CN115073650A - Hydrophobic vinyl ester and olefin copolymer emulsion and preparation method thereof - Google Patents
Hydrophobic vinyl ester and olefin copolymer emulsion and preparation method thereof Download PDFInfo
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- 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
- C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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 a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
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- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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Abstract
The invention relates to a hydrophobic vinyl ester and olefin copolymer emulsion and a preparation method thereof, wherein the emulsion is a copolymer of saturated monocarboxylic acid vinyl ester and olefin, monomers of the copolymer comprise saturated monocarboxylic acid vinyl ester, ethylene and chloro-halogenated olefin, and vinyl acetate is not included. The copolymer emulsion prepared by the invention can not whiten after being soaked in water for 15 days, and has excellent hydrophobic property.
Description
Technical Field
The invention relates to a novel hydrophobic vinyl ester and olefin copolymer emulsion and a preparation method thereof, and the copolymer emulsion can be used as water-based base materials such as hydrophobic coatings, adhesives and the like.
Background
The core function of the coating layer is to prevent water from penetrating into the substrate and to prevent the coating layer itself from being deteriorated by the penetration of water, and thus the coating layer is required to have high hydrophobicity.
The hydrophobicity of the coating depends on the hydrophobicity of the coating base material, and the hydrophobicity of the base material is closely related to the hydrophobicity of the monomer for synthesizing the base material. It is generally accepted by those skilled in the art that monomers are more hydrophobic and polymers are more hydrophobic.
The hydrophobicity of a monomer can be expressed in terms of its solubility in water. The art generally classifies the hydrophobicity of monomers into three categories:
(1) "hydrophobic monomer" means any monomer having a water solubility of no more than about 0.02 grams per 100 grams of water;
(2) "very hydrophobic monomer" means any monomer having a water solubility of no more than about 0.01 grams per 100 grams of water;
(3) "extremely hydrophobic monomer" means any monomer having a water solubility of no more than about 0.001 grams per 100 grams of water.
The solubility of the monomers in water can be measured at 20 ℃ using deionized water as solvent. The solubility in water of some monomers (measured at 20 ℃ and in "g/100 g water") is described in accordance with the literature (D.R. Bassett, "Hydophobic Coatings from emulsions Polymers", Journal of Coatings Technology, 1/2001): 7.1 parts of acrylonitrile; 5.2 parts of methyl acrylate; 2.5 parts of vinyl acetate; ethyl acrylate 1.8; methyl methacrylate 1.5; 1.1 of ethylene; 0.60 of chloroethylene; 0.16 of butyl acrylate; 0.03 parts of styrene; 2-ethylhexyl acrylate 0.01; 0.08 parts of vinyl pivalate; vinyl 2-ethylhexanoate < 0.01; vinyl neononanoate is less than 0.001; the neodecanoic acid vinyl ester is less than 0.001; vinyl neoundecanoate is less than 0.001; the vinyl neododecanoate is less than 0.001. Among them, vinyl versatate monomers (including vinyl neononanoate, vinyl neodecanoate, vinyl neoundecanoate and vinyl neododecanoate collectively referred to as vinyl versatate) have a solubility significantly lower than that of other monomers, and belong to "very hydrophobic monomers". Thus, the vinyl versatate-based monomers have better hydrophobicity, and coating bases and coatings prepared therefrom will also have better water resistance and hydrophobicity.
In view of the great market demand for water-resistant and hydrophobic binders, vinyl versatate has gained more attention and widespread use in the field of emulsion polymerization.
The Chinese invention patent CN201811340179.X discloses vinyl acetate-vinyl versatate copolymer emulsion which is obtained by copolymerizing 18-22% of vinyl acetate and 5-10% of vinyl versatate 10, and the emulsion can show good water resistance and heat resistance after being formed into a film. In the emulsion, the existence of the alpha-position multi-branched chain tertiary carbon group with large steric hindrance of the ethylene versatate improves the hydrophobicity of the ethylene versatate. However, the presence of hydrophilic vinyl acetate monomers adversely affects the hydrophobicity of the emulsion.
The Chinese invention patent CN201210332548.7 discloses a vinyl acetate-ethylene-vinyl versatate copolymer emulsion, which comprises 40-70 parts of vinyl acetate, 5-15 parts of ethylene and 10-30 parts of vinyl versatate, and the prepared coating has good scrubbing resistance. The hydrophobicity of such emulsions is provided by vinyl versatate and vinyl monomers, but hydrophilic monomers of vinyl acetate are still present which affect the hydrophobicity of the emulsion.
Chinese patent CN201810319265.6 discloses a tertiary acrylic emulsion prepared by copolymerizing tertiary ethylene carbonate and acrylic ester, which does not turn white after being soaked in water for 7 days after film forming. The emulsion fully exerts the hydrophobicity of the ethylene versatate, however, the ethylene versatate accounts for 90 percent of the total monomer amount, and the cost of the raw materials is higher, so the cost of the emulsion is higher.
