CN107793516B - Method for preparing EVA elastomer microemulsion - Google Patents
Method for preparing EVA elastomer microemulsion Download PDFInfo
- Publication number
- CN107793516B CN107793516B CN201610806106.XA CN201610806106A CN107793516B CN 107793516 B CN107793516 B CN 107793516B CN 201610806106 A CN201610806106 A CN 201610806106A CN 107793516 B CN107793516 B CN 107793516B
- Authority
- CN
- China
- Prior art keywords
- dosage
- amount
- vinyl acetate
- microemulsion
- vac
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Abstract
The invention relates to a preparation method of EVA elastomer microemulsion, which comprises the following steps: deionized water is used as a water phase, a reactive sulfonate anionic surfactant is used as an emulsifier, a pH regulator and a colloid protective agent are added, and vinyl acetate and ethylene are subjected to copolymerization reaction under the initiation of a water-soluble free radical initiator to obtain the EVA elastomer microemulsion. According to the method disclosed by the invention, the particle size of the microemulsion can be controlled, and the stability is improved.
Description
Technical Field
The invention relates to a method for preparing EVA elastomer microemulsion by adopting a reactive sulfonate anionic emulsifier.
Background
The EVA (ethylene/vinyl acetate) elastomer emulsion produced by the emulsion polymerization method has moderate content of vinyl acetate (VAc), and the product has excellent flexibility, transparency, low-temperature flexibility, weather resistance, chemical corrosion resistance and compatibility with fillers and color masterbatch; the EVA emulsion product has high strength, no toxicity, environmental protection and excellent adhesive property, can be used in the fields of textile, light industry, coating, plastic toughening, building preparation, polymer blend coating, rubber modification and the like, has wide application, continuously increases the domestic and foreign demand and is rapidly developed in recent years.
The patent CN1302027C initiates polymerization at 40-60 ℃ to prepare high-solid EVA latex, the weight of the reaction ethylene is not counted by the pressure, the dosage of the initiator is 0.01-3.0 wt%, and the reaction time is 10.0 h. The VAc content in the polymer is 7.5-99.0 wt%. As a result of the formation of the emulsion and suspension polymers, the resulting dispersion has a bimodal particle size distribution, for example peaks with maxima at 0.2 to 0.5 μm and at 3.0 to 6.0. mu.m. The patent CN101200518A adopts a hydrogen peroxide-ferrous sulfate system, and the polymerization is initiated by two-stage step temperature control at 70-75 ℃ and 75-80 ℃, the ethylene reaction pressure is 9.0-10.0MPa, and the particle diameter is 1.85 μm. The EVA latex prepared by the method has the advantages of uneven particle distribution, overlarge particle size, easy agglomeration of latex particles, poor stability and greatly limited application.
The patent CN102695725A adopts a multi-kettle series connection process, EVA latex is prepared at 50-90 ℃ and 1.0-9.0MPa, and the diameter of latex particles is 1 mu m. The EVA emulsion prepared by the method has large latex particles, easy agglomeration of the particles, general product stability, narrow application range and complex process.
The microemulsion is polymerized to prepare the nano latex, and the nano latex has small average particle size, strong permeability, excellent wettability, high stability and wide application prospect. The preparation of the EVA elastomer nano particle microemulsion is rarely reported at present due to the complex formula and high process control difficulty.
Disclosure of Invention
The traditional EVA emulsion polymerization process has the disadvantages of complex emulsifier formula, overlarge latex particles, easy adhesion, poor particle shape and emulsion stability, difficult storage of products and limited application range. The invention adopts the reactive sulfonate anionic emulsifier to prepare the EVA elastomer microemulsion, can obviously reduce the particle size of latex particles, maintain the particle shape and greatly improve the emulsion stability. The EVA elastomer microemulsion product prepared by the method has good stability, moderate VAc content and excellent performance, and can meet different requirements.
According to one aspect of the present invention, there is provided a method for preparing an EVA elastomer microemulsion, comprising: deionized water is used as a water phase, a reactive sulfonate anionic surfactant is used as an emulsifier, a pH regulator and a colloid protective agent are added, and vinyl acetate and ethylene are subjected to copolymerization reaction under the initiation of a water-soluble free radical initiator to obtain the EVA elastomer microemulsion.
