A water-soluble high-solid content polymer emulsion and preparation method thereof

Abstract

The invention relates to a method for preparing a water-soluble high-solid content polymer emulsion, comprising the following steps: (1) adding 10-20 kg of styrene, 3-6 kg of n-butyl acrylate, 0.2-0.8 kg of + acrylic acid, at least two surfactants such as 100-200 g of sodium dodecyl diphenyl ether disulfonate (dowfax), 200-300 g of sodium dodecylbenzene sulfonate (SDBS), and 15-25 kg of deionized water into a container; (2) placing a formulated amount of an initiator such as ammonium persulfate and deionized water into a container and mixing to prepare an initiator solution; (3) adding a certain amount of deionized water into a reaction kettle, stirring and heating to a certain temperature under an inert gas environment, adding a certain amount of ammonium persulfate, and mixing at a certain stirring speed; and (4) dripping the pre-emulsified emulsion prepared in (1) into (3) using a constant flow pump at a certain dripping speed. The method for preparing the water-soluble high-solid content polymer emulsion has the advantages of high production efficiency, fast film formation and drying, low transportation and storage costs, and non-toxicity and environmental protection.

Description

Technical Field

[0001] The invention relates to the technical field of polymer emulsion preparation, in particular to a water-soluble polymer emulsion with high solid content and low viscosity, specifically to a water-soluble polymer emulsion with high solid content and a preparation method thereof. Background Art

[0002] High solid content polymer emulsions are widely used in industrial fields, such as chemical toner preparation of adhesives, pressure-sensitive adhesives, plastic-wood composite adhesives, wood adhesives, construction adhesives, textile and leather adhesives, automotive adhesives, etc., and have broad development prospects.

[0003] Traditional emulsion polymerization uses water as solvent. Under the action of emulsifier, olefins and their derivatives are polymerized with polymer monomers in water by initiator and mechanical stirring. For example, Berber et al. used potassium persulfate as initiator and sodium dodecyl sulfate as emulsifier to prepare acrylate copolymer emulsion by in-situ emulsion polymerization of acrylate monomers and styrene. Another example is Lu Bo et al. used butyl acrylate as core monomer, methyl methacrylate and ethyl acrylate as shell monomers, and dodecyl mercaptan as emulsifier to prepare core-shell acrylate copolymer by seed emulsion copolymerization method. The solid content of acrylate polymer emulsion prepared by this method is generally 30%~50%, and there are shortcomings such as "hot sticky and cold brittle", high minimum film-forming temperature and poor water property, which limit its application. Summary of the invention

[0004] Technical issues solved In view of the deficiencies of the prior art, the present invention provides a water-soluble high-solid content polymer emulsion and a preparation method thereof, which is dispersed in the oil phase of a non-polar liquid with the aid of an emulsifier to form a water-in-oil (W / O) type pre-emulsion, and polymerized in an aqueous solution under the action of an initiator. The reaction has the advantages of easy heat dissipation, high polymerization rate, and the ability to obtain a water-soluble high molecular polymer, and the product has a wide range of uses, solving the problem of limited application range.

[0005] Technical Solution In order to achieve the above-mentioned purpose of dispersing the emulsifier in the oil phase of the non-polar liquid to form a water-in-oil (W / O) type pre-emulsion, the polymerization is carried out in the aqueous solution under the action of the initiator. It has the advantages of easy heat dissipation, high polymerization rate, and the ability to obtain water-soluble high molecular polymers, and the product has a wide range of uses. The present invention provides the following technical solutions: A water-soluble high solid content polymer emulsion, comprising the following components: Pre-emulsified emulsion and initiator solution The pre-emulsified emulsion is composed of styrene, n-butyl acrylate, acrylic acid, at least two surfactants and water; the mass ratio of styrene, n-butyl acrylate, acrylic acid, two surfactants such as sodium dodecyl diphenyl ether disulfonate (dowfax), sodium dodecyl benzene sulfonate (SDBS), and deionized water is (10-20):(3-6):(0.2-0.8):(0.1-0.2):(0.2-0.3):(15-25); The initiator solution is composed of ammonium persulfate or potassium persulfate and deionized water, and the mass ratio of the initiator such as ammonium persulfate and deionized water is (0.2-0.3):(2-8).

