CN112538128B - Acrylate emulsion and preparation method and application thereof - Google Patents
Acrylate emulsion and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an acrylate emulsion and a preparation method and application thereof, wherein a molecular chain of the prepared acrylate emulsion contains a ketone group and a hydrazide group, cross-linking between molecular chains or in molecular chains can be generated along with the reduction of a PH value in the film forming and drying process, and the acrylate emulsion has excellent performances of tolerance, hardness and the like and can be applied to the fields of metal coatings, wood coatings, textile coatings, furniture coatings, packaging coatings and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and relates to an acrylate emulsion, and a preparation method and application thereof.
Background
The acrylic ester emulsion is widely used in the fields of building coatings, waterproof coatings, wood coatings, metal corrosion prevention, damping coatings, textile coatings, printing coatings and the like due to excellent weather resistance, low VOC (volatile organic compound), excellent glossiness and transparency. However, in the process of preparing the acrylate emulsion, a substance containing hydrophilic groups is needed to be used for water-solubility, and the existence of the hydrophilic groups causes natural defects in resistance compared with the oil-based coating, and in order to compensate the defects, a group capable of post-crosslinking is introduced into the acrylate emulsion, so that the molecular weight is increased in the process of film forming and drying, a crosslinking system is formed among molecular chains, and the resistance of the resin is improved. The post-crosslinking comprises methods such as ketone hydrazine crosslinking, silane coupling agent post-crosslinking, vegetable oil post-crosslinking and the like, wherein the ketone hydrazine post-crosslinking is widely used due to simple process and excellent effect.
In the synthesis of acrylate emulsion, chinese patent CN104004477A uses acrylate monomer with carbonyl group such as diacetone acrylamide, and then adds crosslinking agent such as adipic acid hydrazide. Adipic acid hydrazide and diacetone acrylamide do not react in emulsions with pH >7, but react to form post-crosslinked structures during film-forming drying. However, the reaction activity of adipic acid hydrazide and carbonyl group in the scheme is low, which results in that effective cross-linking between molecules cannot be formed, and the residue of adipic acid hydrazide causes the problem of environmental pollution.
Chinese patent CN105111360A utilizes a mixture of a monomer containing a ketone carbonyl structure and a (meth) acrylate or a vinyl monomer to perform radical polymerization to obtain an acrylic resin containing a carboxyl group, and then performs neutralization, water addition for dispersion, and addition of a monomer containing a hydrazide group for uniform dispersion to obtain a modified acrylate resin. The ketone hydrazine monomer uses dihydrazide, oxalic acid dihydrazide, succinic acid dihydrazide and adipic acid dihydrazide water-soluble monomers, the monomers cannot be grafted to a molecular chain of the acrylic resin, but react with ketone carbonyl during film forming and drying, so that the reaction effect is low, and the residual water-soluble hydrazide monomer brings the problems of environmental pollution and poor resistance.
Therefore, it is required to develop a novel post-crosslinking technique to solve the problems of poor resistance and residue.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the problems of low crosslinking efficiency and residual crosslinking agents such as adipic acid hydrazide and the like in the existing ketone hydrazine crosslinking technology. The invention provides a novel acrylate emulsion which has excellent resistance and hardness and compatibility with polyurethane resin. Meanwhile, the invention also provides a preparation method and application of the acrylate emulsion.
In order to solve the technical problems, the invention is realized by the following technical scheme:
in one aspect of the invention, an acrylate emulsion is provided, which is prepared by radical emulsion polymerization of raw materials comprising the following components:
s1, at least one monovinyl aromatic monomer;
s2, at least one alkyl (meth) acrylate;
s3, an emulsifier;
s4, an acrylate monomer containing a ketone group;
s5, acrylic acid monomer containing carbamido and hydrazide group,
s6, a water-soluble initiator;
s7, a redox initiator.
In the present invention, in the above acrylate emulsion, based on the total mass of the components S1 to S7:
the amount of the component S1 is 15 to 80 wt%, preferably 19.6 to 74.0 wt%;
the amount of the component S2 is 15 to 80 wt%, preferably 19.5 to 74.0 wt%;
the component S3 is used in an amount of 0.5 to 4.5 wt%, preferably 1.20 to 3.92 wt%;
the component S4 is used in an amount of 0.1 to 4.0 wt%, preferably 0.33 to 2.09 wt%;
the component S5 is used in an amount of 0.1 to 4.0 wt%, preferably 0.33 to 2.09 wt%;
the component S6 is used in an amount of 0.1 to 2.0 wt%, preferably 0.33 to 1.31 wt%;
the component S7 is used in an amount of 0.005 to 0.1% by weight, preferably 0.01 to 0.05% by weight.
In the present invention, in the component S1 of the above-mentioned acrylate emulsion, the monovinyl aromatic monomer is one or more selected from the group consisting of styrene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene and 4- (n-decyl) styrene, and styrene is preferred.
In the present invention, in the component S2 of the above acrylate emulsion, the alkyl (meth) acrylate is one or more selected from the group consisting of methyl acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate and isooctyl (meth) acrylate, and is preferably methyl methacrylate.