According to the method provided by the invention, the reactive sulfonate emulsifier has a double bond structure and higher reaction activity, the reactive functional group can participate in emulsion polymerization reaction, and can react and bond on the surface of EVA copolymer particles while solubilizing and coating a monomer/polymer and protecting the latex particles, so that the content of free emulsifier in a continuous phase of a copolymerization system is reduced, the emulsifier is prevented from being desorbed from the surfaces of the copolymer latex particles, the protective effect of the emulsifier on the particles is further enhanced, the adhesion and coalescence among the latex particles are prevented, and the particle size is further reduced. The invention selects one or more of reactive sulfonate anionic emulsifiers for use, can reasonably reduce the particle size of latex particles, stabilize micelles, maintain the particle morphology, prevent adhesion and greatly improve the stability of the emulsion under certain reaction conditions. The invention has simple formula, low raw material cost, simple and convenient operation and good stability of the target emulsion.
According to a specific embodiment of the method, the reactive sulfonate anionic surfactant is selected from the group consisting of sodium allyloxy hydroxypropyl sulfonate, sodium vinyl alkyl ester sulfonate, sodium maleic anhydride monoester sulfonate, sodium propenyl succinic acid diester sulfonate, and sodium isobutenyl succinic acid diester sulfonate. The dosage of the reactive sulfonate anionic surfactant is 0.5-20.0 wt% of the dosage of the vinyl acetate.
According to a specific embodiment of the method, the water-soluble radical initiator is one or more selected from inorganic salts, azo compounds, inorganic peroxides and inorganic redox initiators, preferably one or more selected from ammonium persulfate, sodium persulfate, potassium persulfate, azobisisobutyrimidazoline hydrochloride, azobiscyanovaleric acid, azobisisobutylamidine hydrochloride, hydrogen peroxide and sodium peroxide. According to a particular embodiment of the process, the water-soluble free radical initiator is used in an amount of 0.01 to 5.0 wt.%, such as 0.1 to 2.0 wt.%, based on the amount of vinyl acetate.
According to a specific embodiment of the method, the pH adjusting agent is a reagent commonly used in the art, such as at least one selected from sodium bicarbonate, ammonia, and the like. The pH adjusting agent is used in an amount of 0.05 to 5.0 wt%, such as 0.5 to 2.0 wt%, based on the amount of vinyl acetate. The pH of the reaction system is controlled to be 1.5-9.0 by adding a certain amount of pH regulator.
According to a particular embodiment of said method, said colloidal protective agent is selected from the group consisting of polyvinyl alcohols, polyethers, etherified celluloses and water-soluble cellulose derivatives. The amount of the colloid protective agent is 2.0-8.0 wt%, such as 2.5-5.0 wt%, of the amount of vinyl acetate.
According to a particular embodiment of the process, the ethylene pressure, i.e. the pressure of the reaction system, is between 3.0 and 25.0MPa, such as between 7.5 and 16.5 MPa. The polymerization temperature is 40-125 deg.C, such as 65-82 deg.C, and the reaction time is 3.0-8.0h, such as 4.0-7.0 h.
According to a specific embodiment of the method, the method is a single-kettle intermittent process, the problems of high difficulty in multi-kettle operation, high device cost and energy consumption and the like are solved, and the method has high industrial application value.
According to a particular embodiment of the method, the content of VAC units in the EVA elastomer is 35-75 wt%, preferably 40-70 wt%; the particle size of the microemulsion is 15-130nm, preferably 30-100 nm. The emulsion can be stably stored for more than 7 months, preferably more than 10 months.
On the basis of the existing EVA emulsion polymerization production process, the reactive sulfonate anionic emulsifier is adopted, so that the particle size of latex particles is reduced, and the stability of the emulsion is improved. The reactive sulfonate emulsifier has a double bond structure and higher reactivity, and reactive functional groups can participate in emulsion polymerization reaction, and can react and bond on the surface of EVA copolymer particles while solubilizing and coating monomers/polymers and protecting the latex particles, so that the content of free emulsifier in a copolymerization system continuous phase is reduced, the emulsifier is prevented from being desorbed from the surfaces of the copolymer latex particles, the protective effect of the emulsifier on the particles is further enhanced, the adhesion and coalescence among the latex particles are prevented, and the particle size of the particles is further reduced. The invention selects one or more of reactive sulfonate anionic emulsifiers for use, can reasonably reduce the particle size of latex particles, stabilize micelles, maintain the particle morphology, prevent adhesion and greatly improve the stability of the emulsion under certain reaction conditions. The invention has simple formula, low raw material cost, simple and convenient operation and good stability of the target emulsion; the invention adopts a single kettle intermittent process, avoids the problems of high difficulty of multi-kettle operation, high cost and energy consumption of the device and the like, and has higher industrial application value.