[0006] A method for preparing a water-soluble high-solid content polymer emulsion comprises the following steps: (1) Adding a formulated amount of styrene, n-butyl acrylate, acrylic acid, two surfactants such as sodium dodecyl diphenyl ether disulfonate (dowfax) and sodium dodecyl benzene sulfonate (SDBS), and deionized water into a container, and mixing them under stirring at room temperature to prepare a pre-emulsified emulsion; (2) placing a formulated amount of an initiator such as ammonium persulfate and deionized water in a container and mixing them to prepare an initiator solution; (3) Add a certain amount of deionized water into the reactor, stir and heat to a certain temperature under an inert gas environment, add a certain amount of ammonium persulfate, and mix at a certain stirring speed; (4) adding the pre-emulsified emulsion prepared in (1) to (3) at a certain dripping rate using a constant flow pump; (5) After a period of reaction, the initiator solution prepared in (2) is added dropwise to (3) at a certain dripping rate using a constant flow pump; (6) After the pre-emulsified emulsion in step (1) is added dropwise, the temperature is raised to a certain temperature, and the initiator solution in step (2) is continued to be added dropwise; (7) After the initiator solution in step (2) is added dropwise, the mixture is stirred for a certain period of time while maintaining a certain temperature and a certain stirring speed; (8) Stop heating and stir until the temperature drops to room temperature to obtain a polymer emulsion.

[0007] Preferably, in step (1), the room temperature is 15-30° C.; the mixing is stirring, and the stirring speed is 150-200 r / mim.

[0008] Preferably, in step (3), the certain amount of deionized water is 1.0-5.0 kg; the certain temperature heated is 60-80° C.; the certain amount of ammonium persulfate added is 50-80 g; and the certain stirring speed is 150-200 r / min.

[0009] Preferably, in step (4), the certain dripping rate is 200-300 ml / min.

[0010] Preferably, in step (5), the reaction time period is 10 to 30 minutes; and the certain dripping rate is 50 to 100 ml / min.

[0011] Preferably, in step (6), the certain temperature is 80-95°C.

[0012] Preferably, in step (7), the certain temperature is maintained at 80-95° C.; the certain stirring speed is 150-200 r / min; and the certain stirring time is 2-6 hours.

[0013] Beneficial Effects Compared with the prior art, the present invention provides a water-soluble high-solid content polymer emulsion and a preparation method thereof, which has the following beneficial effects: The water-soluble high-solid content polymer emulsion and the preparation method thereof have the advantages of high production efficiency, fast film formation and drying, low transportation and storage costs, and non-toxicity and environmental protection. DETAILED DESCRIPTION

[0014] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0015] Example 1: Polymer emulsion with a solid content of 53% (1) Add 17.55 kg of styrene, 5.07 kg of n-butyl acrylate, 0.46 kg of acrylic acid, 132.35 g of sodium dodecyl diphenyl ether disulfonate (dowfax), 264.71 g of sodium dodecyl benzene sulfonate (SDBS), and 18.50 kg of deionized water into a container, and stir and mix at room temperature to prepare a pre-emulsified emulsion; (2) 246.24 g of ammonium persulfate and 2.5 kg of deionized water were placed in a container and mixed to prepare an initiator solution; (3) Add 1.6 kg of deionized water into the reactor, stir and heat to 70 °C under an inert gas environment, add 64.64 g of ammonium persulfate, and control the stirring speed to 175 r / min; (4) Add the pre-emulsified emulsion prepared in (1) dropwise into (3) at a rate of 176 ml / min using a constant flow pump; (5) After a period of reaction, add (2) dropwise into (3) using a constant flow pump at 70 ml / min; (6) After the addition of (1) is completed, the temperature rises to 88°C and (2) is continued to be added; (7) After the addition of (2) is complete, maintain 88°C and a stirring speed of 175 r / min for 3 hours; (8) Stop heating and stir until the mixture cools to room temperature.