In the component S3 of the acrylate emulsion, the emulsifier is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate, fatty alcohol-polyoxyethylene ether and salts thereof, and fatty alcohol ether phosphate and salts thereof, preferably sodium dodecyl sulfonate.
In the present invention, in the component S4 of the acrylate emulsion, the acrylate monomer containing a ketone group is one or more monomers selected from diacetone acrylamide, N-methylol acrylamide and acetoacetoxy ethyl (meth) acrylate.
In the invention, in the component S5 of the acrylate emulsion, the structure of the acrylic monomer containing carbamido and hydrazide is shown as formula I:
wherein: r 1 Is H or C n H 2n+1 N is more than or equal to 1, preferably 1 to 5;
R 2 is C n H 2n N is more than or equal to 1, preferably 1 to 5;
R 3 is NH 2 or-C X H Y CONHNH 2 X is more than or equal to 1, and Y is more than or equal to 1; preferably 1. ltoreq. X.ltoreq.10, 1. ltoreq. Y.ltoreq.10; most preferably, X is not less than 1 and not more than 5, and Y is not less than 1 and not more than 5.
Preferably, the acrylic monomer containing both a ureido group and a hydrazide group is one or more of 2- (hydrazide amide) ethyl methacrylic acid, 2- (hydrazide amide) ethyl acrylic acid and 2- (3- (4- (hydrazide amide) phenyl) ureido) ethyl acrylic acid, and the three acrylic monomers containing a ureido group and a hydrazide group can be obtained commercially or prepared by any available method, and the corresponding structural formulas are sequentially as follows:
in the present invention, in the component S6 of the acrylate emulsion, the water-soluble initiator is one or more of ammonium persulfate, sodium persulfate and potassium persulfate.
In the present invention, in the component S7 of the above acrylate emulsion, the redox initiator includes, but is not limited to, one or more of tert-butyl hydroperoxide, tert-amyl hydroperoxide, sodium bisulfite, sodium dithionite, isoascorbic acid, and the like, preferably tert-butyl hydroperoxide and/or isoascorbic acid, and more preferably the mass ratio is 2-3: 1 tert-butyl hydroperoxide with isoascorbic acid.
In another aspect of the present invention, there is also provided a method for preparing the acrylate emulsion, comprising the steps of:
(1) mixing a part component S1, a part component S2, a part component S3 and a component S4 with water to obtain a pre-emulsion A;
(2) mixing the residual component S1, the residual component S2, the residual component S3 and the component S5 with water to obtain a pre-emulsion B;
(3) stirring and heating the pre-emulsion A in the step (1) to 65-90 ℃, then adding part of the aqueous solution of the component S6 to initiate polymerization, wherein the addition time is 1-4h, preferably 2-3h, keeping the temperature for reaction for 0.5-3h after the addition is finished, and then adjusting the pH value to 7.5-9.0;
(4) adding the pre-emulsion B in the step (2) and the residual aqueous solution of the component S6 into the reaction system in the step (3), wherein the addition time is 1-4h, preferably 2-3h, and after the addition is finished, carrying out heat preservation reaction for 0.5-3 h;
(5) and (4) cooling the reaction system to 20-45 ℃, adding the component S7, and carrying out heat preservation reaction for 10-30min to obtain the acrylate emulsion.
Further, in the production method of the present invention,
in the step (3), ammonia water, sodium hydroxide aqueous solution, ethanolamine or triethanolamine and the like are adopted for adjusting the PH, and the ammonia water with the mass fraction of 26-28 percent, the sodium hydroxide aqueous solution with the mass fraction of 32 percent and the most preferable mass fraction of 26-28 percent is adopted.
The mass ratio of the component S1 added in the step (1) to the component S1 added in the step (2) is 0.1-6.0: 1, preferably 0.25 to 4.05: 1;
the mass ratio of the component S2 added in the step (1) to the component S2 added in the step (2) is 0.1-6.0: 1, preferably 0.25 to 4.05: 1;
the mass ratio of the component S3 added in the step (1) to the step (2) is 0.12-5:1, preferably 0.16-3: 1;
the raw materials of the component S6 added in the step (3) and the step (4) have a mass ratio of 0.1-15:1, preferably 0.2-8.9: 1.
The amount of water added in the step (1) is 0.3 to 5 times, preferably 0.67 to 4 times of the total mass of S1, S2 and S4 in the step (1).
The amount of water added in the step (2) is 0.3 to 5 times, preferably 0.67 to 4 times of the total mass of S1, S2 and S5 in the step (1).
In the aqueous solution of the component S6 added in the steps (3) and (4), the using amount of water is 4-100 times, preferably 6-40 times of that of the component S6; the feeding mode preferably adopts a dripping mode.
In some specific embodiments, the preparation method further comprises a filtering operation after the heat preservation reaction in the step (5) is completed, the specific method is not particularly required, the filtering temperature is 15-45 ℃, and residues in the emulsion polymerization synthesis process are filtered to obtain a filtrate.
