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WO2025213375A1 - Water-based polymer dispersions - Google Patents

Water-based polymer dispersions

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Publication number
WO2025213375A1
WO2025213375A1 PCT/CN2024/086930 CN2024086930W WO2025213375A1 WO 2025213375 A1 WO2025213375 A1 WO 2025213375A1 CN 2024086930 W CN2024086930 W CN 2024086930W WO 2025213375 A1 WO2025213375 A1 WO 2025213375A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
based polymer
polymer dispersion
preferably greater
vinyl
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.)
Pending
Application number
PCT/CN2024/086930
Other languages
French (fr)
Inventor
Feng Wang
Jianbo Chen
Jiaxiang Zhou
Yi Zhang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wacker Chemie AG
Original Assignee
Wacker Chemie AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Priority to PCT/CN2024/086930 priority Critical patent/WO2025213375A1/en
Publication of WO2025213375A1 publication Critical patent/WO2025213375A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group, wherein Cn means a carbon skeleton not containing a ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • 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

Definitions

  • the present invention relates to water-based polymer dispersions, in particular to vinyl ester-ethylene copolymer dispersions resistant to biodeterioration.
  • PDMAEMA polymer which is a polymer of Dimethylaminoethyl methacrylate, which is resistant to biodeterioration.
  • CN101044176B discloses a copolymer with acrylic acid the principal monomer, wherein the d1 comonomer may contain (2-dimethylamino) ethyl methacrylate.
  • the copolymer can be used in cosmetics and pharmaceuticals. Its main uses are as binders, film-forming agents, surface-active compounds, or to modify the rheological properties of aqueous systems.
  • CN1328296C discloses a multifunctional copolymer with acrylamide as the principal monomer, which is used as a film-forming agent in the field of cosmetic hair treatment.
  • the comonomers of the copolymer may contain ethylene, vinyl acetate and (2-dimethylamino) ethyl methacrylate.
  • ethylene and vinyl acetate as principal monomers.
  • the present invention provides a water-based polymer dispersion that is resistant to biodeterioration.
  • the dispersion is odorless to the human olfactory system and has stable storage properties and long term resistance to biodeterioration.
  • the residual monomer content in this dispersion is less than 1000ppm, preferable less than 500ppm, more preferable less than 300ppm.
  • the present invention provides a water-based polymer dispersion, which contains
  • Component i) a Copolymer prepared by the polymerization of monomers containing vinyl ester, ethylene and Monomer A according to the formula (1) ,
  • R 1 is H or C1-C4 alkyl
  • R 2 is C1-C4 alkylene
  • R 3 and R 4 are C1-C4 alkyl
  • Monomer A is used in an amount of 0.10 to 5 wt%, preferably from 0.40 to 5 wt%, more preferably from 0.40 to 3 wt%, more preferably from 0.40 to 2 wt%, such as 0.20 wt%, 0.30 wt%, 0.45 wt%, 0.65 wt%, 0.85 wt%, 1.05 wt%, 1.25 wt%, 1.45 wt%, 1.65 wt%, 1.85 wt%, 2.25 wt%, 2.45 wt%, 2.65 wt%, based on the total weight, as 100 wt%, of the vinyl ester and ethylene monomers;
  • the total amount of vinyl ester and ethylene is greater than 80wt%, preferably greater than 85wt%, preferably greater than 90wt%, more preferably greater than 95wt%, more preferably greater than 97wt%, more preferably greater than 98wt%, more preferably greater than 98.5 wt%, based on 100 wt%of the total weight of the Component i) Copolymer.
  • the vinyl ester is one or more selected from the group consisting of vinyl acetate, vinyl butyrate, vinyl propionate, vinyl pivalate, vinyl 2-ethylhexanoate, 1-methyl vinyl acetate, and vinyl laurate, preferably the vinyl ester is vinyl acetate.
  • R 1 is H or C1-C2 alkyl
  • R 2 is C1-C3 alkylene
  • R 3 and R 4 are C1-C2 alkyl, preferably R 1 is H or methyl
  • R 2 is ethylene or propylene
  • R 3 and R 4 are methyl.
  • the Monomer A is one or more selected from the group consisting of (2-dimethylamino) ethyl methacrylate, (2-dimethylamino) ethyl acrylate, Dimethylaminopropyl methacrylate, and 3- (Dimethylamino) propyl acrylate.
  • An anti-biodeterioration water-based dispersion which contains the water-based polymer dispersion as described above.
  • Preferred drying treatment is water removal treatment and/or solvent removal treatment; more preferred drying treatment is spraying drying treatment.
  • the pH value of which is less than or equal to 5 preferably the pH is between 3 and 5, such as 3.5, 3.8, 4.0, 4.2, 4.3, 4.5, 4.8.
  • the pH value of which is more than 5 preferably the pH is between 5 and 9, such as 5.5, 5.8, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5.
  • the dosage of "biocides” and “antibiotics” is below 800 ppm, preferably below 500 ppm, preferably below 200 ppm, more preferably below 100 ppm, more preferably below 50 ppm.
  • the water-based polymer dispersion as described above is essentially free of "biocides” and “antibiotics” .
  • the "resistant to biodeterioration” mentioned in the present invention refers to the effect of killing or inhibiting the growth of microorganisms.
  • Microorganisms generally include bacteria, actinomycetes, spirochetes, mycoplasmas, rickettsiae, and chlamydia belonging to prokaryotes; fungi, algae, protozoa belonging to eukaryotes, and viruses and subviruses.
  • the "resistant to biodeterioration" mentioned in the present invention refers to the effect of killing or inhibiting the growth of bacteria and algae; more preferably, the effect of killing or inhibiting the growth of microorganisms that contaminate the polymer emulsion.
  • water-based polymer dispersions or polymer emulsions become contaminated with microorganisms, this can lead to a range of effects including color changes, odor, viscosity changes, pH changes and visible surface growth. It is known in the art that water-based polymer dispersions or polymer emulsions are susceptible to contamination by a wide variety of microorganisms.
  • the microorganisms found to contaminate water-based polymer dispersions or polymer emulsions are one or more selected from the group consisting of
  • Aeromonas hydrophilia Alcaligenes faecalis, Corynebacterium ammoniagenes, Enterobacter aerogenes, Proteus vulgaris, Providencia rettgeri, Pseudomonas stutzeri, Pseudomonas putida, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aereus, Klebsiella pneumoniae, Shewanella putrefaciens, Serratia liquefaciens, Acinetobacter baumannii, Burkholderia epacian, Chryseobacterium meningosepticum, Sphingobacterium spiritivorum, Ralstonia pickettii, Gluconoacetobacter liquefaciens, Gluconoacetobacter, Geotrichum candidum, Aspergillus species, Sporothrix species, Trichoderma viride, Cladosporium species, Rh
  • the phrase “inhibits and control the growth, ” is defined to mean that the item in question leads to a reduction in the concentration of a broad spectrum of microorganisms by a magnitude of at least 1 log 10 as measured by shaker flask method, liquid droplet challenge test, and/or aerosol challenge test within a period of time.
