxy resin hybrid emulsion.
The artificial colored sand prepared by using the acrylate epoxy resin hybrid emulsion comprises the following raw materials in parts by weight:
the preparation method of the artificial colored sand comprises the following steps:
firstly, mixing quartz sand, inorganic toner, acrylate epoxy resin hybrid emulsion and curing agent according to the formula ratio at a stirring speed of 180r/min for 4min, and drying by hot air at 150 ℃; and curing for 7 days at normal temperature to obtain the artificial colored sand.
Comparative example 1
The difference from the example 1 is only that the mass part of the acrylate monomer is 55 parts and the mass part of the epoxy resin is 45 parts.
Comparative example 2
The difference from the example 5 is only that the mass part of the acrylate monomer is 85 parts, and the mass part of the epoxy resin is 15 parts.
Comparative example 3
The only difference from example 1 is that the acrylate monomer is methyl methacrylate.
Comparative example 4
The only difference from example 1 is that the acrylate monomer is butyl acrylate.
Comparative example 5
The difference from example 1 is that no modified acrylate is added.
Comparative example 6
The difference from the example 1 is that the step (3) of the preparation method of the acrylate epoxy resin hybrid emulsion is as follows:
(3) adding the rest acrylate monomer into the acrylic resin emulsion, heating to 85 ℃, reacting for 1h, adding epoxy resin E44 after the reaction is finished, stirring and mixing uniformly, and adjusting the pH value of an emulsion system to 7.4 to obtain the acrylate epoxy resin hybrid emulsion.
The performance of the acrylate epoxy resin hybrid emulsion and the artificial color sand provided by the above examples 1-5 and comparative examples 1-6 was tested, and the test method and results are as follows:
1. wear resistance
The artificial colored sand provided in examples 1 to 5 and comparative examples 1 to 6 was stirred in water at a high speed of 1000r/min, and was judged to be discolored when contamination of water with toner was clearly observed. The wear resistance is characterized by the time to begin to fade, the longer the time, the better the wear resistance.
The same kind of epoxy resin emulsion as in examples 1-5 and the same kind of acrylic resin emulsion (prepared without adding epoxy resin in step (3)) were used as a comparison to replace the acrylate epoxy resin hybrid emulsion in equal amount to prepare artificial colored sand, and the results of the abrasion resistance test were as shown in table 1 below.
TABLE 1
Because the stone-like coating needs to pursue an extremely stone-like effect, the artificial colored sand is stirred in a cylinder for a long time in the stirring process, the contact time with a stirring paddle is very long, and the mechanical strength of the artificial colored sand adhesive is very important in the color matching process. If the mechanical strength is low, the wear resistance is poor, and in the process of color mixing and stirring, toner is easy to leak into a cylinder body from the surface of sand, so that the stone imitation effect is lost.
As can be seen from the results in Table 1, the acrylic resin has low mechanical strength and poor wear resistance, so that the artificial colored sand adopting the acrylic resin has fast fading; the epoxy resin has high mechanical strength and better wear resistance after being cured, so the artificial colored sand adopting the epoxy resin has slower fading. The hybrid emulsion provided by the invention forms an interpenetrating network of acrylic resin and epoxy resin after being cured, and although the hybrid emulsion contains an acrylic resin part with poor wear resistance, the overall wear resistance is equivalent to that of the epoxy resin.
From the results of comparative examples 1 and 2, it is clear that although the final mechanical strength after curing of the hybrid emulsion is mainly determined by the epoxy resin, the higher the proportion of the epoxy resin is, the better is not. When the proportion of the epoxy resin is too high, the hybrid emulsion shows certain incompatibility, so that the wear resistance of the artificial colored sand is reduced, and the color-losing time is shortened; when the proportion of the epoxy resin is too low, the final mechanical strength is insufficient, the abrasion resistance is poor, and the discoloration time is also shortened.
Comparative examples 3 to 5, compared with example 1, destroyed the compounding relationship between methyl methacrylate, butyl acrylate and modified acrylate. In the acrylic emulsion, methacrylic acid monomer plays a role of hard monomer, butyl acrylate plays a role of soft monomer, only the selection of the pure hard monomer can cause the decrease of the adhesive force of acrylic resin, the selection of the soft monomer can cause the almost no strength of the acrylic resin after the adhesion, and if the modified acrylic ester is not added, the influence on the hydrophobicity of the whole polymerization product is small, so the wear resistance of the obtained artificial colored sand is decreased, and the color fading time is shortened. In comparative example 6, since the epoxy resin is added after the acrylic resin is polymerized, delamination occurs due to the curing time difference between the acrylic resin and the epoxy resin in the use process of the hybrid emulsion, and no network cross-linked structure occurs, the wear resistance is greatly affected.