It can be seen that the current vinyl versatate copolymer emulsion is limited to the copolymerization of vinyl versatate and vinyl acetate, acrylic ester and ethylene, and if the hydrophobic property of these types of emulsion is further improved, the content of vinyl versatate must be increased, which greatly increases the cost of the emulsion in view of the higher cost of the vinyl versatate.
It will be appreciated that there is still a need for innovations and breakthroughs in the field of waterproofing, water-proofing and hydrophobing of vinyl versatate copolymer emulsions.
Disclosure of Invention
The invention aims to provide a novel low-cost ethylene versatate copolymer emulsion with strong hydrophobic property.
The invention also aims to provide a preparation method of the copolymer emulsion.
After extensive research and experiments, the present inventors have unexpectedly found that a vinyl ester and olefin copolymer emulsion with strong hydrophobicity is a copolymer of a saturated monocarboxylic acid vinyl ester and an olefin, wherein vinyl acetate monomers are not included, and is obtained by free radical aqueous emulsion polymerization of the following comonomers, wherein the mass percentages are all based on the total mass of the copolymer:
5 to 60 mass% of one or more saturated monocarboxylic acid vinyl esters, excluding vinyl acetate,
5 to 30 mass percent of ethylene,
monomer (c) 15-80% by mass of a chlorohaloolefin, and
0 to 10 mass% of other copolymerizable ethylenically unsaturated monomer.
Wherein the comonomer (r) is one or more of vinyl laurate, vinyl stearate, vinyl 2-ethylhexanoate, and vinyl versatate containing 5 to 11 carbon atoms, all of which are hydrophobic vinyl esters. The vinyl versatate may be obtained from commercially available products, such as vinyl pivalate available from Shizu Technology Ltd
Vinyl ester of neononanoic acid
Vinyl ester of neodecanoic acid
And vinyl neoundecanoate
A particularly preferred vinyl versatate is vinyl neononanoate
Vinyl ester of neodecanoic acid
And vinyl neoundecanoate
The comonomer is preferably chloroethylene.
Suitable comonomers iv may be stabilizing auxiliary monomers, such as α, β -monoethylenically unsaturated monocarboxylic and dicarboxylic acids and amides or nitriles thereof, for example acrylic acid, methacrylic acid, acrylamide; ethylenically unsaturated sulfonic acids or salts thereof, preferably vinylsulfonic acid, 2-acrylamidopropanesulfonic acid ester; n-vinyl pyrrolidone.
The comonomer iv may also be a crosslinking monomer. Crosslinking monomers include, but are not limited to, N-methylolacrylamide, N-methylolmethacrylamide, N- (alkoxymethyl) acrylamide or N- (alkoxymethyl) methacrylamide having C1-to C6-alkyl groups, such as N- (isobutoxymethyl) acrylamide (IBMA), N- (isobutoxymethyl) methacrylamide (IBMMA), N- (N-butoxymethyl) acrylamide (NBMA), and N- (N-butoxymethyl) methacrylamide (NBMMA); multiethylenically unsaturated comonomers, for example ethylene glycol diacrylate, 1, 3-butanediol diacrylate, 1, 4-butanediol diacrylate, propylene glycol diacrylate, divinyl adipate, divinylbenzene, vinyl methacrylate, allyl acrylate, diallyl maleate, diallyl phthalate, diallyl fumarate, triallyl cyanurate and the like. Comonomer units suitable for modifying the adhesion of the polymer include, but are not limited to, hydroxyalkyl esters of methacrylic acid and acrylic acid, such as hydroxyethyl, hydroxypropyl, or hydroxybutyl acrylate or methacrylate, diacetone acrylamide, acetoacetoxyethyl acrylate or methacrylate, and the like, allyl derivatives of aminoethylethylene urea, cyclic imine derivatives of urea/ureido monomers, and the like.
The crosslinking monomers may also include silanes, such as vinyltrimethoxysilane, vinyl-tris- (2-methoxyethoxysilane), gamma-methacryloxypropyltrimethoxysilane, acryloyl or methacryloyl polyesters of polyols, divinyl esters of polycarboxylic acids, diallyl terephthalate, N' -methylenebisacrylamide, hexamethylenebismaleimide, triallyl phosphate, trivinyl trimellitate, glycerol trimethacrylate, diallyl succinate, divinyl ethers of ethylene glycol or diethylene glycol, ethylene glycol diacrylate, polyethylene glycol diacrylate or methacrylate, N-methylolacrylamide, N-isobutoxymethacrylamide, trimethylolpropane triacrylate, ethylene glycol diacrylate or methacrylate, and mixtures thereof, Pentaerythritol triacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, divinyl benzene, tri or tetraethylene glycol diacrylate or methacrylate, butanediol diacrylate or dimethacrylate, and the like. Preferably, a mixture of crosslinking monomers may be used.