In another aspect of the invention, the use of the above acrylate emulsion is also provided. The acrylate emulsion disclosed by the invention has good resistance, hardness and compatibility with aqueous polyurethane emulsion, and can be applied to the fields of wood coatings, metal coatings, textile coatings and the like.
The application example of the invention comprises a water-based woodware high gloss varnish, which comprises the acrylic ester emulsion and has the mass percentage content range of 75-85%.
Further, the water-based woodware high gloss varnish also comprises other auxiliary agents, such as a defoaming agent, a film forming agent, a thickening agent, water and the like.
In the research and development process, the acrylate emulsion subjected to ketone hydrazine post-crosslinking is adopted in the film forming and drying process, and if a hydrazide post-crosslinking group is also connected to a molecular chain instead of a common external addition mode, a ketone group and a hydrazide group are introduced to the molecular chain at the same time, so that the residual problems of hydrazine hydrate and adipic acid hydrazide and the problem of poor resistance can be obviously improved.
Meanwhile, the inventor further finds that not all substances containing hydrazide groups can achieve the effect, the component S5 is used for introducing the hydrazide groups, the molecular chain also has conjugated double bonds, the conjugated double bonds can be well polymerized with other acrylate monomers, and the hydrazide groups do not participate in free radical polymerization, so that the hydrazide groups can be remained on the side groups of the molecular chain. The present invention comprises reacting a ketone group-containing monomer and a hydrazide group-containing monomer in steps, and after the ketone group-containing monomer is reacted, adjusting the pH to 7.5 to 9 so that the whole emulsion exhibits basicity, in which case the ketone group cannot react with the hydrazide group. After the reaction is finished, the molecular chain contains ketone groups and hydrazide groups, so that the crosslinking between the molecular chains is not only formed like adipic hydrazide in the film forming and drying process, but also the crosslinking inside the molecular chain can be formed, and the defects that the reaction of the adipic hydrazide is incomplete, the performance is influenced, and the residual adipic hydrazide pollutes the environment are overcome.
The beneficial effects of the invention are mainly embodied in the following aspects:
(1) the invention simultaneously uses the acrylate monomer containing ketone group and hydrazide group, the ketone group and the hydrazide group are on the side chain of the molecular chain, and the ketone group and the hydrazide group can react to form intermolecular and intramolecular crosslinking in the film-forming and drying process, thereby improving the tolerance of the resin.
(2) The invention uses a special hydrazide group monomer which contains not only hydrazide groups but also carbamido groups, can improve the hardness of the resin, and because the acrylate emulsion is frequently required to be compounded with waterborne polyurethane in use, the defects of the acrylic resin are compensated by the high fullness and the high film-forming property of the polyurethane resin, but the two resins have larger structural difference and poor compatibility. The polyurethane resin generally contains urethane and urea groups, so that the urea groups in the acrylate and the urea groups in the polyurethane have the same structure, and the compatibility of the two can be improved.
(3) The preparation process is simple, and the crosslinking agent adipic acid hydrazide is not required to be added later, so that the pollution to the environment can be reduced.
(4) The invention has simple production process, convenient operation, safety and no toxicity.
Detailed Description
First, the embodiment adopts the main raw material sources:
methyl methacrylate: vanhua chemical Co., Ltd;
sodium dodecyl sulfate: shanghai jin Yue chemical Co., Ltd;
diacetone acrylamide: henan Detai chemical Co., Ltd;
butyl methacrylate: wanhua chemical Co., Ltd;
2- (hydrazide amide) ethyl methacrylic acid: the preparation method comprises the following steps: putting 50g of hydrazine hydrate into a flask with a stirring thermometer, putting the flask into an ice bath, then dripping 155.15g of isocyano ethyl methacrylate within 1 hour, and keeping the ice bath for 30 minutes after dripping;
potassium persulfate: guangzhou Qingxuan chemical science and technology limited;
2-methylstyrene: vanhua chemical Co., Ltd;
t-BHP: t-butyl hydroperoxide, Shandonghao Shunhai chemical Co., Ltd;
sodium dithionite: west longa chemical ltd;
alkyl polyoxyethylene ether LCN 407: crainen chemical Co., Ltd;
sodium dodecylbenzenesulfonate: shanghai jin Yue chemical Co., Ltd;
butyl acrylate: vanhua chemical Co., Ltd;
ammonium persulfate: guangzhou Qingxuan chemical science and technology Co., Ltd;
4-methylstyrene: vanhua chemical Co., Ltd;
2- (hydrazide amide) ethacrylic acid: the preparation method comprises the following steps: putting 50g of hydrazine hydrate into a flask with a stirring thermometer, putting the flask into an ice bath, then dripping 141.12g of isocyanate ethyl acrylate within 1 hour, and keeping the ice bath for 30 minutes after dripping;
2- (3- (2- (hydrazide amide) phenyl) ureido) ethacrylic acid: the preparation method comprises the following steps: placing 151g of 2-aminobenzoyl hydrazide in a flask with a stirrer and a thermometer, adding 300g of acetone, placing the flask in a water bath, keeping the temperature at 30-40 ℃, then dropwise adding 141.12g of isocyanate ethyl acrylate within 1 hour, and preserving the temperature for 30 minutes after dropwise adding;
pentyl methacrylate: vanhua chemical Co., Ltd;
other raw materials are purchased from the market unless otherwise specified.