2. Drying Property
The acrylate epoxy resin hybrid emulsion provided in the above examples 1 to 5 was mixed with a pigment (accounting for 30% of the total volume), and then a curing agent ethylenediamine was added in an amount of 8% by mass of the acrylate epoxy resin hybrid emulsion to prepare a paint film having a thickness of 200 μm, and the drying time at room temperature was measured. Wherein, the surface drying is that the paint film cannot be damaged by finger pressing; actual drying means that the whole paint film is completely dried from top to bottom. The drying time of the epoxy resin E44 emulsion was measured in the same manner, and the results are shown in Table 2 below.
TABLE 2
As can be seen from the test results in Table 2, the paint film prepared from the acrylate epoxy resin hybrid emulsion provided by the invention has faster surface drying and actual drying speeds, and the actual drying speed is much higher than that of the paint film prepared from the epoxy resin emulsion. The acrylic ester epoxy resin hybrid emulsion provided by the invention contains acrylic resin, and the acrylic resin is dried quickly, so that the initial surface strength can be quickly established, and the surface drying is quick; the solid drying speed is determined by the proportion of the epoxy resin, and the solid drying speed is higher when the content of the epoxy resin is less.
3. Pot life
The acrylate epoxy resin hybrid emulsion provided in the above examples 1 to 5 was mixed with a pigment (accounting for 30% of the total volume), and then a curing agent ethylenediamine was added, wherein the amount of the curing agent added was 8% of the mass of the acrylate epoxy resin hybrid emulsion, and the amount of increase in viscosity from the initial viscosity after standing at room temperature for 4 hours and 10 hours was measured, respectively. The increase in viscosity was determined in the same manner as for the epoxy resin E44 emulsion. The results are shown in table 3 below.
TABLE 3
In the industrial preparation of artificial colored sand, resin and a curing agent are usually mixed to prepare an adhesive, but the prepared adhesive is often not used immediately. At this time, if the adhesive is cured quickly, the adhesive will be quickly ineffective, which is not beneficial to practical application. As can be seen from the test results in Table 3, since the epoxy resin is dispersed in the network of the acrylic resin and the active groups are embedded in the hybrid emulsion provided by the present invention, the initial crosslinking rate is low, the viscosity is increased slowly, and the pot life is long (when the pot life is tested, since the emulsion is not coated into a paint film, the solvent is volatilized slowly, the viscosity is determined by the crosslinking degree of the epoxy resin). Meanwhile, after the curing agent is added, the epoxy resin with a small proportion is cured less and is slow, and all the epoxy resin is fast in crosslinking due to the fact that active groups are all exposed, the viscosity is obviously increased within 4 hours, the epoxy resin cannot be used after 10 hours, and the working life is short.
4. Rate of intensity build-up
The wear resistance of the artificial color sand provided in examples 1-5 above at different curing time points was determined to characterize the strength build rate of the acrylate epoxy hybrid emulsion. The artificial color sand prepared by adopting the epoxy resin emulsion is used as a comparison, and the same method is adopted to determine the strength establishing rate. The test results are shown in table 4 below.
TABLE 4
From the results in table 4, it can be seen that the acrylate epoxy hybrid emulsion provided by the present invention has lower strength established in the first day than epoxy, but the strength is established significantly faster in the second day, and the final mechanical strength can be reached in 3 days, and the production efficiency is higher than that of epoxy. The acrylic ester epoxy resin hybrid emulsion provided by the invention contains acrylic resin, which is dried firstly to establish initial surface strength, so that not only active groups of the epoxy resin are embedded, but also the movement steric hindrance of the epoxy resin is increased, and the crosslinking rate of the epoxy resin is slower, and the strength of the acrylic resin is far lower than that of the cured epoxy resin; and the crosslinking degree of the single epoxy resin is higher in the first day, so that the artificial colored sand prepared by the acrylate epoxy resin hybrid emulsion provided by the invention has higher fading speed than the artificial colored sand prepared by the epoxy resin emulsion in the first day.
However, as the epoxy resin is cured, the physical steric hindrance formed by the acrylic resin can also accelerate the crosslinking rate of the whole epoxy resin, so that the acrylate epoxy resin hybrid emulsion provided by the invention has the advantages that the strength is established faster on the next day, and the acrylate epoxy resin hybrid emulsion is completely crosslinked and cured on the third day to achieve the final mechanical strength.