  • it leads to a reduction in microbial concentration by a factor of 3 log 10 (i.e., reduction by 10 3 colony forming units per gram of material (CFU/g) ) within 1day or 4days or 7 days.
  • CFU/g colony forming units per gram of material
  • biocides is a general term describing a chemical agent, such as a pesticide, usually broad spectrum, which inactivates living microorganisms.
  • antibiotics refer to a synthetic or naturally-derived organic chemical substance, used most often at low concentrations, in the treatment of infectious diseases of man, animals, and plants, which prevents or inhibits the growth of microorganisms.
  • antibiotics include therapeutic drugs, like penicillin, while biocides are disinfectants or antiseptics like iodine.
  • Antibiotics typically have a single target and a very specific mode of action, thus interacting with either receptors in the cellular membrane, or the metabolic or nucleic functions of the cell, causing inhibition of enzymatic or metabolic processes, similar to a “lock and key” to achieve microbicidal action, whereas biocides have multiple targets and modes of action, which for instance, may include physical disruption and permanent damage to the outer cell membrane of a bacterial microbe.
  • Antibiotics and biocides are as different from one another as trying to open a door with a key versus a sledge hammer.
  • the biocide is one or more selected from the group consisting of
  • biguanides e.g., : chlorhexidine, alexidine, polyhexamethylene biguanide, and relevant salts thereof
  • biguanides e.g., : chlorhexidine, alexidine, polyhexamethylene biguanide, and relevant salts thereof
  • halogen-releasing agents e.g., : iodine, iodophors, sodium hypochlorite, N-halamine, etc.
  • stabilized peroxide e.g., urea peroxide, mannitol peroxide
  • metal-containing species and oxides thereof e.g., : silver, copper, selenium, etc. either in particle form or incorporated into a support matrix such as a zeolite or polymer
  • a support matrix such as a zeolite or polymer
  • sulfides e.g., sodium metabisulfite
  • bis-phenols e.g., triclosan, hexachlorophene, etc
  • quaternary ammonium compounds e.g., benzalkonium chloride, cetrimide, cetylpyridium chloride, quaternized cellulose and other quaternized polymers, etc.
  • various “naturally occurring” agents e.g., polyphenols from green or black tea extract, citric acid, chitosan, anatase TiO 2 , tourmaline, bamboo extract, neem oil, etc. ) ,
  • the biocide is one or more selected from 1, 2-benzisothiazolin-3-one (BIT) , 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) , 2-methyl-4-isothiazolin-3-one (MIT) .
  • BIT 2-benzisothiazolin-3-one
  • CIT 5-chloro-2-methyl-4-isothiazolin-3-one
  • MIT 2-methyl-4-isothiazolin-3-one
  • the amount of anionic surfactant and/or cationic surfactant in the water-based polymer dispersion is less than 1 wt%, preferably less than 0.5 wt%, and more preferably less than 0.1 wt%, which are based on the total weight of vinyl acetate and ethylene monomer as 100wt%.
  • the vinyl ester is present in the water-based polymer dispersion in an amount of from 70 to 95 wt%, preferably from 70 to 90 wt%, more preferably from 70 to 85 wt%, most preferably from 71-75wt%or from 81 to 85 wt%, and ethylene is present in an amount of from 5 to 30 wt%, preferably from 10 to 25 wt%, more preferably from 15 to 30 wt%, most preferably from 25 to 29 wt%or from 15 to 19 wt%, based on the total weight of the vinyl acetate and ethylene monomers.
  • the polyvinyl alcohols can be medium molecular weight polyvinyl alcohols, low molecular weight polyvinyl alcohols, or a combination thereof, preferably comprising at least one medium molecular weight polyvinyl alcohol and at least one low molecular weight polyvinyl alcohol.
  • the term “medium molecular weight polyvinyl alcohol” refers to polyvinyl alcohols having a viscosity, in 4 wt%aqueous solution, of from 10 to 35 mPa ⁇ s measured at 20°Caccording to DIN 53015.
  • the term “low molecular weight polyvinyl alcohol” herein refers to polyvinyl alcohols having a viscosity, in 4 wt%aqueous solution, of from 3 to 10 mPa ⁇ s measured at 20°C according to DIN 53015.
  • the medium molecular weight polyvinyl alcohols have a degree of hydrolysis of from 85 to 99 mol%and the low molecular weight polyvinyl alcohols have a degree of hydrolysis of from 75 to 90 mol%.
  • Suitable medium molecular weight polyvinyl alcohols can be PVOH 25/88 and /or PVOH 117 but are not limited thereto.
  • Suitable low molecular weight polyvinyl alcohols can be PVOH 04/88 but are not limited thereto.
  • the polyvinyl alcohols can be used in an amount of suitably from 2 to 8 wt%, preferably from 2 to 6 wt%, for example, 2 wt%, 3 wt%, 4 wt%, 5 wt%or 6 wt%, based on the total weight of the vinyl acetate and ethylene monomers.
  • the polyvinyl alcohols comprise one medium molecular weight polyvinyl alcohol and one low molecular weight polyvinyl alcohol, wherein the former has a degree of hydrolysis of from 85 to 99 mol%, and the latter has a degree of hydrolysis of from 75 to 90 mol%
  • the polyvinyl alcohols comprise two medium molecular weight polyvinyl alcohols and one low molecular weight polyvinyl alcohol, wherein the first medium molecular weight polyvinyl alcohol has a degree of hydrolysis of from 85 to 95 mol%and a viscosity, in 4 wt%aqueous solution, of from 20 to 30 mPa ⁇ s measured at 20°C according to DIN 53015, the second medium molecular weight polyvinyl alcohol has a degree of hydrolysis of from 95 to 99 mol%and a viscosity, in 4 wt%aqueous solution, of from 10 to 20 mPa ⁇ s measured at 20°C according to DIN 53015, the low molecular weight polyvinyl alcohol has a degree of hydrolysis of from 75 to 90 mol%and a viscosity, in 4 wt%aqueous solution, of from 3 to 10 mPa ⁇ s measured at 20°Caccording to DIN 53015.
  • the copolymerization is initiated by a redox initiator.