[0016] Example 2: Polymer emulsion with a solid content of 55% (1) Add 20.22 kg of styrene, 6.54 kg of n-butyl acrylate, 0.62 kg of acrylic acid, 138.05 g of sodium dodecyl diphenyl ether disulfonate (dowfax), 270.52 g of sodium dodecyl benzene sulfonate (SDBS), and 19.20 kg of deionized water into a container, and stir and mix at 20° C. to prepare a pre-emulsified emulsion; (2) 280.56 g of ammonium persulfate and 2.8 kg of deionized water were placed in a container and mixed to prepare an initiator solution; (3) Add 2.2 kg of deionized water into the reactor, stir and heat to 75 °C under an inert gas environment, add 65.32 g of ammonium persulfate, and control the stirring speed to 175 r / min; (4) Add the pre-emulsified emulsion prepared in (1) dropwise into (3) at a rate of 180 ml / min using a constant flow pump; (5) After a period of reaction, add (2) dropwise into (3) using a constant flow pump at 75 ml / min; (6) After the addition of (1) is completed, the temperature rises to 86°C and (2) is continued to be added; (7) After the addition of (2) was completed, the mixture was stirred at 86°C and 175 r / min for 4 h. (8) Stop heating and stir until the mixture cools to room temperature.

[0017] Example 3: Polymer emulsion with a solid content of 58% (1) Add 23.31 kg of styrene, 6.54 kg of n-butyl acrylate, 0.82 kg of acrylic acid, 140.20 g of sodium dodecyl diphenyl ether disulfonate (dowfax), 272.45 g of sodium dodecyl benzene sulfonate (SDBS), and 19.50 kg of deionized water into a reaction kettle, and stir and mix at 20°C to prepare a pre-emulsified emulsion; (2) Place 275.50 g of ammonium persulfate and 3.0 kg of deionized water in a container and mix to prepare an initiator solution; (3) Add 1.8 kg of deionized water into the reactor, stir and heat to 80 °C under an inert gas environment, add 66.50 g of ammonium persulfate, and control the stirring speed to 175 r / min; (4) Add the pre-emulsified emulsion prepared in (1) dropwise into (3) at a rate of 185 ml / min using a constant flow pump; (5) After a period of reaction, add (2) dropwise into (3) using a constant flow pump at 75 ml / min; (6) After the addition of (1) is completed, the temperature is raised to 90°C and (2) is continued to be added; (7) After the addition of (2) is complete, maintain 90°C and a stirring speed of 175 r / min for 2 hours; (8) Stop heating and stir until the mixture cools to room temperature.

[0018] Example 4: Polymer emulsion with a solid content of 60% (1) Add 28.50 kg of styrene, 7.50 kg of n-butyl acrylate, 0.75 kg of acrylic acid, 143.50 g of sodium dodecyl diphenyl ether disulfonate (dowfax), 275.50 g of sodium dodecyl benzene sulfonate (SDBS), and 20.50 kg of deionized water into a reactor, and stir and mix at 20°C to prepare a pre-emulsified emulsion; (2) 297.50 g of ammonium persulfate and 3.0 kg of deionized water were placed in a container and mixed to prepare an initiator solution; (3) Add 2.5 kg of deionized water into the reactor, stir and heat to 78 °C under an inert gas environment, add 70.50 g of ammonium persulfate, and control the stirring speed to 175 r / min; (4) Add the pre-emulsified emulsion prepared in (1) dropwise into (3) at a rate of 190 ml / min using a constant flow pump; (5) After a period of reaction, (2) was added dropwise to (3) using a constant flow pump at 80 ml / min; (6) After the addition of (1) is completed, the temperature rises to 92°C and (2) is continued to be added; (7) After the addition of (2) was completed, the mixture was stirred at 92°C and 175 r / min for 5 hours; (8) Stop heating and stir until the mixture cools to room temperature.

[0019] Observation of polymer emulsion performance: 1. Centrifugal stability: Place the polymer emulsion sample in a TD5G desktop centrifuge and centrifuge it at 3000 rpm for 15 min to observe whether there is stratification. 2. Storage stability: After the polymer emulsion is sealed and stored at room temperature for a period of time, observe whether there is stratification.

[0020] 3. Dispersibility: Drop the polymer emulsion into water and observe its diffusion rate in water.

[0021] 4. Optical properties: When the product is placed in a beaker, the surface will show colorful light under natural light.

[0022] The polymer emulsion prepared by the present invention has no stratification phenomenon in centrifugal stability test. There is no stratification phenomenon after being placed at room temperature for one month. It can be quickly dispersed in water and presents colorful light on the surface under natural light.

[0023] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A water-soluble high solid content polymer emulsion, characterized in that: Includes the following ingredients: Pre-emulsified emulsion and initiator solution The pre-emulsified emulsion is composed of styrene, n-butyl acrylate, acrylic acid, at least two surfactants and water; the mass ratio of styrene, n-butyl acrylate, acrylic acid, two surfactants such as sodium dodecyl diphenyl ether disulfonate (dowfax), sodium dodecyl benzene sulfonate (SDBS), and deionized water is (10-20):(3-6):(0.2-0.8):(0.1-0.2):(0.2-0.3):(15-25); The initiator solution is composed of ammonium persulfate or potassium persulfate and deionized water, and the mass ratio of the initiator such as ammonium persulfate and deionized water is (0.2-0.3):(2-8).

2. A method for preparing a water-soluble high-solid content polymer emulsion, characterized in that: The following steps are involved: (1) Adding a formulated amount of styrene, n-butyl acrylate, acrylic acid, two surfactants such as sodium dodecyl diphenyl ether disulfonate (dowfax) and sodium dodecyl benzene sulfonate (SDBS), and deionized water into a container, and mixing them under stirring at room temperature to prepare a pre-emulsified emulsion; (2) placing a formulated amount of an initiator such as ammonium persulfate and deionized water in a container and mixing them to prepare an initiator solution; (3) Add a certain amount of deionized water into the reactor, stir and heat to a certain temperature under an inert gas environment, add a certain amount of ammonium persulfate, and mix at a certain stirring speed; (4) adding the pre-emulsified emulsion prepared in (1) to (3) at a certain dripping rate using a constant flow pump; (5) After a period of reaction, the initiator solution prepared in (2) is added dropwise to (3) at a certain dripping rate using a constant flow pump; (6) After the pre-emulsified emulsion in step (1) is added dropwise, the temperature is raised to a certain temperature, and the initiator solution in step (2) is continued to be added dropwise; (7) After the initiator solution in step (2) is added dropwise, the mixture is stirred for a certain period of time while maintaining a certain temperature and a certain stirring speed; (8) Stop heating and stir until the temperature drops to room temperature to obtain a polymer emulsion.

3. The method for preparing a water-soluble high-solid content polymer emulsion according to claim 2, characterized in that: In step (1), the room temperature is 15-30° C.; the mixing is stirring, and the stirring speed is 150-200 r / mim.

4. The method for preparing a water-soluble high-solid content polymer emulsion according to claim 2, characterized in that: In step (3), the certain amount of deionized water is 1.0-5.0 kg; the certain temperature heated is 60-80° C.; the certain amount of ammonium persulfate added is 50-80 g; and the certain stirring speed is 150-200 r / min.

5. The method for preparing a water-soluble high-solid content polymer emulsion according to claim 2, characterized in that: In step (4), the certain dripping rate is 200-300 ml / min.

6. The method for preparing a water-soluble high-solid content polymer emulsion according to claim 2, characterized in that: In step (5), the reaction time is 10 to 30 minutes; and the certain dripping rate is 50 to 100 ml / min.

7. The method for preparing a water-soluble high-solid content polymer emulsion according to claim 2, characterized in that: In step (6), the certain temperature is 80-95°C.

8. The method for preparing a water-soluble high-solid content polymer emulsion according to claim 2, characterized in that: In step (7), the certain temperature is maintained at 80-95° C.; the certain stirring speed is 150-200 r / min; and the certain stirring time is 2-6 hours.