The embodiment adopts a main analytical instrument and a test method:
the swing rod hardness testing method comprises the following steps: TQC pendulum hardometer, SP 0500;
the solid content testing method comprises the following steps: weighing appropriate amount of the emulsion in a container made of tinfoil paper, weighing the weight change at 150 deg.C for 20min, and calculating the solid content.
The particle size test method comprises the following steps: a malvern particle size instrument was used.
Method for testing resistance: varnishes were prepared according to table 1 by brushing the prepared varnish on a wood board, then reversing the varnish on the wood board using a disposable paper cup containing solvent, and observing the discoloration after standing for 7 days, with a score of 1-5, with 1 being the worst and 5 being the best.
Example 1
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, adding 3g of sodium dodecyl sulfate and 135.34g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring and dissolving, sequentially adding 100g of styrene, 100g of methyl methacrylate and 1g of diacetone acrylamide, and fully stirring for 20min for later use;
2) preparation of pre-emulsion B: at normal temperature and normal pressure, adding 1g of sodium dodecyl sulfate and 68.34g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring and dissolving, sequentially adding 50g of 2-methylstyrene, 50g of butyl methacrylate and 1g of 2- (hydrazide amide) ethyl methacrylic acid, and fully stirring for 20min for later use;
3) stirring the pre-emulsion A obtained in the step 1), heating to 65 ℃, dropwise adding a mixed solution of 0.5g of potassium persulfate and 20g of water to initiate polymerization, wherein the dropwise adding time is 2 hours, keeping the temperature for 0.5 hour after the addition is finished, and then adjusting the pH to 7.5 by adopting ammonia water with the mass fraction of 26%;
4) then, dropwise adding the pre-emulsion B, 4.5g of mixed solution of potassium persulfate and 27g of water into the system in the step 3), wherein the dropwise adding time is 2 hours, and keeping the temperature for 0.5 hour after the dropwise adding is finished;
5) cooling to 45 ℃, dropwise adding 0.09g of t-BHP and 0.045g of sodium hydrosulfite into the system in the step 4), reacting for 10min under heat preservation, filtering and collecting filtrate to obtain the acrylic ester emulsion 1, wherein the solid content is 55%, and the particle size is 200 nm.
Example 2
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, adding 3g of sodium dodecyl benzene sulfonate, 1g of alkyl polyoxyethylene ether LCN407 and 500g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring for dissolving, sequentially adding 15g of 2-methyl styrene, 227g of butyl methacrylate and 8g of diacetone acrylamide, and fully stirring for 30min for later use;
2) preparation of pre-emulsion B: at normal temperature and normal pressure, adding 1g of sodium dodecyl sulfate, 1g of alkyl polyoxyethylene ether LCN407 and 248g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring and dissolving, then sequentially adding 60g of 2-methyl styrene, 56g of butyl acrylate and 8g of 2- (hydrazide amide) ethyl acrylic acid, and fully stirring for 30min for later use;
3) heating the pre-emulsion A obtained in the step 1) to 90 ℃, starting to dropwise add a mixed solution of 2.4g of ammonium persulfate and 24g of water to initiate polymerization, wherein the dropwise adding time is 3 hours, keeping the temperature for 1 hour after the addition is finished, and then adjusting the pH to 8.0 by adopting ammonia water with the mass fraction of 27%;
4) then, dropwise adding the pre-emulsion B and a mixed solution of 0.27g of ammonium persulfate and 10.8g of water into the system in the step 3), wherein the dropwise adding time is 3 hours, and keeping the temperature for 3 hours after the addition is finished;
5) cooling to 20 ℃, dropwise adding 0.02g of t-BHP and 0.02g of sodium hydrosulfite into the system in the step 4), keeping the temperature, reacting for 30min, and filtering to obtain the acrylic ester emulsion 2, wherein the solid content is 31% and the particle size is 180 nm.