  • Suitable oxidizing agents can be one or more members selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl peroxides (e.g. t-butyl hydroperoxide) , potassium peroxodisulfate, t-butyl peroxypivalate, cumyl hydroperoxide and azobisisobutyronitrile, preferably one, or a combination, of sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide and t-butyl peroxide.
  • the oxidizing agent is suitably used in an amount of from 0.1 to 2 wt%, preferably from 0.2 to 1 wt%, based on the total weight of the vinyl ester and ethylene monomers.
  • Suitable reducing agents are one or more members selected from the group consisting of alkali metal or ammonium sulfites, bisulfites (e.g. sodium sulfite) , derivatives of sulfoxylates (e.g. formaldehyde-zinc sulfoxylate or formaldehyde-sodium sulfoxylate) , sulfinic acid or salts thereof (e.g. 2-hydroxy-2-sulfinatoacetate, disodium 2-hydroxy-2-sulfinatoacetate, zinc 2-hydroxy-2-sulfinatoacetate, or disodium 2-hydroxy-2-sulfinopropionate) , ascorbic acid or salts thereof (e.g.
  • Other comonomer refers to one or more monomer other than vinyl acetate, ethylene, and Monomer A according to the formula (1) that can undergo radical polymerization.
  • halogenated ethylenes such as vinyl chloride
  • olefins with more than 2 carbon atoms such as propylene
  • ethylenically unsaturated carboxylic acids and derivatives thereof such as fumaric acid, maleic acid, maleic anhydride, acrylamide, and acrylonitrile
  • precrosslinking comonomers or postcrosslinking comonomers such as divinyl adipate, diallyl maleate, allyl methacrylate, triallyl cyanurate, acrylamidoglycolic acid (AGA) , methacrylamide glycolate methyl ester (MAGME) , N-methylol acrylamide (NMA) , N-methylol methacrylamide (NMMA) , N-methylolallyl carbamate, isobutoxy ethers or esters of N-methylol acrylamide, isobutoxy ethers or esters of N-methylol acrylamide, isobutoxy ethers or esters of
  • the Other comonomers can be used in an amount of 10 wt%or less, for example, 5 wt%or less, 2 wt%or less, 1 wt%or less, 0.5 wt%or less, 0.1 wt%or less, or 0.01 wt%or less, based on the total weight of the vinyl ester and ethylene monomers as 100wt%.
  • the Other comonomers can be used in an amount of 10 wt%or less, for example, 5 wt%or less, 2 wt%or less, 1 wt%or less, 0.5 wt%or less, 0.1 wt%or less, or 0.01 wt%or less, based on the total weight of the vinyl acetate and ethylene monomers as 100wt%.
  • the water-based polymer dispersion can be prepared by a solution, dispersion or suspension polymerization process, preferably a dispersion polymerization process.
  • the polymerization process can be divided into three stages: (1) prior to the initiation of the polymerization, (2) during polymerization, and (3) post-polymerization.
  • the stage prior to the initiation of the polymerization refers to the stage before the polymerization of monomers is initiated by an initiator.
  • the post-polymerization stage refers to the stage where the reaction between the vinyl ester and ethylene monomers is mostly completed and the residual vinyl ester monomer content is 2 wt%or less (based on the total weight of the vinyl ester monomer) , even 1 wt%or 5, 000 ppm or less.
  • the initial materials added to the reactor include:
  • At least part suitably from 40 to 100 wt%, preferably from 50 to 85 wt%, of ethylene, based on the total amount thereof;
  • the initial materials prepared prior to the initiation of the polymerization comprise 50 to 80 wt%of the vinyl ester based on the total amount thereof, 50 to 75 wt%of ethylene based on the total amount thereof, and 100 wt%of polyvinyl alcohol.
  • the pH value of the initial materials Prior to the initiation of the polymerization, it is necessary to adjust the pH value of the initial materials, once prepared and charged into the reactor, to less than 6, preferably less than 5, more preferably from 3 to 4.
  • An organic or inorganic acid preferably phosphoric or formic acid, is commonly used to adjust the pH.
  • a catalyst such as ferrous ammonium sulfate, can also be usually added to the initial materials in the reactor to initiate and catalyze the polymerization reaction.
  • the polymerization is carried out typically at from 20 to150 °C, preferably from 50 to120 °C.
  • the pressure in the reactor is usually stable during the polymerization, which is achieved by controlling the charge of ethylene, and can be set at different levels to meet the requirements of different formulations for the pressure.
  • Suitable pressure during the polymerization is typically between 2 and 100 bar, preferably between 40 and 80 bar.
  • the initial materials are usually heated to a temperature 10 to 40°C lower than the desired temperature, and the reactor is further heated to the reaction temperature by the heat released from the polymerization reaction before the remaining monomers are metered and fed while the redox initiator is kept feeding.
  • the Monomer A is preferably added in the stage of “ During the polymerization” , and preferably added to the reaction kettle in a dropwise manner in the stage of “ During the polymerization” .
  • defoamers can be optionally added to the dispersion after the vinyl ester-ethylene polymerization is completed.
  • Suitable defoamers can be one, or a combination, of mineral oil-based defoamers, higher aliphatic alcohol-based defoamers, polyether-based defoamers and silicone-based defoamers, preferably mineral oil-based defoamers, wherein the mineral oil-based defoamers are defoamers with mineral oils (such as white oil, diesel or kerosene) as a carrier and hydrophobic substances (such as fatty acid/fatty acid metal soap, fatty acid amide and higher aliphatic alcohol) as an active defoaming ingredient.
  • mineral oils such as white oil, diesel or kerosene
  • hydrophobic substances such as fatty acid/fatty acid metal soap, fatty acid amide and higher aliphatic alcohol
  • the defoamer can be used in an amount of 2 wt%or less, for example, 1 wt%or less, 0.5 wt%or less, or 0.2 wt%or less, based on the total weight of the vinyl ester and ethylene monomers as 100wt%.
  • the samples After passing the sterility test, the samples are used for the wet state challenge test.
  • each round lasts for 7 days, and score on the 1 st, 4th, and 7th days respectively. If the score is 0 on the 7th day, the round passes. If the score on the 7th day is 4 or higher, this round fails.
  • BG11 culture fluid Mix 1.7g BG11 culture medium (Haibo Biotechnology) and 1000ml distilled water, heat and dissolve; sterilize with high-pressure steam at about 121°C; then cool to room temperature (25°C) for use.
  • step (3) Place the test tube obtained in step (2) into the artificial climate box (25°C) , connect the air inlet and outlet pipeline, adjust the bubbling rate, and start culture in the artificial climate box.
  • RT means the sample in room temperature condition is inoculated, then being subjected to the wet state challenge test.
  • 50°C*2w means that the sample is stored at 50°C for 2 weeks before the inoculation and the wet state challenge test.