The invention adopts a single kettle intermittent process, and raw materials are directly pumped into a polymerization reaction kettle from the kettle top through a high-pressure metering pump. Commercially availableThe VAC monomer usually contains a polymerization inhibitor, and the VAc monomer used is distilled to remove the polymerization inhibitor before use. When preparing EVA elastomers, nitrogen is generally introduced into the system before reaction for oxygen removal. The copolymerization reaction apparatus of the present invention used for the above method comprises: the copolymerization reaction kettle is used for providing a reaction site for the copolymerization reaction of ethylene and vinyl acetate emulsion; and the stirring mechanism is used for realizing the mixing of the raw materials in the copolymerization reaction kettle. In one embodiment of the invention, the upper part of the copolymerization reaction kettle is provided with a surfactant, a colloid protective agent, an initiator, a pH regulator and a vinyl acetate liquid phase feed inlet, and N2The lower part of the ethylene feed port is provided with a discharge port which is communicated with the material defoaming tank and the degassing tank. The upper part of the material defoaming tank is provided with a pH regulator tank and a defoaming agent tank. The raw materials and the products are added and led out in the whole polymerization process by adopting a high-pressure metering pump. In one embodiment of the invention, the stirring mechanism is located at the central axis position in the copolymerization reaction kettle and consists of a driving device, a transmission device, a stirring shaft and a stirring paddle which are connected in sequence. The stirring paddle can use an anchor paddle, a turbine paddle, a ribbon paddle or a composite paddle combination of the anchor paddle and the turbine paddle. In one embodiment of the invention, a stirring shaft is longitudinally arranged in the center of the copolymerization reaction kettle, blades are arranged on the stirring shaft, and a motor positioned on the upper side of the kettle body drives the stirring shaft to rotate through a transmission mechanism. The lower end of the kettle body is provided with an end enclosure, and a discharge hole is reserved at the bottom of the end enclosure. Pumping raw materials and an initiator into a kettle from a liquid phase feed inlet, introducing nitrogen and removing oxygen, adding ethylene for polymerization reaction, and adopting a single kettle intermittent process.
In one embodiment of the invention, the process for preparing the EVA elastomer microemulsion by using the reactive sulfonate anionic emulsifier comprises the steps of continuously introducing vinyl acetate, an initiator, an emulsifier/colloid protective agent, a pH regulator and ethylene into a copolymerization reaction kettle during feeding, continuously leading out a copolymerization reaction product from the copolymerization reaction kettle during discharging, and carrying out treatment and subsequent separation of the product. The demulsification of the product and the extraction of the polymer can be carried out to characterize the performance of the related polymer.
The invention can also add other polymerization monomers for copolymerization while EVA is polymerized. The polymerization monomer used in the copolymerization may be an olefin such as propylene, n-butene, isobutylene, 1-hexene or 1-octene. In a specific example, the addition ratio of these polymerization monomers is selected within a range not to hinder the present invention from achieving the object of the present invention.
According to the invention, the particle size of the EAV elastomer microemulsion can be controlled by adopting the method provided by the invention, and the emulsion stability is improved. The invention has simple formula, low raw material cost, simple and convenient operation and good stability of the target emulsion, and the emulsion can be stored for more than 7 months, such as more than 10 months. The invention adopts a single kettle intermittent process, avoids the problems of high difficulty of multi-kettle operation, high cost and energy consumption of the device and the like, and has higher industrial application value.
Drawings
FIG. 1 is a schematic diagram of an ethylene-vinyl acetate emulsion single-kettle copolymerization batch process device of the invention.
In the figure: 1-a polymerization reactor; 2-surfactant/colloid protectant tank; 3-an initiator tank; 4-a pH regulator tank; 5-a monomer tank; 6-high pressure metering pump; 7-material defoaming tank; 8-a defoamer tank; 9-defoaming/removing ethylene.
Detailed Description
The invention is further illustrated by the following examples.