Example 3
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, adding 6g of sodium dodecyl sulfate and 500g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring and dissolving, sequentially adding 227g of 4-methylstyrene, 15g of butyl acrylate and 2g of diacetone acrylamide, and fully stirring for 25min for later use;
2) preparation of pre-emulsion B: at normal temperature and normal pressure, 9g of sodium dodecyl sulfate and 200g of deionized water are added into a pre-emulsification tank with a monomer metering tank and a stirrer, after the sodium dodecyl sulfate and the deionized water are fully stirred and dissolved, 56g of 4-methyl styrene, 60g of amyl methacrylate and 2g of 2- (hydrazide amide) ethyl acrylic acid are sequentially added, and the mixture is fully stirred for 25min for later use;
3) heating the pre-emulsion A obtained in the step 1) to 80 ℃, starting to dropwise add a mixed solution of 0.5g of ammonium persulfate and 20g of water to initiate polymerization, wherein the dropwise adding time is 2.5 hours, keeping the temperature for 0.8 hour after the addition is finished, and then adjusting the pH to 9.0 by adopting ammonia water with the mass fraction of 28%;
4) then, dropwise adding the pre-emulsion B and a mixed solution of 4.5g of ammonium persulfate and 45g of water into the system in the step 3), wherein the dropwise adding time is 2.5 hours, and keeping the temperature for 2 hours after the addition is finished;
5) cooling to 30 ℃, dropwise adding 0.1g of t-BHP and 0.1g of sodium hydrosulfite into the system in the step 4), keeping the temperature, reacting for 20min, and filtering to obtain a filtrate, namely the acrylic ester emulsion 3, wherein the solid content is 31% and the particle size is 100 nm.
Example 4
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, adding 1g of sodium dodecyl sulfate and 496g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring and dissolving, sequentially adding 56g of 4-methyl styrene, 60g of butyl acrylate and 8g of diacetone acrylamide, and fully stirring for 25min for later use;
2) preparation of pre-emulsion B: at normal temperature and normal pressure, adding 6g of sodium dodecyl sulfate and 1000g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring and dissolving, sequentially adding 227g of 4-methyl styrene, 15g of amyl methacrylate and 8g of 2- (hydrazide amide) ethyl acrylic acid, and fully stirring for 25min for later use;
3) heating the pre-emulsion A obtained in the step 1 to 80 ℃, starting to dropwise add a mixed solution of 2.4g of ammonium persulfate and 48g of water to initiate polymerization, wherein the dropwise adding time is 2.5 hours, keeping the temperature for 0.8 hour after the addition is finished, and then adjusting the pH to 9.0 by adopting ammonia water with the mass fraction of 26%;
4) then, dropwise adding the pre-emulsion B and a mixed solution of 0.27g of ammonium persulfate and 10.8g of water into the system in the step 3), wherein the dropwise adding time is 2.5h, and keeping the temperature for 2h after the addition is finished;
5) cooling to 30 ℃, dropwise adding 0.02g of t-BHP and 0.02g of sodium hydrosulfite into the system in the step 4), keeping the temperature, reacting for 20min, and filtering to obtain a filtrate, namely the acrylic ester emulsion 4, wherein the solid content is 19% and the particle size is 150 nm.
Example 5
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, adding 3g of sodium dodecyl sulfate and 135.34g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring and dissolving, sequentially adding 100g of styrene, 100g of methyl methacrylate and 1g of diacetone acrylamide, and fully stirring for 20min for later use;
2) preparation of pre-emulsion B: at normal temperature and normal pressure, adding 1g of sodium dodecyl sulfate and 68.34g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring and dissolving, sequentially adding 50g of 2-methylstyrene, 50g of butyl methacrylate and 1g of 2- (3- (2- (hydrazide amide) phenyl) ureido) ethacrylic acid, and fully stirring for 20min for later use;
3) stirring the pre-emulsion A obtained in the step 1), heating to 65 ℃, dropwise adding a mixed solution of 0.5g of potassium persulfate and 20g of water to initiate polymerization, wherein the dropwise adding time is 2 hours, keeping the temperature for 0.5 hour after the addition is finished, and then adjusting the pH to 7.5 by adopting ammonia water with the mass fraction of 26%;
4) then, dropwise adding the pre-emulsion B, 4.5g of mixed solution of potassium persulfate and 27g of water into the system in the step 3), wherein the dropwise adding time is 2 hours, and keeping the temperature for 0.5 hour after the dropwise adding is finished;
5) cooling to 45 ℃, dropwise adding 0.09g of t-BHP and 0.045g of sodium hydrosulfite into the system in the step 4), reacting for 10min under heat preservation, filtering and collecting filtrate to obtain the acrylic ester emulsion 1, wherein the solid content is 55%, and the particle size is 250 nm.
Comparative example 1
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, 3g of sodium dodecyl sulfate and 135.34g of deionized water are added into a pre-emulsification tank with a monomer metering tank and a stirrer, after full stirring and dissolution, 100g of styrene, 100g of methyl methacrylate and 2g of diacetone acrylamide are sequentially added, and full stirring is carried out for 20min for standby
2) Preparation of pre-emulsion B: at normal temperature and normal pressure, 1g of sodium dodecyl sulfate and 68.34g of deionized water are added into a pre-emulsification tank with a monomer metering tank and a stirrer, after full stirring and dissolution, 50g of 2-methyl styrene and 50g of butyl methacrylate are sequentially added, and full stirring is carried out for 20min for standby
3) Heating the pre-emulsion A obtained in the step 1 to 50 ℃, and starting stirring and heating; heating the temperature to 65 ℃, dropwise adding a mixed solution of 0.5g of potassium persulfate and 20g of water to initiate polymerization, wherein the dropwise adding time is 2 hours, the temperature is saturated for 0.5 hour after the addition is finished, and then adjusting the pH to 7.5 by adopting ammonia water with the mass fraction of 26%;
4) then, dropwise adding the pre-emulsion B, 4.5g of mixed solution of potassium persulfate and 27g of water into the system in the step 3), wherein the dropwise adding time is 2 hours, and keeping the temperature for 0.5 hour after the dropwise adding is finished;
5) cooling to 45 ℃, dropwise adding 0.09g of t-BHP and 0.045g of sodium hydrosulfite into the system in the step 4), preserving the temperature for 10min, filtering to obtain filtrate, and then adding 1g of adipic acid hydrazide to obtain the acrylic ester emulsion 5 with the solid content of 55% and the particle size of 220 nm.