  • pphm refers to parts per hundred principal monomers, i.e., parts per hundred of the vinyl acetate and ethylene.
  • C. Ex. 7 does not contain comonomers. After the polymerization is completed, 200 ppm isothiazolinone complex is added to the water-based ethylene-vinyl acetate base polymer dispersion to obtain the C. Ex. 7 product. Isothiazolinone complex is a mixture of CIT, MIT and BIT. The dosage is 200ppm, calculated based on the mass of water-based polymer dispersion being 100wt%. C. Ex. 8 product has a good effect on inhibiting bacteria but has a poor effect on inhibiting algae.
  • C. Ex. 8 2- (dimethylamino) ethyl methacrylate is polymerized alone to obtain the homopolymer PDMAEMA.
  • PDMAEMA is added to the aqueous ethylene-vinyl acetate base polymer dispersion to obtain C. Ex. 8 product, in which the dosage of 2- (dimethylamino) ethyl methacrylate Dimethylaminoethyl methacrylate is 1 pphm. After 2 weeks of storage at 50°C, the C. Ex. 8 product phase separated, and a uniform and stable aqueous dispersion could not be obtained.

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Abstract

A water-based ethylene-vinyl ester copolymer dispersion containing acrylate monomers. The water-based dispersion is resistant to biodeterioration.

Description

Water-based Polymer Dispersions Field of the Invention
The present invention relates to water-based polymer dispersions, in particular to vinyl ester-ethylene copolymer dispersions resistant to biodeterioration.
Background of the Invention
Ao Chen, Hui Peng, Idriss Blakey &Andrew K. Whittaker (2016) : Biocidal Polymers: A Mechanistic Overview, Polymer Reviews, DOI: 10.1080/15583724.2016.1223131 discloses a PDMAEMA polymer, which is a polymer of Dimethylaminoethyl methacrylate, which is resistant to biodeterioration.
CN101044176B discloses a copolymer with acrylic acid the principal monomer, wherein the d1 comonomer may contain (2-dimethylamino) ethyl methacrylate. The copolymer can be used in cosmetics and pharmaceuticals. Its main uses are as binders, film-forming agents, surface-active compounds, or to modify the rheological properties of aqueous systems.
CN1328296C discloses a multifunctional copolymer with acrylamide as the principal monomer, which is used as a film-forming agent in the field of cosmetic hair treatment. The comonomers of the copolymer may contain ethylene, vinyl acetate and (2-dimethylamino) ethyl methacrylate. However, there is no disclosure of copolymers with ethylene and vinyl acetate as principal monomers.
Summary of the Invention
The present invention provides a water-based polymer dispersion that is resistant to biodeterioration.
The dispersion is odorless to the human olfactory system and has stable storage properties and long term resistance to biodeterioration. The residual monomer content in this dispersion is less than 1000ppm, preferable less than 500ppm, more preferable less than 300ppm.
The present invention provides a water-based polymer dispersion, which contains
Component i) a Copolymer prepared by the polymerization of monomers containing vinyl ester, ethylene and Monomer A according to the formula (1) ,
Where R1 is H or C1-C4 alkyl; R2 is C1-C4 alkylene; R3 and R4 are C1-C4 alkyl,
Component iv) water,
wherein Monomer A is used in an amount of 0.10 to 5 wt%, preferably from 0.40 to 5 wt%, more preferably from 0.40 to 3 wt%, more preferably from 0.40 to 2 wt%, such as 0.20 wt%, 0.30 wt%, 0.45 wt%, 0.65 wt%, 0.85 wt%, 1.05 wt%, 1.25 wt%, 1.45 wt%, 1.65 wt%, 1.85 wt%, 2.25 wt%, 2.45 wt%, 2.65 wt%, based on the total weight, as 100 wt%, of the vinyl ester and ethylene monomers;
wherein the total amount of vinyl ester and ethylene is greater than 80wt%, preferably greater than  85wt%, preferably greater than 90wt%, more preferably greater than 95wt%, more preferably greater than 97wt%, more preferably greater than 98wt%, more preferably greater than 98.5 wt%, based on 100 wt%of the total weight of the Component i) Copolymer.
The water-based polymer dispersion according to above, the vinyl ester is one or more selected from the group consisting of vinyl acetate, vinyl butyrate, vinyl propionate, vinyl pivalate, vinyl 2-ethylhexanoate, 1-methyl vinyl acetate, and vinyl laurate, preferably the vinyl ester is vinyl acetate.
The water-based polymer dispersion as above, wherein in the Monomer A, R1 is H or C1-C2 alkyl; R2 is C1-C3 alkylene; R3 and R4 are C1-C2 alkyl, preferably R1 is H or methyl; R2 is ethylene or propylene; R3 and R4 are methyl.
The water-based polymer dispersion as described above, wherein the Monomer A is one or more selected from the group consisting of (2-dimethylamino) ethyl methacrylate, (2-dimethylamino) ethyl acrylate, Dimethylaminopropyl methacrylate, and 3- (Dimethylamino) propyl acrylate.
As mentioned above, the use of the water-based polymer dispersion in the field of anti-biodeterioration, preferably in the field of anti-biodeterioration of polymer emulsions.
An anti-biodeterioration water-based dispersion, which contains the water-based polymer dispersion as described above.
A composition containing a product obtained by drying the water-based polymer dispersion as described above. Preferred drying treatment is water removal treatment and/or solvent removal treatment; more preferred drying treatment is spraying drying treatment.
According to the water-based polymer dispersion as described above, wherein Component i) , the Copolymer, is prepared by using Component iii) , polyvinyl alcohol and/or hydroxyethyl cellulose, as a protective colloid.
According to the water-based polymer dispersion as described above, which contains
39-60 wt%of Component i) , a copolymer prepared by the polymerization of monomers containing vinyl ester, ethylene and Monomer A according to the formula (1) ,
0.6-4 wt%of Component iii) , a protective colloid, and
39-60 wt%of Component iv) , water,
based on the total weight, as 100 wt%, of the water-based polymer dispersion.
According to the water-based polymer dispersion as described above, which contains
49-60 wt%of Component i) , a copolymer prepared by the polymerization of monomers comprising vinyl ester, ethylene and Monomer A according to the formula (1) ,
0.9-3 wt%of Component iii) , a protective colloid, and
39-50 wt%of Component iv) , water,
based on the total weight, as 100 wt%, of the water-based polymer dispersion.
According to the water-based polymer dispersion as described above, the pH value of which is less than or equal to 5, preferably the pH is between 3 and 5, such as 3.5, 3.8, 4.0, 4.2, 4.3, 4.5, 4.8.
According to the water-based polymer dispersion as described above, the pH value of which is more than 5, preferably the pH is between 5 and 9, such as 5.5, 5.8, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5.
The water-based polymer dispersion as above, wherein the total amount of vinyl acetate and ethylene is greater than 85wt%, preferably greater than 90wt%, more preferably greater than 95wt%, more preferably greater than 97wt%, more preferably greater than 98wt%, more preferably greater than 98.5 wt%, based on 100 wt%of the total weight of the Component i) Copolymer.
The water-based polymer dispersion as above, wherein the total amount of vinyl acetate, ethylene and Monomer A is greater than 85wt%, preferably greater than 90wt%, more preferably greater than 95wt%, more preferably greater than 97wt%, more preferably greater than 98wt%, more preferably greater than 99 wt%, more preferably greater than 99.5 wt%, more preferably greater than 99.9 wt%, based on 100 wt%of the total weight of the Component i) Copolymer.
According to the water-based polymer dispersion as described above, wherein the dosage of "biocides" and "antibiotics" is below 800 ppm, preferably below 500 ppm, preferably below 200 ppm, more preferably below 100 ppm, more preferably below 50 ppm.
The water-based polymer dispersion as described above is essentially free of "biocides" and "antibiotics" .
The "resistant to biodeterioration" mentioned in the present invention refers to the effect of killing or inhibiting the growth of microorganisms.
Microorganisms generally include bacteria, actinomycetes, spirochetes, mycoplasmas, rickettsiae, and chlamydia belonging to prokaryotes; fungi, algae, protozoa belonging to eukaryotes, and viruses and subviruses.
Preferably, the "resistant to biodeterioration" mentioned in the present invention refers to the effect of killing or inhibiting the growth of bacteria and algae; more preferably, the effect of killing or inhibiting the growth of microorganisms that contaminate the polymer emulsion.
When water-based polymer dispersions or polymer emulsions become contaminated with microorganisms, this can lead to a range of effects including color changes, odor, viscosity changes, pH changes and visible surface growth. It is known in the art that water-based polymer dispersions or polymer emulsions are susceptible to contamination by a wide variety of microorganisms.
In present invention, the microorganisms found to contaminate water-based polymer dispersions or polymer emulsions are one or more selected from the group consisting of
Aeromonas hydrophilia, Alcaligenes faecalis, Corynebacterium ammoniagenes, Enterobacter aerogenes, Proteus vulgaris, Providencia rettgeri, Pseudomonas stutzeri, Pseudomonas putida, Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aereus, Klebsiella pneumoniae, Shewanella putrefaciens, Serratia liquefaciens, Acinetobacter baumannii, Burkholderia epacian, Chryseobacterium meningosepticum, Sphingobacterium spiritivorum, Ralstonia pickettii, Gluconoacetobacter liquefaciens, Gluconoacetobacter, Geotrichum candidum, Aspergillus species, Sporothrix species, Trichoderma viride, Cladosporium species, Rhodoturula glutinis, Candida guillermondi, Penicillium species, Candida tropicalis, Saccharomyces cerevisiae、Candida albicans、Rhodotorula rubra, and Vacuoliviride species algae.
As used herein, the phrase “inhibits and control the growth, ” is defined to mean that the item in question leads to a reduction in the concentration of a broad spectrum of microorganisms by a magnitude of at least 1 log10 as measured by shaker flask method, liquid droplet challenge test, and/or aerosol challenge test within a period of time. Preferably, it leads to a reduction in microbial concentration by a factor of 3 log10 (i.e., reduction by 103 colony forming units per gram of material (CFU/g) ) within 1day or 4days or 7 days. Most preferably, it leads to a reduction in microbial concentration by a factor of 4 log10 or more within 1 day or 4 days or 7 days.
The term “biocides” is a general term describing a chemical agent, such as a pesticide, usually broad spectrum, which inactivates living microorganisms.
The term “antibiotics” refer to a synthetic or naturally-derived organic chemical substance, used most often at low concentrations, in the treatment of infectious diseases of man, animals, and plants, which prevents or inhibits the growth of microorganisms.
Examples of antibiotics include therapeutic drugs, like penicillin, while biocides are disinfectants or antiseptics like iodine.
Antibiotics typically have a single target and a very specific mode of action, thus interacting with either receptors in the cellular membrane, or the metabolic or nucleic functions of the cell, causing inhibition of enzymatic or metabolic processes, similar to a “lock and key” to achieve microbicidal action, whereas biocides have multiple targets and modes of action, which for instance, may include physical disruption and permanent damage to the outer cell membrane of a bacterial microbe. Antibiotics and biocides are as different from one another as trying to open a door with a key versus a sledge hammer.
In present invention, the biocide is one or more selected from the group consisting of
biguanides (e.g., : chlorhexidine, alexidine, polyhexamethylene biguanide, and relevant salts thereof) ,
halogen-releasing agents (e.g., : iodine, iodophors, sodium hypochlorite, N-halamine, etc. ) ,
stabilized oxidants such as chlorine dioxide,
stabilized peroxide (e.g., urea peroxide, mannitol peroxide)
metal-containing species and oxides thereof (e.g., : silver, copper, selenium, etc. either in particle form or incorporated into a support matrix such as a zeolite or polymer) ,
sulfides (e.g., sodium metabisulfite) ,
bis-phenols (e.g., triclosan, hexachlorophene, etc) ,
quaternary ammonium compounds (e.g., benzalkonium chloride, cetrimide, cetylpyridium chloride, quaternized cellulose and other quaternized polymers, etc. ) ,
various “naturally occurring” agents (e.g., polyphenols from green or black tea extract, citric acid, chitosan, anatase TiO2, tourmaline, bamboo extract, neem oil, etc. ) ,
1, 2-benzisothiazolin-3-one (BIT) , 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) , 2-methyl-4-isothiazolin-3-one (MIT) ,
1, 2-dibromo-2, 4-dicyanobutane (DBDCB) , 2, 2-dibromo-3-nitrilo-propionamide (DBNPA) , 2-bromo-2-nitro-1, 3-propanediol (BNPD) , aldehyde derivatives, formaldehyde releasing agents, hydantoins, and chlorinated aromatics.
Perferablely, the biocide is one or more selected from 1, 2-benzisothiazolin-3-one (BIT) , 5-chloro-2-methyl-4-isothiazolin-3-one (CIT) , 2-methyl-4-isothiazolin-3-one (MIT) .
According to the water-based polymer dispersion as described above, the amount of anionic surfactant and/or cationic surfactant in the water-based polymer dispersion is less than 1 wt%, preferably less than 0.5 wt%, and more preferably less than 0.1 wt%, which are based on the total weight of vinyl acetate and ethylene monomer as 100wt%.