The copolymer emulsions according to the invention are particularly preferably vinyl ester-ethylene copolymers comprising the following monomer components:
10-55% by mass of ethylene versatate,
(ii) 5 to 30 mass% of ethylene, and
(iii) 30 to 70 mass% of chloropropene.
For use in coating preparation, the glass transition temperature Tg of the polymers of the invention is generally from about-15 to 20 deg.C, preferably from about-10 to 10 deg.C, more preferably from about 0 to 5 deg.C. Techniques for measuring the glass transition temperature of a polymer are known to those skilled in the art. For example, differential scanning calorimetry, and the FOX equation can also be used for preliminary predictions. For the preferred monomers and comonomers of the present invention, these homopolymers have glass transition temperatures of: ethylene-125 ℃, chloropropene 80 ℃, vinyl neodecanoate-3 ℃, vinyl neononanoate 70 ℃, vinyl pivalate 86 ℃, vinyl neoundecanoate-40 ℃, vinyl 2-ethylhexanoate-50 ℃. The glass transition temperature Tg of the copolymers of the invention is in the range from-70 to 60 ℃ and can be achieved by adjusting the comonomer combination involved in the copolymerization.
The present invention is preferably prepared by emulsion polymerization in the presence of an initiator and a chain transfer agent. The polymerization process employed is a conventional emulsion polymerization process, and may be any of batch, semi-continuous, and seeded emulsion polymerization.
In carrying out the emulsion polymerization, the initiator is added in an amount sufficient to initiate polymerization and may be present in an amount of from about 0.01% to about 3%, preferably from about 0.05% to 2%, and most preferably from about 0.1% to about 1% by weight of the total monomer. As will be appreciated by those skilled in the art, the initiator concentration will depend on the particular monomer mixture being reacted and the particular initiator being used. Initiators used include hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl hydroperoxide, dibenzoyl peroxide, perbenzoic acid, 2, 4-dichlorobenzoyl peroxide, 2, 5-dimethyl-2, 5-bis (hydroperoxy) hexane, perbenzoic acid, t-butyl peroxypivalate, t-butyl peracetate, dilauroyl peroxide, dioctanoyl peroxide, distearoyl peroxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate, didecyl peroxydicarbonate, dieicosyl peroxydicarbonate, di-t-butyl perbenzoate, 2' -azo bis-2, 4-dimethylvaleronitrile, ammonium persulfate, potassium persulfate, sodium perphosphate, and azobisisobutyronitrile, and any other known initiator. Of course, redox initiator systems such as sodium persulfate-sodium formaldehyde sulfoxylate, t-butyl hydroperoxide-sodium metabisulfite, hydrogen peroxide-ascorbic acid, and other known redox systems can also be used as the initiator. In addition, trace amounts of certain metal ions can be added as activators to improve the polymerization rate.
When a chain transfer agent is used, it is added in an amount of about 0.01% to about 5%, preferably about 0.1% to about 1%, based on the total mass of the monomers to be polymerized. Water insoluble and water soluble chain transfer agents may be used in the present invention. The water-soluble chain transfer agent includes: alkyl and aryl mercaptans such as butanethiol, isooctyl-3-mercaptopropionate, mercaptoacetic acid, mercaptoethanol, 3-mercaptopropanediol-1, 2-propanediol, and 2-methyl-2-propanethiol, and the like. The water-insoluble chain transfer agent includes t-dodecyl mercaptan, thiophenol, pentaerythritol tetramercaptopropionate, octyl decyl mercaptan, tetradecyl mercaptan, 2-ethylhexyl-3-mercaptopropionate, and the like.
Emulsifiers useful in the emulsion polymerization of the present invention include anionic emulsifiers, nonionic emulsifiers, or a combination of both. Since the vinyl ester monomers used in the present invention all have a strong hydrophobicity, it is necessary to use at least one hydrophobic surfactant. By "hydrophobic surfactant" is meant any surfactant having a critical micelle concentration below 0.05 mass% (concentration of surfactant in water), such as: diester sulfosuccinates, monoester sulfosuccinates, sulfosuccinamates, nonylphenol ether sulfates, and sodium salts of alkylaryl polyether sulfonates, fatty alcohol ether sulfates, alkylphenol ether sulfates, and low CMC phosphate surfactants, such as fatty phosphate esters containing 3, 6, and 10 moles of ethylene oxide. Nonionic emulsifiers include: alkylaryl polyether alcohols, alkylphenol ethoxylates, fatty alcohol ethoxylates, fatty acid esters, and the like. A preferred hydrophobic surfactant is sodium ditridecyl sulfosuccinate.