Comparative example 2
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, 3g of sodium dodecyl sulfate and 135.34g of deionized water are added into a pre-emulsification tank with a monomer metering tank and a stirrer, after full stirring and dissolution, 100g of styrene, 100g of methyl methacrylate and 2g of diacetone acrylamide are sequentially added, and full stirring is carried out for 20min for standby
2) Preparation of pre-emulsion B: at normal temperature and normal pressure, 1g of sodium dodecyl sulfate and 68.34g of deionized water are added into a pre-emulsification tank with a monomer metering tank and a stirrer, after full stirring and dissolution, 50g of 2-methyl styrene, 50g of butyl methacrylate and 2g of 2- (hydrazide amide) ethyl methacrylic acid are sequentially added, and full stirring is carried out for 20min for standby
3) Heating the pre-emulsion obtained in the step 1 to 50 ℃, wherein the pH value is 7.0, and starting stirring and heating; the temperature is raised to 65 ℃, and 0.5g of mixed solution of potassium persulfate and 20g of water is dripped to initiate polymerization, wherein the dripping time is 2 hours;
4) after the addition is finished, the temperature is saturated for 0.5h, then the pre-emulsion B and a mixed solution of 4.5g of potassium persulfate and 27g of water are dropwise added for 2h, and the temperature is kept for 0.5h after the dropwise addition is finished; the viscosity of the system was found to be high and could not be used.
Comparative example 3
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, 3g of sodium dodecyl sulfate and 135.34g of deionized water are added into a pre-emulsification tank with a monomer metering tank and a stirrer, after full stirring and dissolution, 100g of styrene, 100g of methyl methacrylate and 2g of diacetone acrylamide are sequentially added, and full stirring is carried out for 20min for standby
2) Preparation of pre-emulsion B: at normal temperature and normal pressure, 1g of sodium dodecyl sulfate and 68.34g of deionized water are added into a pre-emulsification tank with a monomer metering tank and a stirrer, after full stirring and dissolution, 50g of 2-methyl styrene and 50g of butyl methacrylate are sequentially added, and full stirring is carried out for 20min for standby
3) Heating the pre-emulsion A obtained in the step 1 to 50 ℃, and starting stirring and heating; and (3) heating the belt temperature to 65 ℃, dropwise adding a mixed solution of 0.5g of potassium persulfate and 20g of water to initiate polymerization, wherein the dropwise adding time is 2 hours, the temperature is saturated for 0.5 hour after the addition is finished, then adjusting the pH to 9.5 by adopting ammonia water with the mass fraction of 26%, and finding that the emulsion is relatively serious in slag discharge.
Comparative example 4
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, 3g of sodium dodecyl sulfate and 135.34g of deionized water are added into a pre-emulsification tank with a monomer metering tank and a stirrer, after the sodium dodecyl sulfate and the 135.34g of deionized water are fully stirred and dissolved, 100g of styrene, 100g of methyl methacrylate and 2g of diacetone acrylamide are sequentially added, and the mixture is fully stirred for 20min for later use
2) Preparation of pre-emulsion B: at normal temperature and normal pressure, 1g of sodium dodecyl sulfate and 68.34g of deionized water are added into a pre-emulsification tank with a monomer metering tank and a stirrer, after the sodium dodecyl sulfate and the 68.34g of deionized water are fully stirred and dissolved, 50g of 2-methyl styrene, 50g of butyl methacrylate and 2g of acrylhydrazide are sequentially added, and the mixture is fully stirred for 20min for later use
3) Heating the pre-emulsion A obtained in the step 1 to 50 ℃, and starting stirring and heating; heating the temperature to 65 ℃, dropwise adding a mixed solution of 0.5g of potassium persulfate and 20g of water to initiate polymerization, wherein the dropwise adding time is 2 hours, the temperature is saturated for 0.5 hour after the addition is finished, and then adjusting the pH to 7.5 by adopting ammonia water with the mass fraction of 26%;
4) then, dropwise adding the pre-emulsion B, 4.5g of mixed solution of potassium persulfate and 27g of water into the system in the step 3), wherein the dropwise adding time is 2 hours, and keeping the temperature for 0.5 hour after the dropwise adding is finished;
5) cooling to 45 ℃, dropwise adding 0.09g of t-BHP and 0.045g of sodium hydrosulfite into the system in the step 4), preserving the temperature for 10min, and filtering to obtain filtrate, thereby obtaining the acrylic ester emulsion 5, wherein the solid content is 55%, and the particle size is 210 nm.
Application example (Water woodenware high gloss varnish)
The formula of the water-based woodware high-gloss varnish is shown in the following table 1, and the preparation method comprises the following steps: the components in the table 1 are added in sequence according to the weight ratio at room temperature under the stirring of 1500r/min, and the mixture is stirred for 15-30min until the components are completely dispersed, and the result is shown in 2.
TABLE 1 composition of raw materials in parts by weight
Evaluation results (acetic acid resistance, ethanol resistance, alkali resistance, water resistance of 5 points, best 5 points, worst 1 point)
TABLE 2 evaluation results
Claims (15)
1. The acrylic ester emulsion is characterized by being prepared by carrying out free radical emulsion polymerization on raw materials comprising the following components:
s1, at least one monovinyl aromatic monomer;
s2, at least one alkyl (meth) acrylate;
s3, an emulsifier;
s4, a ketone group-containing monomer selected from one or more of diacetone acrylamide, N-methylol acrylamide and acetoacetoxy ethyl (meth) acrylate monomers;
s5, and the acrylic monomer containing both ureido and hydrazide groups has the structure shown in the formula I:
wherein: r 1 Is H or C n H 2n+1 ，n≥1；
R 2 Is C n H 2n ，n≥1；
R 3 Is NH 2 or-C X H Y CONHNH 2 ，X≥1，Y≥1；
S6, a water-soluble initiator;
s7, a redox initiator;
the preparation method of the acrylate emulsion comprises the following steps:
(1) mixing a part component S1, a part component S2, a part component S3 and a component S4 with water to obtain a pre-emulsion A;
(2) mixing the residual component S1, the residual component S2, the residual component S3 and the component S5 with water to obtain a pre-emulsion B;
(3) stirring and heating the pre-emulsion A in the step (1) to 65-90 ℃, then adding part of the aqueous solution of the component S6 to initiate polymerization, wherein the adding time is 1-4h, keeping the temperature for reaction for 0.5-3h after the adding is finished, and then adjusting the pH value to 7.5-9.0;
(4) adding the pre-emulsion B in the step (2) and the residual aqueous solution of the component S6 into the reaction system in the step (3), wherein the adding time is 1-4h, and after the adding is finished, keeping the temperature and reacting for 0.5-3 h;
(5) and (4) cooling the reaction system to 20-45 ℃, adding the component S7, and carrying out heat preservation reaction for 10-30min to obtain the acrylate emulsion.
2. The acrylate emulsion according to claim 1, characterized in that, based on the total mass of components S1 to S7:
the amount of the component S1 is 15-80 wt%;
the amount of the component S2 is 15-80 wt%;
the amount of the component S3 is 0.5-4.5 wt%;
the amount of the component S4 is 0.1-4.0 wt%;
the amount of the component S5 is 0.1-4.0 wt%;
the amount of the component S6 is 0.1-2.0 wt%;
the component S7 is used in an amount of 0.005 to 0.1 wt%.
3. The acrylate emulsion according to claim 2, characterized in that, based on the total mass of components S1 to S7:
the amount of the component S1 is 19.6-74.0 wt%;
the amount of the component S2 is 19.5-74.0 wt%;
the amount of the component S3 is 1.20-3.92 wt%;
the amount of the component S4 is 0.33-2.09 wt%;
the amount of the component S5 is 0.33-2.09 wt%;
the amount of the component S6 is 0.33-1.31 wt%;
the component S7 is used in an amount of 0.01-0.05 wt%.
4. The acrylic ester emulsion according to claim 1, wherein in component S1, the monovinyl aromatic monomer is selected from one or more of styrene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene and 4- (n-decyl) styrene.
5. The acrylic ester emulsion according to claim 1, wherein in component S2, the alkyl (meth) acrylate is selected from one or more of methyl acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, and isooctyl (meth) acrylate.
6. The acrylic ester emulsion according to claim 1, wherein in component S5, the acrylic monomer containing both the ureido group and the hydrazide group has the structure shown in formula i: r 1 Is C n H 2n+1 When n is more than or equal to 1 and less than or equal to 5;
R 2 is C n H 2n When n is more than or equal to 1 and less than or equal to 5;
R 3 is-C X H Y CONHNH 2 When X is more than or equal to 1 and less than or equal to 10, and Y is more than or equal to 1 and less than or equal to 10.
7. The acrylate emulsion of claim 6 wherein R is 3 is-C X H Y CONHNH 2 When the ratio is more than or equal to 1 and less than or equal to 5, and the ratio is more than or equal to 1 and less than or equal to 5.
8. The acrylic ester emulsion according to claim 1, wherein the acrylic monomer containing both the ureido group and the hydrazide group is one or more of 2- (hydrazide amide) ethyl methacrylate, 2- (hydrazide amide) ethyl acrylate and 2- (3- (4- (hydrazide amide) phenyl) ureido) ethyl acrylate.
9. The acrylate emulsion according to claim 1, wherein in component S3, the emulsifier is one or more of sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, fatty alcohol-polyoxyethylene ether and its salts, and fatty alcohol ether phosphate and its salts;
in the component S6, the water-soluble initiator is one or more of ammonium persulfate, sodium persulfate and potassium persulfate;
in component S7, the redox initiator includes, but is not limited to, one or more of tert-butyl hydroperoxide, tert-amyl hydroperoxide, sodium bisulfite, sodium dithionite and isoascorbic acid.
10. The acrylate emulsion according to claim 9, wherein in component S7, the redox initiator is a mixture of 2 to 3:1 tert-butyl hydroperoxide with isoascorbic acid.
11. A method for preparing the acrylate emulsion according to any one of claims 1 to 10, comprising the steps of:
(1) mixing a part component S1, a part component S2, a part component S3 and a component S4 with water to obtain a pre-emulsion A;
(2) mixing the residual component S1, the residual component S2, the residual component S3 and the component S5 with water to obtain a pre-emulsion B;
(3) stirring and heating the pre-emulsion A in the step (1) to 65-90 ℃, then adding part of the aqueous solution of the component S6 to initiate polymerization, wherein the adding time is 1-4h, keeping the temperature for reaction for 0.5-3h after the adding is finished, and then adjusting the pH value to 7.5-9.0;
(4) adding the pre-emulsion B in the step (2) and the residual aqueous solution of the component S6 into the reaction system in the step (3), wherein the adding time is 1-4h, and after the adding is finished, keeping the temperature and reacting for 0.5-3 h;
(5) and (4) cooling the reaction system to 20-45 ℃, adding the component S7, and carrying out heat preservation reaction for 10-30min to obtain the acrylate emulsion.
12. The method of claim 11, wherein:
in the step (3), ammonia water, sodium hydroxide aqueous solution, ethanolamine or triethanolamine is adopted for adjusting the PH; and/or
The mass ratio of the component S1 added in the step (1) to the component S1 added in the step (2) is 0.1-6.0: 1; and/or
The mass ratio of the component S2 added in the step (1) to the component S2 added in the step (2) is 0.1-6.0: 1; and/or
The mass ratio of the component S3 added in the step (1) to the component S3 added in the step (2) is 0.12-5: 1; and/or
The raw materials of the component S6 added in the step (3) and the step (4) have the mass ratio of 0.1-15: 1; and/or
The amount of the water added in the step (1) is 0.3-5 times of the total mass of S1, S2 and S4 in the step (1); and/or
The amount of the water added in the step (2) is 0.3-5 times of the total mass of S1, S2 and S5 in the step (1); and/or
In the aqueous solution of the component S6 added in the steps (3) and (4), the using amount of water is 4-100 times of that of the component S6; and/or
The feeding mode adopts a dripping mode.
13. The method of manufacturing according to claim 12, wherein:
the mass ratio of the component S1 added in the step (1) to the component S1 added in the step (2) is 0.25-4.05: 1; and/or
The mass ratio of the component S2 added in the step (1) to the component S2 added in the step (2) is 0.25-4.05: 1; and/or
The mass ratio of the component S3 added in the step (1) to the component S3 added in the step (2) is 0.16-3: 1; and/or
The raw materials of the component S6 added in the step (3) and the step (4) have the mass ratio of 0.2-8.9: 1; and/or
The amount of the water added in the step (1) is 0.67-4 times of the total mass of S1, S2 and S4 in the step (1); and/or
The amount of the water added in the step (2) is 0.67-4 times of the total mass of S1, S2 and S5 in the step (1); and/or
In the aqueous solution of the component S6 added in the step (3) and the step (4), the amount of water is 6-40 times of that of the component S6.
14. The method of claim 11, wherein: the feeding time in the step (3) is 2-3 h;
and (4) the feeding time is 2-3 h.
15. Use of the acrylate emulsion according to any of claims 1 to 10 or prepared by the process according to any of claims 11 to 14 in the fields of wood coatings, metal coatings, textile coatings.
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| JP2001335670A (en) * | 2000-05-26 | 2001-12-04 | Mitsubishi Chemicals Corp | Aqueous resin composition and cross-linking agent |
| WO2015041403A1 (en) * | 2013-09-23 | 2015-03-26 | 주식회사 엘지화학 | Acrylic emulsion adhesive, and production method for same |
| CN109504171A (en) * | 2017-09-14 | 2019-03-22 | 星光Pmc株式会社 | Resin dispersion liquid used for water color ink and its manufacturing method |
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| JP2001335670A (en) * | 2000-05-26 | 2001-12-04 | Mitsubishi Chemicals Corp | Aqueous resin composition and cross-linking agent |
| WO2015041403A1 (en) * | 2013-09-23 | 2015-03-26 | 주식회사 엘지화학 | Acrylic emulsion adhesive, and production method for same |
| CN109504171A (en) * | 2017-09-14 | 2019-03-22 | 星光Pmc株式会社 | Resin dispersion liquid used for water color ink and its manufacturing method |
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