According to the water-based polymer dispersion as described above, the vinyl ester is present in the water-based polymer dispersion in an amount of from 70 to 95 wt%, preferably from 70 to 90 wt%, more preferably from 70 to 85 wt%, most preferably from 71-75wt%or from 81 to 85 wt%, and ethylene is present in an amount of from 5 to 30 wt%, preferably from 10 to 25 wt%, more preferably from 15 to 30 wt%, most preferably from 25 to 29 wt%or from 15 to 19 wt%, based on the total weight of the vinyl acetate and ethylene monomers.
Polyvinyl alcohol
According to the invention, the polyvinyl alcohols can be medium molecular weight polyvinyl alcohols, low molecular weight polyvinyl alcohols, or a combination thereof, preferably comprising at least one medium molecular weight polyvinyl alcohol and at least one low molecular weight polyvinyl alcohol.
As used herein, the term “medium molecular weight polyvinyl alcohol” refers to polyvinyl alcohols having aviscosity, in 4 wt%aqueous solution, of from 10 to 35 mPa·s measured at 20℃according to DIN 53015. The term “low molecular weight polyvinyl alcohol” herein refers to polyvinyl alcohols having aviscosity, in 4 wt%aqueous solution, of from 3 to 10 mPa·s measured at 20℃ according to DIN 53015. Typically, the medium molecular weight polyvinyl alcohols have a degree of hydrolysis of from 85 to 99 mol%and the low molecular weight polyvinyl alcohols have a degree of hydrolysis of from 75 to 90 mol%.
Suitable medium molecular weight polyvinyl alcohols can be PVOH 25/88 and /or PVOH 117 but are not limited thereto. Suitable low molecular weight polyvinyl alcohols can be PVOH 04/88 but are not limited thereto.
According to the invention, the polyvinyl alcohols can be used in an amount of suitably from 2 to 8  wt%, preferably from 2 to 6 wt%, for example, 2 wt%, 3 wt%, 4 wt%, 5 wt%or 6 wt%, based on the total weight of the vinyl acetate and ethylene monomers.
In certain embodiments of the invention, the polyvinyl alcohols comprise one medium molecular weight polyvinyl alcohol and one low molecular weight polyvinyl alcohol, wherein the former has a degree of hydrolysis of from 85 to 99 mol%, and the latter has a degree of hydrolysis of from 75 to 90 mol%
In other embodiments of the invention, the polyvinyl alcohols comprise two medium molecular weight polyvinyl alcohols and one low molecular weight polyvinyl alcohol, wherein the first medium molecular weight polyvinyl alcohol has a degree of hydrolysis of from 85 to 95 mol%and aviscosity, in 4 wt%aqueous solution, of from 20 to 30 mPa·s measured at 20℃ according to DIN 53015, the second medium molecular weight polyvinyl alcohol has a degree of hydrolysis of from 95 to 99 mol%and aviscosity, in 4 wt%aqueous solution, of from 10 to 20 mPa·s measured at 20℃ according to DIN 53015, the low molecular weight polyvinyl alcohol has a degree of hydrolysis of from 75 to 90 mol%and aviscosity, in 4 wt%aqueous solution, of from 3 to 10 mPa·s measured at 20℃according to DIN 53015.
Redox initiator
According to the invention, the copolymerization is initiated by a redox initiator. Suitable oxidizing agents can be one or more members selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl peroxides (e.g. t-butyl hydroperoxide) , potassium peroxodisulfate, t-butyl peroxypivalate, cumyl hydroperoxide and azobisisobutyronitrile, preferably one, or a combination, of sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide and t-butyl peroxide. According to the invention, the oxidizing agent is suitably used in an amount of from 0.1 to 2 wt%, preferably from 0.2 to 1 wt%, based on the total weight of the vinyl ester and ethylene monomers.
Suitable reducing agents are one or more members selected from the group consisting of alkali metal or ammonium sulfites, bisulfites (e.g. sodium sulfite) , derivatives of sulfoxylates (e.g. formaldehyde-zinc sulfoxylate or formaldehyde-sodium sulfoxylate) , sulfinic acid or salts thereof (e.g. 2-hydroxy-2-sulfinatoacetate, disodium 2-hydroxy-2-sulfinatoacetate, zinc 2-hydroxy-2-sulfinatoacetate, or disodium 2-hydroxy-2-sulfinopropionate) , ascorbic acid or salts thereof (e.g. sodium ascorbate) , isoascorbic acid or salts thereof (e.g. sodium erythorbate) and tartaric acid, preferably one or more members selected from among sulfinic acid or salts thereof, ascorbic acid or salts thereof and isoascorbic acid or salts thereof. The sulfinic acids or salts thereof can also be commercially available, for example, FF6, FF6M orFF7 supplied by BrüggemannChemical, Germany. According to the invention, the reducing agent is suitably used in an amount of from 0.02 to 2 wt%, preferably from 0.05 to 1 wt%, based on the total weight of the vinyl ester and ethylene monomers.
Other comonomers
In present invention, Other comonomer refers to one or more monomer other than vinyl acetate, ethylene, and Monomer A according to the formula (1) that can undergo radical polymerization.
In present invention, the examples of Other comonomer are listed below: halogenated ethylenes, such as vinyl chloride; olefins with more than 2 carbon atoms, such as propylene; ethylenically  unsaturated carboxylic acids and derivatives thereof, such as fumaric acid, maleic acid, maleic anhydride, acrylamide, and acrylonitrile; precrosslinking comonomers or postcrosslinking comonomers, such as divinyl adipate, diallyl maleate, allyl methacrylate, triallyl cyanurate, acrylamidoglycolic acid (AGA) , methacrylamide glycolate methyl ester (MAGME) , N-methylol acrylamide (NMA) , N-methylol methacrylamide (NMMA) , N-methylolallyl carbamate, isobutoxy ethers or esters of N-methylol acrylamide, isobutoxy ethers or esters of N-methylol methacrylamide, isobutoxy ethers or esters of N-methylolallyl carbamate; epoxy-functional comonomers such as glycidyl methacrylate (GAM) and glycidyl acrylate; and silicon-functional comonomers such as vinyl trialkoxysilanes, vinyl methyl dialkoxysilanes.
According to the invention, the Other comonomers can be used in an amount of 10 wt%or less, for example, 5 wt%or less, 2 wt%or less, 1 wt%or less, 0.5 wt%or less, 0.1 wt%or less, or 0.01 wt%or less, based on the total weight of the vinyl ester and ethylene monomers as 100wt%.