FIG. 1 shows a copolymerization reaction device for preparing EVA elastomer microemulsion by using reactive sulfonate anionic emulsifier. The process adopts single-kettle intermittent operation and comprises a copolymerization reaction kettle 1, a stirring mechanism and a product post-treatment part; the stirring mechanism comprises a stirring motor, a transmission device (not shown in the figures), a stirring shaft and a stirring paddle fixed on the stirring shaft. When the reaction kettle works, the stirring paddle and part of the stirring shaft are positioned below the reaction liquid level. In the production process, the surfactant, the colloid protective agent, the initiator, the pH regulator and the vinyl acetate are respectively pumped into a copolymerization reaction kettle 1 by a high-pressure metering pump 6, and N is introduced2And (3) discharging oxygen, pressing ethylene into the copolymerization reaction kettle 1 from an ethylene feed port to reach a preset constant pressure, and carrying out ethylene-vinyl acetate microemulsion copolymerization reaction under a proper reaction condition. After the reaction is finished, discharging the reaction materials from a discharge hole. The material enters a defoaming tank 7 and is added with a pH regulatorAnd the defoaming agent is added into the material defoaming tank from the pH regulator tank 4 and the defoaming agent tank 8 for product post-treatment, and the material is finally pumped into a defoaming machine 9 to remove unreacted ethylene gas.
In the embodiment, four methods of nuclear magnetism, element analysis, thermogravimetry and infrared are adopted to represent the VAc content in the EVA product; the particle size and morphology were characterized by Hitachi H-800 transmission electron microscopy.
The process in the embodiment of the invention comprises the following steps: adding deionized water as a water phase, adding a surfactant to form an O/W system, adding a colloid protective agent, an initiator, a pH regulator and vinyl acetate, introducing ethylene, carrying out copolymerization reaction at a polymerization reaction temperature, and carrying out certain polymerization reaction time to obtain the EVA microemulsion.
Taking ammonium persulfate water-soluble initiator, allyloxy hydroxypropyl sodium sulfonate (COPS-1) anionic emulsifier, sodium bicarbonate as pH regulator and polyvinyl alcohol PVA (with the trade name of 17-88) as colloid protective agent as an example:
example 1
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 20.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 58.4% by weight, and the average particle diameter of the miniemulsion was 16 nm. The microemulsion has good stability and can be stably stored for 12 months.
Example 2
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 18.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 58.4% by weight, and the average particle diameter of the miniemulsion was 27 nm. The microemulsion has good stability and can be stably stored for 12 months.
Example 3
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 16.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 58.2% by weight, and the average particle diameter of the miniemulsion was 36 nm. The microemulsion has good stability and can be stably stored for 11 months.
Example 4
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 14.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 58.1% by weight, and the average particle diameter of the miniemulsion was 48 nm. The microemulsion has good stability and can be stably stored for 10 months.
Example 5
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 12.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 58.3% by weight, and the average particle diameter of the miniemulsion was 59 nm. The microemulsion has good stability and can be stably stored for 9 months.
Example 6
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 10.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under the conditions, the VAc content of the polymerization product was 58.3% by weight, and the average particle diameter of the microemulsion was 70 nm. The microemulsion has good stability and can be stably stored for 9 months.
Example 7
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 8.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 58.4% by weight, and the average particle diameter of the microemulsion was 89 nm. The microemulsion has good stability and can be stably stored for 8 months.
Example 8
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 6.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under the conditions, the VAc content of the polymerization product was 58.4% by weight, and the average particle diameter of the microemulsion was 99 nm. The microemulsion has good stability and can be stably stored for 7.5 months.
Example 9
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 4.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 58.1% by weight, and the average particle diameter of the miniemulsion was 115 nm. The microemulsion has good stability and can be stably stored for 7.5 months.
Example 10
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 2.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 58.2% by weight, and the average particle diameter of the miniemulsion was 121 nm. The microemulsion has good stability and can be stably stored for 7.5 months.
Example 11
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 0.5 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 58.2% by weight, and the average particle diameter of the microemulsion was 129 nm. The microemulsion has good stability and can be stably stored for 7 months.
Example 12
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 20.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 3.0MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 74.5% by weight, and the average particle diameter of the microemulsion was 22 nm. The microemulsion has good stability and can be stably stored for 12 months.
Example 13
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 20.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 12.0MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 52.6% by weight, and the average particle diameter of the microemulsion was 21 nm. The microemulsion has good stability and can be stably stored for 12 months.
Example 14
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 20.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 16.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 48.9% by weight, and the average particle diameter of the microemulsion was 21 nm. The microemulsion has good stability and can be stably stored for 12 months.