After the epoxy resin is completely cured, because the hybrid emulsion provided by the invention forms an interpenetrating network of the acrylic resin and the epoxy resin after being cured, the overall wear resistance is equivalent to that of the completely cured epoxy resin although the hybrid emulsion contains an acrylic resin part with poor wear resistance.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (18)
1. The acrylate epoxy resin hybrid emulsion is characterized by comprising acrylic resin, epoxy resin and an emulsifier, wherein the epoxy resin is dispersed in a network of the acrylic resin;
the acrylic resin is a polymerization product of acrylate monomers, and the acrylate monomers consist of 64-70 wt% of methyl methacrylate, 29-35 wt% of butyl acrylate and 1-3 wt% of modified acrylate;
the mass ratio of the acrylate monomer to the epoxy resin is (60-80) to (20-40);
the modified acrylate is organosilicon modified acrylate and/or organic fluorine modified acrylate;
the organic silicon modified acrylate is an acrylate modified by an organic silicon active monomer containing a carbon-carbon double bond;
the organosilicon active monomer is selected from methyl vinyl chlorosilane and/or vinyl trichlorosilane.
2. The acrylate epoxy hybrid emulsion according to claim 1 wherein the epoxy value of the epoxy resin is 0.4-0.5.
3. The acrylate epoxy hybrid emulsion according to claim 1, characterized in that the emulsifier accounts for 7-11% of the mass of the acrylate monomer.
4. The acrylate epoxy resin hybrid emulsion according to claim 1, wherein the emulsifier is a composite emulsifier of alkylphenol ethoxylate and sodium dodecylbenzenesulfonate.
5. The acrylate epoxy resin hybrid emulsion as claimed in claim 4, wherein the mass ratio of the alkylphenol ethoxylate to sodium dodecylbenzenesulfonate is 6: 1.
6. A method for preparing the acrylate epoxy resin hybrid emulsion as claimed in any one of claims 1 to 5, wherein the method comprises the following steps:
(1) dispersing 70-90% of acrylate monomer with formula amount in an aqueous solution of an emulsifier, and adjusting the pH to 7-8 to obtain acrylate emulsion;
(2) carrying out emulsion polymerization on the acrylate emulsion under the action of an initiator to obtain an acrylic resin emulsion;
(3) and dissolving epoxy resin by using the residual acrylate monomer, adding the epoxy resin into the acrylic resin emulsion, and heating for reaction to obtain the acrylate epoxy resin hybrid emulsion.
7. The method according to claim 6, wherein the initiator in the step (2) accounts for 0.1-1% of the total mass of the acrylate monomer.
8. The method according to claim 6, wherein the initiator is ammonium persulfate or a peroxide.
9. The method according to claim 6, wherein the emulsion polymerization in the step (2) is carried out by:
taking 10-20% of the acrylate emulsion, adding 30-50% of initiator according to the formula amount, reacting until the emulsion system turns blue, and dropwise adding the rest acrylate emulsion and the initiator while reacting until the dropwise adding is finished to obtain the acrylic resin emulsion.
10. The production method according to claim 9, wherein the reaction temperature in the step (2) is 75 to 85 ℃.
11. The preparation method according to claim 9, wherein the rest of the acrylate emulsion and the initiator are added dropwise within 3-5 h.
12. The method according to claim 6, wherein the reaction temperature in the step (3) is 80 to 90 ℃ and the reaction time is 1 to 3 hours.
13. The production method according to claim 6, wherein, after the reaction in step (3) is completed, the following operation is further performed: adjusting the pH value of the emulsion system to 7-8.
14. The method of claim 6, comprising the steps of:
(1) dispersing 70-90% of acrylate monomer with formula amount in an aqueous solution of an emulsifier, and adjusting the pH to 7-8 to obtain acrylate emulsion;
(2) taking 10-20% of the acrylate emulsion, adding 30-50% of initiator according to the formula amount, reacting at 75 ℃ until the emulsion system turns blue, dropwise adding the rest acrylate emulsion and initiator while reacting, and completing dropwise adding within 3h to obtain acrylic resin emulsion;
(3) and dissolving epoxy resin by using the residual acrylate monomer, adding the epoxy resin into the acrylic resin emulsion, heating to 85 ℃, reacting for 1h, and adjusting the pH value of an emulsion system to 7-8 to obtain the acrylate epoxy resin hybrid emulsion.
15. Use of the acrylate epoxy hybrid emulsion according to any one of claims 1 to 5 for adhesives of artificial color sand.
16. The artificial colored sand is characterized in that the raw materials for preparing the artificial colored sand comprise:
the acrylate epoxy resin hybrid emulsion is the acrylate epoxy resin hybrid emulsion as defined in any one of claims 1 to 5.
17. The artificial colored sand of claim 16, wherein the curing agent is an aliphatic polyamine and/or an aromatic polyamine.
18. The method for preparing artificial colored sand according to claim 16 or 17, which comprises the following steps:
firstly, mixing quartz sand, inorganic toner, acrylate epoxy resin hybrid emulsion and curing agent in a formula ratio for 3-5min at a stirring speed of 100-200r/min, and drying by hot air at the temperature of 120-150 ℃; and dehydrating and curing at the temperature of 100 ℃ and 200 ℃, or curing at normal temperature for at least 3 days to obtain the artificial colored sand.
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