According to the invention, the Other comonomers can be used in an amount of 10 wt%or less, for example, 5 wt%or less, 2 wt%or less, 1 wt%or less, 0.5 wt%or less, 0.1 wt%or less, or 0.01 wt%or less, based on the total weight of the vinyl acetate and ethylene monomers as 100wt%.
According to the invention, the water-based polymer dispersion can be prepared by a solution, dispersion or suspension polymerization process, preferably a dispersion polymerization process. The polymerization process can be divided into three stages: (1) prior to the initiation of the polymerization, (2) during polymerization, and (3) post-polymerization.
According to the invention, the stage prior to the initiation of the polymerization refers to the stage before the polymerization of monomers is initiated by an initiator. The post-polymerization stage refers to the stage where the reaction between the vinyl ester and ethylene monomers is mostly completed and the residual vinyl ester monomer content is 2 wt%or less (based on the total weight of the vinyl ester monomer) , even 1 wt%or 5, 000 ppm or less.
Prior to the initiation of the polymerization, the initial materials added to the reactor include:
a) at least part, suitably from 40 to 100 wt%, preferably from 50 to 85 wt%, of ethylene, based on the total amount thereof;
b) at least part, suitably from 40 to 90%wt%, preferably from 30 to 85 wt%, of the vinyl ester, based on the total amount thereof; and optionally,
c) at least part, suitably at least 20 wt%, preferably at least 50 wt%, more preferably 100 wt%, of the polyvinyl alcohol, based on the total weight thereof.
In some embodiments of the invention, the initial materials prepared prior to the initiation of the polymerization comprise 50 to 80 wt%of the vinyl ester based on the total amount thereof, 50 to 75 wt%of ethylene based on the total amount thereof, and 100 wt%of polyvinyl alcohol.
Prior to the initiation of the polymerization, it is necessary to adjust the pH value of the initial materials, once prepared and charged into the reactor, to less than 6, preferably less than 5, more preferably from 3 to 4. An organic or inorganic acid, preferably phosphoric or formic acid, is commonly  used to adjust the pH. A catalyst, such as ferrous ammonium sulfate, can also be usually added to the initial materials in the reactor to initiate and catalyze the polymerization reaction.
According to the invention, the polymerization is carried out typically at from 20 to150 ℃, preferably from 50 to120 ℃. The pressure in the reactor is usually stable during the polymerization, which is achieved by controlling the charge of ethylene, and can be set at different levels to meet the requirements of different formulations for the pressure. Suitable pressure during the polymerization is typically between 2 and 100 bar, preferably between 40 and 80 bar.
During the polymerization, the initial materials are usually heated to a temperature 10 to 40℃ lower than the desired temperature, and the reactor is further heated to the reaction temperature by the heat released from the polymerization reaction before the remaining monomers are metered and fed while the redox initiator is kept feeding.
The Monomer A is preferably added in the stage of “During the polymerization” , and preferably added to the reaction kettle in a dropwise manner in the stage of “During the polymerization” .
According to the invention, defoamers can be optionally added to the dispersion after the vinyl ester-ethylene polymerization is completed. Suitable defoamers can be one, or a combination, of mineral oil-based defoamers, higher aliphatic alcohol-based defoamers, polyether-based defoamers and silicone-based defoamers, preferably mineral oil-based defoamers, wherein the mineral oil-based defoamers are defoamers with mineral oils (such as white oil, diesel or kerosene) as a carrier and hydrophobic substances (such as fatty acid/fatty acid metal soap, fatty acid amide and higher aliphatic alcohol) as an active defoaming ingredient. The defoamer can be used in an amount of 2 wt%or less, for example, 1 wt%or less, 0.5 wt%or less, or 0.2 wt%or less, based on the total weight of the vinyl ester and ethylene monomers as 100wt%.
Detailed Description of the Preferred Embodiments
The present invention is further illustrated by the following examples but is not limited to the scope thereof. Any experimental methods with no conditions specified in the following examples are selected according to the conventional methods and conditions, or product specifications.
Testing of anti-biodeterioration properties
Sterility test
Around 10ug of each sample was screened on NA (Nutrient agar) and PDA (potato dextrose agar) and incubated in 30℃/25℃ for 2-5 days, to check if the sample was contaminated by bacteria or fungi. The detection limitation of this method is around 100 CFU/g or 100 CFU/ml.
After passing the sterility test, the samples are used for the wet state challenge test.
Wet state challenge test
Inoculate samples at weekly intervals with the Mixed microbial suspension (containing bacterial and yeast) or acetic acid bacteria suspension with 1 ml of inoculum per 50 g of samples. Shake well or mix  with an agitator. Incubate the samples at 30 ±2℃. After incubation shake or mix each sample thoroughly and determine the presence of surviving or growing bacteria. Normal incubation periods are 1, 4 and 7 days. Assessment of streak plates is same as sterility test.
Conduct three rounds of testing on the sample, each round lasts for 7 days, and score on the 1 st, 4th, and 7th days respectively. If the score is 0 on the 7th day, the round passes. If the score on the 7th day is 4 or higher, this round fails.
If the score on the 7th day of each of the three rounds of testing is 0, it is recorded as passing 3  rounds of testing. If the score on day 7 of the first two rounds is 0, it is recorded as passing 2 rounds of  testing. If only the score on the 7th day of the first round is 0, it is recorded as passing 1 round of testing.
Table 1
Table 2
Algae challenge test
(1) Prepare BG11 culture fluid: Mix 1.7g BG11 culture medium (Haibo Biotechnology) and 1000ml distilled water, heat and dissolve; sterilize with high-pressure steam at about 121℃; then cool to room temperature (25℃) for use.
(2) In a glass test tube, mix 100±5g of BG11 culture fluid and 10g of the inoculated emulsion sample evenly. The inoculum concentration was 250 cells/mL, and the algal species was V algae, belonging to Vacuoliviride, Stramenopiles, Eustigmatophyceae.
(3) Place the test tube obtained in step (2) into the artificial climate box (25℃) , connect the air inlet and outlet pipeline, adjust the bubbling rate, and start culture in the artificial climate box.
(4) Continue to culture, observe with the naked eye every day whether there is algae growth and record it; when algae are visible to the naked eye (the culture liquid is green, or there is green precipitate at the bottom of the test tube) , record the number of culture days at this time.
Table 3
Table 4
Table 5

In Table 5, RT means the sample in room temperature condition is inoculated, then being subjected to the wet state challenge test.
50℃*2w means that the sample is stored at 50℃ for 2 weeks before the inoculation and the wet state challenge test.
In Table 4, in every example of Ex. 1-2, 6 and C. Ex. 3-5, 7-8, the water-based ethylene-vinyl acetate base polymer dispersion used is almost the same, which contains 39-60wt%Component i ) , a copolymer prepared by the polymerization of vinyl acetate, ethylene and optional comonomers, 0.6-4wt%Component iii) a polyvinyl alcohol; and 39-60wt%Component iv) , water, of which only the optional comonomers are different.
1 pphm or 0.4 pphm of the comonomer was added in Ex. 1-2, 6 and C. Ex. 3-5 during the polymerization. Among them, 2- (dimethylamino) ethyl methacrylate, and 2- (dimethylamino) ethyl acrylate, belong to the Monomer A of the invention, while N- [3- (Dimethylamino) propyl] methacrylamide and Methacrylamido propyl trimethyl ammonium chloride do not belong to the Monomer A.
The products in Table 1 are still uniform and stable after being stored at 50℃ for 2 weeks. The stability is good.
As used herein, the term "pphm" refers to parts per hundred principal monomers, i.e., parts per hundred of the vinyl acetate and ethylene.
C. Ex. 7 does not contain comonomers. After the polymerization is completed, 200 ppm isothiazolinone complex is added to the water-based ethylene-vinyl acetate base polymer dispersion to obtain the C. Ex. 7 product. Isothiazolinone complex is a mixture of CIT, MIT and BIT. The dosage is 200ppm, calculated based on the mass of water-based polymer dispersion being 100wt%. C. Ex. 8 product has a good effect on inhibiting bacteria but has a poor effect on inhibiting algae.
In addition, in C. Ex. 8, 2- (dimethylamino) ethyl methacrylate is polymerized alone to obtain the homopolymer PDMAEMA. PDMAEMA is added to the aqueous ethylene-vinyl acetate base polymer dispersion to obtain C. Ex. 8 product, in which the dosage of 2- (dimethylamino) ethyl methacrylate Dimethylaminoethyl methacrylate is 1 pphm. After 2 weeks of storage at 50℃, the C. Ex. 8 product phase separated, and a uniform and stable aqueous dispersion could not be obtained.

Claims (10)

  1. A water-based polymer dispersion, which containing
    Component i) a Copolymer prepared by the polymerization of monomers containing vinyl ester, ethylene and Monomer A according to the formula (1) ,
    Where R1 is H or C1-C4 alkyl; R2 is C1-C4 alkylene; R3 and R4 are C1-C4 alkyl,
    Component iv) water,
    wherein Monomer A is used in an amount of 0.10 to 5 wt%, preferably from 0.40 to 5 wt%, more preferably from 0.40 to 3 wt%, more preferably from 0.40 to 2 wt%, based on the total weight, as 100 wt%, of the vinyl ester and ethylene monomers,
    wherein the total amount of vinyl ester and ethylene is greater than 80wt%, preferably greater than 85wt%, preferably greater than 90wt%, more preferably greater than 95wt%, more preferably greater than 97wt%, more preferably greater than 98wt%, more preferably greater than 98.5 wt%, based on 100 wt%of the total weight of the Component i) Copolymer.
  2. The water-based polymer dispersion according to Claim 1, the vinyl ester is one or more selected from vinyl acetate, vinyl butyrate, vinyl propionate, vinyl pivalate, vinyl 2-ethylhexanoate, 1-methyl vinyl acetate, and vinyl laurate, preferably the vinyl ester is vinyl acetate.
  3. The water-based polymer dispersion according to Claim 1 or 2, wherein in the Monomer A, R1 is H or C1-C2 alkyl; R2 is C1-C3 alkylene; R3 and R4 are C1-C2 alkyl, preferably R1 is H or methyl; R2 is ethylene or propylene; R3 and R4 are methyl.
  4. The water-based polymer dispersion according to any of Claim 1-3, wherein the Monomer A is one or more selected from the group consisting of (2-dimethylamino) ethyl methacrylate, (2-dimethylamino) ethyl acrylate, Dimethylaminopropyl methacrylate, and 3- (Dimethylamino) propyl acrylate.
  5. The water-based polymer dispersion according to any of Claim 1-4, wherein the dosage of "biocides" and "antibiotics" is below 800 ppm, preferably below 500 ppm, more preferably below 200 ppm, more preferably below 100 ppm, more preferably below 50 ppm.
  6. The water-based polymer dispersion according to any of Claim 1-5, wherein the total amount of vinyl acetate, ethylene and Monomer A is greater than 85wt%, preferably greater than 90wt%, more preferably greater than 95wt%, more preferably greater than 97wt%, more preferably greater than 98wt%, more preferably greater than 99 wt%, more preferably greater than 99.5 wt%, more preferably greater than 99.9 wt%, based on 100 wt%of the total weight of the Component i) Copolymer.
  7. The water-based polymer dispersion according to any of Claim 1-6, which containing
    39-60 wt%of Component i) , a copolymer prepared by the polymerization of monomers containing vinyl ester, ethylene and Monomer A according to the formula (1) ,
    0.6-4 wt%of Component iii) , a protective colloid, and
    39-60 wt%of Component iv) , water,
    based on the total weight, as 100 wt%, of the water-based polymer dispersion.
  8. The water-based polymer dispersion according to any of Claim 1-7 in the field of anti-biodeterioration, preferably in the field of anti-biodeterioration of polymer emulsions.
  9. An anti-biodeterioration water-based dispersion, which contains the water-based polymer dispersion according to any of Claim 1-7.
  10. A composition containing a product obtained by drying the water-based polymer dispersion according to any of Claim 1-7.
PCT/CN2024/086930 2024-04-10 2024-04-10 Water-based polymer dispersions Pending WO2025213375A1 (en)

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Publication number Priority date Publication date Assignee Title
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US6890969B2 (en) * 2000-09-06 2005-05-10 Air Products Polymers, L.P. Polymer emulsion preservation using cationic compounds
CN1328296C (en) 2003-06-17 2007-07-25 罗姆和哈斯公司 Polymer compositions and process for preparing polymers
CN101044176A (en) 2004-10-22 2007-09-26 巴斯福股份公司 Amphoteric ethyl methacrylate copolymer and its use
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US5208016A (en) * 1988-03-03 1993-05-04 Sumitomo Chemical Co., Ltd. Antimicrobial substance and antimicrobial resin composition containing ethylene copolymer
US6890969B2 (en) * 2000-09-06 2005-05-10 Air Products Polymers, L.P. Polymer emulsion preservation using cationic compounds
CN1328296C (en) 2003-06-17 2007-07-25 罗姆和哈斯公司 Polymer compositions and process for preparing polymers
CN101044176A (en) 2004-10-22 2007-09-26 巴斯福股份公司 Amphoteric ethyl methacrylate copolymer and its use
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