Example 15
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 20.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 21.0MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 48.9% by weight, and the average particle diameter of the miniemulsion was 23 nm. The microemulsion has good stability and can be stably stored for 12 months.
Example 16
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 20.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 25.0MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 46.4% by weight, and the average particle diameter of the microemulsion was 20 nm. The emulsion has good stability, and can be stably stored for 12 months.
Example 17
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 20.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 65 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 70.2% by weight, and the average particle diameter of the microemulsion was 22 nm. The microemulsion has good stability and can be stably stored for 12 months.
Example 18
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 20.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 85 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 5 h. Under these conditions, the VAc content of the polymerization product was 54.6% by weight, and the average particle diameter of the microemulsion was 26 nm. The microemulsion has good stability and can be stably stored for 12 months.
Example 19
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 20.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 4 h. Under these conditions, the VAc content of the polymerization product was 70.3% by weight, and the average particle diameter of the microemulsion was 21 nm. The microemulsion has good stability and can be stably stored for 12 months.
Example 20
Ammonium persulfate is used as an initiator, the total dosage is 0.1 wt% of vinyl acetate, an O/W system, the dosage of a surfactant COPS-1 is 20.0 wt% of the dosage of a monomer VAc, the dosage of a colloid protective agent PVA is 2.5 wt% of the dosage of the monomer VAc, the dosage of a pH regulator is 0.5 wt% of the dosage of the monomer VAc, the polymerization temperature is 75 ℃, the ethylene reaction pressure is 7.5MPa, and the polymerization time is 7 h. Under these conditions, the VAc content of the polymerization product was 52.2% by weight, and the average particle diameter of the microemulsion was 21 nm. The microemulsion has good stability and can be stably stored for 12 months.
Comparative example 1
The reaction type sulfonate anionic emulsifier is not adopted, the common sulfonate anionic emulsifier sodium dodecyl sulfate is adopted, and other reaction conditions are the same as those in example 1. Under these conditions, the VAc content of the polymerization product was 64.7% by weight, and the particle size of the latex particles was 139 nm. The VAc content is higher, the particle size of the particles is larger, a small part of the particles are sticky, and emulsion breaking precipitation can occur after the emulsion is placed for 4 months.
Comparative example 2
The reaction type sulfonate anionic emulsifier is not adopted, the common sulfate anionic emulsifier sodium dodecyl sulfate is adopted, and other reaction conditions are the same as those in example 1. Under these conditions, the VAc content of the polymerization product was 66.9% by weight, and the particle size of the latex particles was 189 nm. The VAc content is higher, the particle size of the particles is larger, a small part of the particles are sticky, and the emulsion breaking precipitation can occur after the emulsion is placed for 3.5 months.
Comparative example 3
The reaction type sulfonate anionic emulsifier COPS-1 is used in the amount of 0.4 wt% of monomer VAc, and the other reaction conditions are the same as in example 1. Under the condition, the monomer is added to generate precipitation, and the emulsion copolymerization reaction is not carried out. The dosage of the emulsifier is too low, the system generates too few micelles, and the monomers can not be encapsulated.
Comparative example 4
The reaction type sulfonate anionic emulsifier COPS-1 is used in the amount of 20.1 wt% of monomer VAc, and the other reaction conditions are the same as in example 1. Under these conditions, the VAc content of the polymerization product was 58.6% by weight, and the particle size of the emulsion was 17 nm. The emulsifier dosage is higher, the system is complex, and the meaning of continuously increasing the dosage to reduce the particle size of the latex is not great.
Compared with the data of comparative examples 1-3, the reactive sulfonate anionic emulsifier used in the design of the invention is adopted to prepare the EVA elastomer microemulsion process, the VAc content and the particle size of the emulsion product are moderate, and the system is stable; compared with the data of comparative examples 4 and 5, the reactive sulfonate anionic emulsifier designed by the invention is adopted to prepare the EVA elastomer microemulsion, the VAc content and the particle size of the emulsion product are moderate within a certain dosage range, and the system is stable.