Reactive surfactants may also be used in the present invention. By "reactive surfactant" is meant a compound that bears at least one unsaturated double bond for free radical polymerization with monomers and monomer mixtures while also containing hydrophobic and hydrophilic moieties similar to conventional surfactants to maintain surface activity. Surfactant monomers include long chain alkoxy-or alkylphenoxy-polyalkylene oxide (meth) acrylates, e.g. C 18 H 27 - (ethylene oxide) 20 Methacrylic acid esters and C 12 H 25 - (ethylene oxide) 23 Methacrylates and the like.
The hydrophobic surfactant is added in an amount effective to enhance polymerization of the monomer mixture containing the hydrophobic monomer under emulsion polymerization conditions. The hydrophobic surfactant is preferably added to the polymerization mixture in an amount of 0.01 to 5% by weight of the total mass of the monomers, more preferably 0.05 to 3% by weight of the total mass of the monomers, and most preferably 0.1 to 1.5% by weight of the total mass of the monomers. The amount of other surfactants than the hydrophobic surfactant which may be present during the polymerization of the monomers of the present invention is from 0% to 5% of the total mass of the monomers, preferably from 0% to 3% of the total mass of the monomers, more preferably from 0% to 1.5% of the total mass of the monomers. The above surfactant mass percentages are based on the mass of dry surfactant (surfactant without water).
The present invention makes it possible to use protective colloids optionally in emulsion polymerization. The protective colloid is selected from cellulose or cellulose derivatives, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone or polymethacrylic acid, etc. The preferred emulsion for use in the coating art is hydroxyethyl cellulose.
The amount of protective colloid added is adjusted according to the requirements of monomers, emulsion and viscosity, and the addition amount is 0.05 to 2 percent of the total mass of the emulsion, and is preferably 0.15 to 0.9 percent. The protective colloid concentration is preferably kept at a minimum level in order to ensure the hydrophobicity of the emulsion.
In order to ensure the desired pH of the system, an alkaline buffer may be added in an amount of 0.1 to 0.5% by mass based on the total mass of the monomers to adjust the pH of the system to the desired value, and the alkaline buffer may include sodium acetate, ammonium bicarbonate, sodium bicarbonate, disodium phosphate and the like.
The invention can prepare emulsion with higher solid content. Emulsion polymerization can be carried out at lower temperatures, which increases the average molecular weight of the copolymer. The reaction temperature can be controlled by controlling the rate of addition of the initiator, as well as the rate of heat transfer. In general, the polymerization temperature of the present invention is preferably 70 ℃ on average, and the polymerization temperature is prevented from exceeding 80 ℃.
The polymerization time of the present invention is 3 to 10 hours, and can be determined depending on the temperature, the amount of the initiator and the desired polymerization conversion, and the polymerization can be completed in usually 6 hours. The end point of the reaction is expected to be less than 0.5% without significant exotherm and residual monomer content.
In the polymerization of the present invention, the amount of ethylene monomer copolymerized is dependent on a number of factors, including: the concentration and kind of the emulsifier, the reaction pressure, the stirring speed and the viscosity of the reaction solution during the polymerization. To increase the ethylene content in the copolymer, higher reaction pressures can be used. However, even if the amount of ethylene monomer in the copolymer is to be 30%, a pressure exceeding 12MPa is not necessary, and the minimum reaction pressure should be more than 2.5 MPa. In addition, in order to obtain a higher ethylene content in the copolymer, it is possible to increase the stirring speed and to reduce the viscosity of the reaction medium in the process, the viscosity of the reaction medium preferably being less than 1000mPa · s.
The particle size of the copolymer emulsion obtained by the invention can be adjusted by the addition of the emulsifier and the protective colloid during polymerization. If smaller emulsion particles are desired, the amount of emulsifier added is increased, while the amount of protective colloid added is decreased. For example, to prepare emulsion particle sizes below 0.25 microns, it is preferred to add very little protective colloid. Conversely, preparing larger average emulsion particle sizes requires a reduction in the amount of emulsifier used in the polymerization and an increase in the amount of protective colloid added.
The emulsion polymerization process of the present invention: firstly, preparing an aqueous solution containing an emulsifier, a protective colloid (if any), a pH regulator and the like, adding the aqueous solution and monomers (including vinyl chloride) which are required to be added in the initial stage into a polymerization kettle, then introducing ethylene into the polymerization kettle to a set pressure, starting stirring and fully stirring, and generally requiring 15 minutes for achieving full mass transfer balance. If the stirring efficiency is high or the reaction system is special, the time can be shortened. At the same time the temperature of the reaction medium is raised to the set reaction temperature. The polymerization was started by continuing the addition of the initial amount of initiator. After the polymerization has started, the initiator, vinyl ester monomer and vinyl chloride (if not added to the initial charge) are added continuously, depending on the progress of the polymerization, and the reaction is carried out at a constant polymerization pressure by adjusting the amount of ethylene added. After all the reaction materials are added, the temperature needs to be kept for a period of time so as to ensure that the polymerization reaction is carried out more completely. Followed by post-initiation with addition of initiator while maintaining this temperature to further reduce the residual monomer content.
The polymerization is terminated when the residual monomer content is below 0.5%, the polymerization product is cooled to room temperature, the pH of the polymerization product is adjusted to 4.5 to 7, preferably 6 to 6.5, and the product is discharged.
The inventor surprisingly found that the invention adopts the comonomer combination to obtain a novel vinyl ester and olefin copolymerization emulsion, and the emulsion has excellent hydrophobic property and low cost.
The copolymer emulsion can be used for preparing various coatings, preferably waterproof coatings, metal anticorrosive coatings, woodware coatings with larger deformation, surfaces which are difficult to adhere, such as plastic coatings, fireproof coatings and the like.
The copolymer emulsion can also be used for preparing various adhesives, such as pressure-sensitive adhesives, redispersible latex powder and the like.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the copolymer emulsion of the invention does not whiten after being soaked in water for 15 days, and the record of the non-whitening of the tertiary acrylic emulsion for longer than 7 days of the tertiary acrylic emulsion with the content of the vinyl versatate as high as 90 percent (which is described in Chinese invention patent CN108484835A) shows that the hydrophobicity of the polymer emulsion of the invention is superior to that of the tertiary acrylic emulsion.
This result is surprising in that the comonomers ethylene and vinyl chloride used in the polymer emulsions according to the invention do not belong to the group of hydrophobic monomers from the viewpoint of their solubility in water, but the hydrophobic properties of the copolymers with vinyl versatate are surprisingly better than those of vinyl versatate copolymers having an ethylene versatate content of up to 90% of the "very hydrophobic monomers".
This indicates that the degree of hydrophobicity of the polymer is not comprehensive enough to be judged by the solubility of the monomer in water. The monomer has low solubility in water and high hydrophobicity, and the polymer formed therefrom has high hydrophobicity, but the monomer has relatively high solubility in water, and the polymer formed therefrom does not necessarily have low hydrophobicity, depending on the condition of the monomer itself. The polymers of the invention in which ethylene and vinyl chloride are non-hydrophobic monomers but the polymerized segments thereof, such as polyethylene, polyvinyl chloride and their combination with very hydrophobic vinyl versatate, are extremely insoluble in water, are so hydrophobic that the copolymers of the invention are beyond the foreseeable ambit of the person skilled in the art.
(2) The copolymer emulsion has the other remarkable characteristics of easily obtained monomer raw materials and low cost, takes ethylene and chloropropene which are bulk upstream basic chemical raw materials as comonomers, has competitive advantage in cost, has good economy, and is easy for large-scale production and wide application.
(3) The copolymer emulsion takes vinyl chloride as a comonomer, a series of advantages of the vinyl chloride monomer are also incorporated, and the formed coating has excellent flame retardance and wear resistance; excellent resistance to plasticizers, water, ethanol, acids and bases; has excellent adhesion on PVC film.
(4) The copolymer emulsion also contains ethylene monomer, the low glass transition temperature and the flexibility of ethylene, the high glass transition temperature rigidity of vinyl chloride is matched, and the glass transition temperature of vinyl versatate covers-40-70 ℃, so that the emulsion with different glass transition temperatures can be designed according to the monomer proportion, and the application is more diversified.
(5) The copolymer emulsion has ingenious design and preparation scheme and is extremely creative. The vinyl versatate monomer is a good solvent, and dissolves ethylene and vinyl chloride in polymerization, so that the original gas-liquid two-phase polymerization can be completed under lower pressure, and the addition of ethylene is increased. The presence of tertiary carbon groups of the ethylene versatate forms large steric hindrance, so that the polymerization of the ethylene versatate is difficult, and the ethylene and the vinyl chloride are added for copolymerization and are embedded between the ethylene versatate monomers, so that the influence of the steric hindrance is overcome, and the polymer preparation can be smoothly carried out. Ethylene and vinyl chloride both have certain solubility in water, the requirement for the hydrophobicity of the surfactant is reduced, and the emulsification and polymerization can be completed by using common surfactants and protective colloids. Even if the vinyl versatate in the comonomer has low solubility in water and emulsification is difficult, emulsion polymerization is successful because at least one surfactant having a critical micelle concentration of less than 0.05 mass% is used as an emulsifier.
Detailed Description
The following examples are intended to illustrate the technical aspects of the present invention, and the scope of the present invention is not limited to these embodiments. For the sake of brevity, all possible combinations of features in the various embodiments or examples are not described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
In the following examples, the hydrophobicity of the copolymer emulsion was determined by the water-whitening resistance test method, which was as follows:
(1) selecting glass plates of the same batch, and removing oil stains and dirt on the surfaces of the glass plates by using ethanol;
(2) uniformly coating the emulsion on a clean glass plate by using a 100-micron wire bar coater, and coating 3 glass plates on each sample to be tested;
(3) the glass plate is put into an oven with the temperature of 50 +/-2 ℃ for 4 hours, taken out and cooled at room temperature.