In conclusion, in the ethylene-vinyl acetate copolymerization single-kettle batch production process, the EVA elastomer microemulsion product is prepared by adopting the reactive sulfonate anionic emulsifier. The reactive sulfonate anionic emulsifier provided by the invention can be used within a certain dosage range, so that the particle size of latex particles can be remarkably reduced, an EVA microemulsion product with excellent particle morphology and good stability can be obtained, the application range of the EVA emulsion is greatly expanded, and different requirements are met. The invention adopts a single kettle intermittent process, avoids the problems of high difficulty of multi-kettle operation, high cost and energy consumption of the device and the like, and has higher industrial application value.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (24)
1. A preparation method of EVA elastomer microemulsion comprises the following steps: deionized water is used as a water phase, a reactive sulfonate anionic surfactant is used as an emulsifier, a pH regulator and a colloid protective agent are added, and vinyl acetate and ethylene are subjected to copolymerization reaction under the initiation of a water-soluble free radical initiator to obtain an EVA elastomer microemulsion;
wherein the reactive sulfonate anionic surfactant is allyloxy hydroxypropyl sodium sulfonate; the dosage of the reactive sulfonate anionic surfactant is 0.5-20.0 wt% of the dosage of the vinyl acetate.
2. The method of claim 1 wherein the reactive sulfonate anionic surfactant is present in an amount of from 2 to 18 weight percent based on the amount of vinyl acetate present.
3. The method according to claim 1 or 2, wherein the water-soluble radical initiator is selected from one or more of inorganic salts, azo compounds and inorganic peroxides.
4. The process according to claim 1 or 2, characterized in that the water-soluble radical initiator is selected from inorganic redox-type initiators.
5. The method of claim 3, wherein the water-soluble free radical initiator is selected from one or more of ammonium persulfate, sodium persulfate, potassium persulfate, azobisisobutyrimidazoline hydrochloride, azobiscyanovaleric acid, azobisisobutylamidine hydrochloride, hydrogen peroxide, and sodium peroxide.
6. The process according to claim 1 or 2, characterized in that the amount of water-soluble radical initiator is 0.01-5.0% by weight of the amount of vinyl acetate.
7. The method of claim 6, wherein the water-soluble free radical initiator is present in an amount of 0.1 to 2.0 wt.% based on the amount of vinyl acetate.
8. The method according to claim 1 or 2, wherein the pH adjusting agent is selected from sodium bicarbonate and ammonia.
9. The method of claim 8, wherein the amount of the pH adjusting agent is 0.05 to 5.0 wt% based on the amount of vinyl acetate.
10. The method of claim 9, wherein the pH adjusting agent is used in an amount of 0.5 to 2.0 wt% based on the amount of vinyl acetate.
11. The method according to claim 1 or 2, characterized in that the colloidal protective agent is selected from polyvinyl alcohol, polyethers, etherified cellulose and water-soluble cellulose derivatives.
12. The method of claim 11, wherein the colloidal protective agent is present in an amount of 2.0 to 8.0 wt% based on the amount of vinyl acetate present.
13. The method of claim 12, wherein the colloidal protective agent is present in an amount of 2.5 to 5.0 wt% based on the amount of vinyl acetate present.
14. The process according to claim 1 or 2, characterized in that the pressure of the ethylene is 3.0-25.0 MPa.
15. The process according to claim 14, characterized in that the pressure of the ethylene is 7.5-16.5 MPa.
16. The process of claim 1 or 2, wherein the process is a single pot batch process.
17. The process according to claim 1 or 2, characterized in that the copolymerization reaction temperature is 40-125 ℃; the reaction time is 3-8 h.
18. The method of claim 17, wherein the copolymerization reaction temperature is 65-85 ℃; the reaction time is 4-7 h.
19. The process according to claim 1 or 2, characterized in that the EVA elastomer has a VAC unit content of 35-75 wt% and the microemulsion has a particle size of 15-130 nm.
20. The method of claim 19, wherein the EVA elastomer has a VAC unit content of 40-70 wt% and the microemulsion has a particle size of 30-100 nm.
21. The method of claim 1 or 2, wherein the emulsion is stable for more than 7 months.
22. The method of claim 21, wherein the emulsion is shelf stable for more than 10 months.
23. A process according to claim 1 or 2, characterized in that it comprises the addition of further comonomers for copolymerization.