(5) The panels were placed in a deionized water bath (23. + -. 2 ℃ C.) and submerged in film 2/3.
(6) After a specified time, the test plate is taken out to observe the state, and whether the phenomena of whitening, bubbling, shedding and the like exist.
The formulations of the examples and comparative examples are given below, all in mass percent unless otherwise indicated.
The preparation method comprises the following steps:
the monomers and substances under the monomer mixture item were transferred to a mixing vessel according to the above examples, comparative example formulation table, and the monomer mixture was prepared by starting stirring and mixing.
After replacement with nitrogen, the materials under the initial charge were added to a stainless steel autoclave equipped with a variable speed stainless steel disc turbine high speed stirrer, according to the recipe, and stirred uniformly. The initial monomer was charged thereto. The temperature required for the polymerization is obtained by adjusting the temperature set point of the thermostatic water bath. Ethylene was added to the desired pressure at the autoclave temperature of 50 ℃. After the addition of ethylene, the kettle contents were thoroughly mixed for 15 minutes at a stirring speed of 300rpm (revolutions per minute).
An initial initiator-oxidant is added to the reaction kettle, followed by an initial initiator-reductant. The stirrer was run continuously at 300rpm for 30 minutes during the initiation, after which the speed was increased to 600 rpm. The reactor temperature and total pressure increased due to the exotherm caused by the polymerization of the initial charge, and the cooling water flow was adjusted to control the temperature at 70 ℃.
After the heat release, each feed valve into the reaction tank was opened, and the remaining monomer and polymerization initiator were added dropwise thereto over 3 hours, and the feed amount of ethylene was controlled to control the pressure of the reaction tank to be lower than the pressure required for the polymerization.
When all feeds were complete, the contents of the kettle were allowed to react for a further 60 minutes, maintaining 70 ℃, to facilitate the reduction of residual monomer.
Thereafter, a post-initiation step was started, maintained at 70 ℃, and the post-initiator was added over 60 minutes to ensure that the residual monomer content was less than 0.5% of the emulsion volume.
After the post-initiation is completed, cooling the reaction kettle to be lower than 30 ℃, pressing the product out of the reaction kettle, degassing and defoaming to obtain the copolymer emulsion.
Example 1
The reaction was carried out in an autoclave having a capacity of 2 liters and a pressure resistance of 20 MPa. The polymerization pressure is 3MPa, and the ethylene incorporation is low. The product is ethylene-chloroethylene-ethylene terpolymer of neodecanoic acid.
The ethylene-vinyl chloride-ethylene terpolymer of neodecanoic acid has the following physical properties:
| solid content | 53％ |
| Glass transition temperature | 16 |
| PH | 3.8 |
| Particle size (micron) | 0.4 |
| Viscosity (mPa. s) | 70 |
Example 2
The reaction was carried out in an autoclave having a capacity of 2 liters and a pressure resistance of 20 MPa. The polymerization pressure is 5MPa, and the vinyl chloride incorporation is high. The product is ethylene-chloroethylene-ethylene terpolymer of neodecanoic acid.
The ethylene-vinyl chloride-ethylene terpolymer of neodecanoic acid has the following physical properties:
| solid content | 52.8％ |
| Glass transition temperature | 16 |
| PH | 4 |
| Particle size (micron) | 0.33 |
| Viscosity (mPa. s) | 52 |
Example 3
The reaction was carried out in an autoclave having a capacity of 2 liters and a pressure resistance of 20 MPa. The polymerization pressure is 6MPa, the vinyl chloride incorporation is low, and the vinyl versatate incorporation is high. The product is ethylene neononanoate-vinyl chloride-ethylene terpolymer.
The physical properties of the ethylene-vinyl chloride-ethylene terpolymer of neononanoic acid are as follows:
| solid content | 52.2％ |
| Glass transition temperature | 15 |
| PH | 3.4 |
| Particle size (micron) | 0.37 |
| Viscosity (mPa. s) | 45 |
Example 4
The reaction was carried out in an autoclave having a capacity of 2 liters and a pressure resistance of 20 MPa. The polymerization pressure is 10MPa, the incorporation of ethylene and vinyl chloride is high, the incorporation of ethylene versatate is low, the glass transition temperature is low, and the method is suitable for preparing pressure-sensitive adhesives and the like. The product is ethylene neononanoate-vinyl chloride-ethylene terpolymer.
The ethylene-vinyl chloride-ethylene terpolymer neononanoate had the following physical properties:
| solid content | 52％ |
| Glass transition temperature | -24 |
| PH | 4.1 |
| Particle size (micron) | 0.31 |
| Viscosity (mPa. s) | 69 |
Example 5
The reaction was carried out in an autoclave having a capacity of 2 liters and a pressure resistance of 20 MPa. The polymerization pressure was 5MPa, and methacrylic acid and the crosslinking monomer 2-hydroxyethyl acrylate were used in the polymerization. The product is four-component copolymer of neodecanoic acid ethylene-neononanoic acid ethylene-chloroethylene-ethylene.
The neodecanoic acid ethylene-neononanoic acid ethylene-vinyl chloride-ethylene quadripolymer has the following physical properties:
| solid content | 53.6％ |
| Glass transition temperature | 13 |
| PH | 3.6 |
| Particle size (micron) | 0.39 |
| Viscosity (mPa. s) | 90 |
Example 6
The reaction was carried out in an autoclave having a capacity of 2 liters and a pressure resistance of 20 MPa. The polymerization pressure was 5MPa, and a small amount of hydroxyethyl cellulose was used in the polymerization. The product is four-component copolymer of neodecanoic acid ethylene-neononanoic acid ethylene-chloroethylene-ethylene.
The neodecanoic acid ethylene-neononanoic acid ethylene-vinyl chloride-ethylene quadripolymer has the following physical properties:
| solid content | 53.7％ |
| Glass transition temperature | 13 |
| PH | 3.6 |
| Particle size (micron) | 0.4 |
| Viscosity (mPa. s) | 120 |
Example 7
The reaction was carried out in an autoclave having a capacity of 100 liters and a pressure resistance of 10 MPa. The polymerization pressure was 5MPa for scale-up experiments. The product is four-component copolymer of neodecanoic acid ethylene-neononanoic acid ethylene-chloroethylene-ethylene.
The neodecanoic acid ethylene-neononanoic acid ethylene-vinyl chloride-ethylene quadripolymer has the following physical properties:
| solid content | 52.9％ |
| Glass transition temperature | 13 |
| PH | 3.9 |
| Particle size (micron) | 0.28 |
| Viscosity (mPa. s) | 35 |
Example 8
The reaction was carried out in an autoclave having a capacity of 2 liters and a pressure resistance of 20 MPa. The polymerization pressure is 4.5MPa, and the vinyl ester is ethylene-2-ethyl vinyl hexanoate neodecanoate. The product is ethylene neodecanoate-2-ethyl vinyl hexanoate-chloroethylene-ethylene quadripolymer.
The ethylene-2-ethyl vinyl hexanoate-vinyl chloride-ethylene tetrapolymer of neodecanoic acid has the following physical properties:
| solid content | 53％ |
| Glass transition temperature | -2 |
| PH | 3.5 |
| Particle size (micron) | 0.44 |
| Viscosity (mPa. s) | 59 |
Example 9
The reaction was carried out in an autoclave having a capacity of 2 liters and a pressure resistance of 20 MPa. The polymerization pressure is 4.5MPa, and the vinyl ester is vinyl neodecanoate and vinyl laurate. The product is a quaternary copolymer of neodecanoic acid vinyl ester-vinyl laurate-chloroethylene-ethylene.
The physical properties of the copolymer of neodecanoic acid vinyl ester-vinyl laurate-vinyl chloride-ethylene are as follows:
| solid content | 53.1％ |
| Glass transition temperature | -7 |
| PH | 3.5 |
| Particle size (micron) | 0.42 |
| Viscosity (mPa. s) | 55 |
Comparative example 1
The reaction was carried out in an autoclave having a capacity of 2 liters and a pressure resistance of 20 MPa. The polymerization pressure is 6MPa, and the product is vinyl acetate-vinyl chloride-ethylene terpolymer.
The physical properties of the vinyl acetate-vinyl chloride-ethylene terpolymer are as follows:
| solid content | 52.5％ |
| Glass transition temperature | 13 |
| PH | 3.8 |
| Particle size (micron) | 0.52 |
| Viscosity (mPa. s) | 66 |
Comparative example 2
The reaction was carried out in an autoclave having a capacity of 2 liters and a pressure resistance of 20 MPa. The polymerization pressure is 4.5MPa, and the product is ethylene-vinyl acetate-ethylene terpolymer of neodecanoic acid.
The neodecanoic acid ethylene-vinyl acetate-ethylene terpolymer has the following physical properties:
| solid content | 52.9％ |
| Glass transition temperature | -7 |
| PH | 3.4 |
| Particle size (micron) | 0.55 |
| Viscosity (mPa. s) | 70 |
Performance testing of the examples and comparative examples
The emulsions obtained in examples 1 to 9 and comparative examples 1 to 2 were subjected to a whitening resistance test, and the emulsion film became white within 1 day after soaking in water in comparative examples 1 and 2. The latex film of example 6 was slightly whitened after soaking in water for 7 days, and the latex films of other examples were not whitened after soaking in water for 15 days, and were excellent in water resistance. The experimental result also shows that the addition of the protective colloid in example 6 has an influence on the hydrophobicity of the copolymer emulsion due to the hydrophilicity of the protective colloid, and the hydrophobicity of the latex film is slightly reduced.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the previous embodiments can be modified, or the preparation reaction conditions can be replaced, or part of technical features can be replaced equivalently; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (11)
1. A hydrophobic vinyl ester and olefin copolymer emulsion, which is a copolymer of a saturated monocarboxylic acid vinyl ester and an olefin, obtained by free radical aqueous emulsion polymerization of the following comonomers:
5 to 60 mass% of one or more saturated monocarboxylic acid vinyl esters, excluding vinyl acetate,
5 to 30 mass percent of ethylene,
monomer (c) 15-80% by mass of a chlorohaloolefin, and
0 to 10 mass% of other copolymerizable ethylenically unsaturated monomer.
2. The copolymer emulsion according to claim 1, wherein the monomer(s) is one or more of vinyl laurate, vinyl stearate, vinyl 2-ethylhexanoate, and vinyl versatate containing from 5 to 11 carbon atoms; preference is given to vinyl versatate having 9, 10 or 11 carbon atoms.
3. The copolymer emulsion of claim 1, wherein said monomer (c) is vinyl chloride.
4. The copolymer emulsion according to claim 1, wherein the monomer (iv) is an α, β -monoethylenically unsaturated mono-or dicarboxylic acid and amides or nitriles thereof, preferably acrylic acid, methacrylic acid, acrylamide; or ethylenically unsaturated sulfonic acids or salts thereof, preferably vinylsulfonic acid, 2-acrylamidopropanesulfonic acid esters, N-vinylpyrrolidone; or a crosslinking monomer.
5. The copolymer emulsion of claim 1, obtained by free radical aqueous emulsion polymerization of the following comonomers:
10-55 mass% of vinyl versatate with 5-11 carbon atoms,
monomer (c) 5 to 30 mass% of ethylene, and
30-70% by mass of chloropropene.
6. The copolymer emulsion according to any of claims 1 to 5, wherein at least one surfactant having a critical micelle concentration of less than 0.05 mass%, preferably sodium ditridecyl sulfosuccinate, is added as an emulsifier during the preparation of the emulsion.
7. The copolymer emulsion of claim 6, wherein the surfactant having a critical micelle concentration of less than 0.05 mass% based on the mass of the dry surfactant not containing water is present in the polymer mixture in an amount of 0.01% to 5%, preferably 0.05% to 3%, more preferably 0.1% to 1.5% by mass of the total monomer mass; the other surfactants account for 0% to 5%, preferably 0% to 3%, more preferably 0% to 1.5% of the total mass of the monomers.
8. The copolymer emulsion of claim 6, wherein the emulsion is prepared by an emulsion polymerization process in the presence of an initiator and a chain transfer agent; the initiator accounts for 0.01-3%, preferably 0.05-2%, more preferably 0.1-0.01% of the total mass of the monomers; the chain transfer agent accounts for 0.01-5%, preferably 0.1-1% of the total mass of the monomers.
9. The copolymer emulsion according to any one of claims 1 to 5, wherein an alkaline buffer is added to the polymerization in an amount of 0.1 to 0.5% by mass based on the total mass of the monomers.
10. A process for the preparation of a hydrophobic vinyl ester and olefin copolymer emulsion as claimed in any of claims 1 to 9, wherein at least one surfactant having a critical micelle concentration of less than 0.05% by mass is added as an emulsifier in the emulsion polymerization at a polymerization pressure of 2.5 to 12MPa and a polymerization temperature of not more than 80 ℃.
11. Use of the copolymer emulsion as claimed in any of claims 1 to 9 for the preparation of coatings, adhesives.
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| CN117844350A (en) * | 2024-01-16 | 2024-04-09 | 广东金高丽新材料有限公司 | Hydrophobic powder coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1274368A (en) * | 1998-05-22 | 2000-11-22 | 联合碳化化学品及塑料技术公司 | Ethylene latex copolymer compsns. |
| US20030114583A1 (en) * | 2001-10-31 | 2003-06-19 | Wacker Polymer Systems Gmbh & Co., Kg | Hydrophobicized copolymers |
| CN101039969A (en) * | 2004-10-15 | 2007-09-19 | 陶氏环球技术公司 | Emulsion polymerization of hydrophobic monomers |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1274368A (en) * | 1998-05-22 | 2000-11-22 | 联合碳化化学品及塑料技术公司 | Ethylene latex copolymer compsns. |
| US20030114583A1 (en) * | 2001-10-31 | 2003-06-19 | Wacker Polymer Systems Gmbh & Co., Kg | Hydrophobicized copolymers |
| CN101039969A (en) * | 2004-10-15 | 2007-09-19 | 陶氏环球技术公司 | Emulsion polymerization of hydrophobic monomers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117844350A (en) * | 2024-01-16 | 2024-04-09 | 广东金高丽新材料有限公司 | Hydrophobic powder coating and preparation method thereof |
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