24. The process of claim 23, wherein the other comonomer is selected from the group consisting of propylene, n-butene, isobutylene, 1-hexene and 1-octene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610806106.XA CN107793516B (en) | 2016-09-07 | 2016-09-07 | Method for preparing EVA elastomer microemulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610806106.XA CN107793516B (en) | 2016-09-07 | 2016-09-07 | Method for preparing EVA elastomer microemulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107793516A CN107793516A (en) | 2018-03-13 |
| CN107793516B true CN107793516B (en) | 2020-12-18 |
Family
ID=61530870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610806106.XA Active CN107793516B (en) | 2016-09-07 | 2016-09-07 | Method for preparing EVA elastomer microemulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107793516B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041704A (en) * | 2007-04-20 | 2007-09-26 | 上海三瑞化学有限公司 | Novel ethane-acetic acid ethyenyl ester copolymer emulsion |
| EP2314636A1 (en) * | 2009-10-23 | 2011-04-27 | Universidad Del Pais Vasco-Euskal Herriko Unibertsitatea | Aqueous hybrid polyurethane-acrylic adhesives |
| CN102712722A (en) * | 2009-12-03 | 2012-10-03 | Ppg工业俄亥俄公司 | Waterborne coating compositions, related methods and coated substrates |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050050792A1 (en) * | 2003-08-13 | 2005-03-10 | The Lubrizol Corporation, A Corporation Of The State Of Ohio | Low temperature stable concentrate containing fatty acid based composition and fuel composition and method thereof |
| CN102030858B (en) * | 2009-09-30 | 2014-06-04 | 中国石油化工集团公司 | Vinyl acetate-ethylene copolymer emulsion (VAE emulsion) and synthesis method thereof |
-
2016
- 2016-09-07 CN CN201610806106.XA patent/CN107793516B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041704A (en) * | 2007-04-20 | 2007-09-26 | 上海三瑞化学有限公司 | Novel ethane-acetic acid ethyenyl ester copolymer emulsion |
| EP2314636A1 (en) * | 2009-10-23 | 2011-04-27 | Universidad Del Pais Vasco-Euskal Herriko Unibertsitatea | Aqueous hybrid polyurethane-acrylic adhesives |
| CN102712722A (en) * | 2009-12-03 | 2012-10-03 | Ppg工业俄亥俄公司 | Waterborne coating compositions, related methods and coated substrates |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107793516A (en) | 2018-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO1995008598A1 (en) | Aqueous dispersion of vinylidene fluoride polymer and process for producing the same | |
| US8916650B2 (en) | Vinyl chloride-based copolymer resin and a method of preparing the same | |
| US6245851B1 (en) | Vinyl acetate/ethylene high solids emulsions | |
| JP5306349B2 (en) | Continuous polymerization method | |
| JPS6132321B2 (en) | ||
| CN112457444B (en) | Vinyl chloride copolymer resin containing carboxyl and preparation method thereof | |
| KR101154469B1 (en) | Vinyl chloride resin with low viscosity and method of manufacturing the same | |
| CN107793516B (en) | Method for preparing EVA elastomer microemulsion | |
| KR20110139326A (en) | Method for producing vinyl chloride-based resin paste having reduced change of elapsed time in viscosity | |
| WO2019126913A1 (en) | A method for preparing aqueous copolymer dispersions | |
| CN106543298B (en) | A method of addition assistant for emulsifying agent prepares EVA lotion | |
| EP3752568A1 (en) | Water-based polymer dispersions and uses thereof | |
| CN107793519B (en) | Method for preparing EVA elastomer microemulsion | |
| CN107793511B (en) | Method for preparing EVA elastomer microemulsion | |
| CN106543342B (en) | Method for preparing low-viscosity EVA emulsion by adopting acrylic acid | |
| US20050043463A1 (en) | Preparation of multimodal polymer dispersions using polymeric stabilizer, and use thereof | |
| KR101366953B1 (en) | A Method for producing vinyl chloride based polymer | |
| CN106543326B (en) | Method for preparing low-viscosity EVA emulsion | |
| CN107793520B (en) | Method for preparing polyethylene-polyvinyl acetate elastomer soap-free microemulsion | |
| US8642698B2 (en) | Copolymerizable (meth)acrylic acid esters | |
| CN111234085B (en) | Formula and preparation method of bulk polymerization chlorinated polyether resin | |
| CN107793518A (en) | Application of the nertralizer in the emulsion particle diameter of control EVA elastomer emulsions | |
| KR101563766B1 (en) | A method for preparing vinyl chlorides resin having improved polymerization degree | |
| KR20180093976A (en) | A multistage aqueous emulsion polymer and an aqueous coating composition formed therefrom | |
| CN106543337B (en) | A kind of method that ethylene segmentation pressurization prepares EVA lotion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |