WO2025146113A1 - Procédé de préparation d'un copolymère de série de chlorure de vinyle, et latex de copolymère de série de chlorure de vinyle, résine en pâte, composition liquide et composition solide - Google Patents

Procédé de préparation d'un copolymère de série de chlorure de vinyle, et latex de copolymère de série de chlorure de vinyle, résine en pâte, composition liquide et composition solide Download PDF

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WO2025146113A1
WO2025146113A1 PCT/CN2025/070325 CN2025070325W WO2025146113A1 WO 2025146113 A1 WO2025146113 A1 WO 2025146113A1 CN 2025070325 W CN2025070325 W CN 2025070325W WO 2025146113 A1 WO2025146113 A1 WO 2025146113A1
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vinyl chloride
functional monomer
latex
mass
monomer
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Chinese (zh)
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杨万泰
樊立军
张先宏
赵长稳
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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
    • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
    • 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
    • C08F222/00—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 carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/38—Amides

Definitions

  • the invention relates to a preparation method of a vinyl chloride copolymer, a vinyl chloride copolymer latex, a paste resin, a liquid composition and a solid composition.
  • Vinyl chloride is a byproduct of the chlor-alkali industry. It is low-cost and an important raw material for plastics chemical industry.
  • the solid product of polyvinyl chloride prepared by emulsion polymerization is called "paste resin", which is one of the important varieties of polyvinyl chloride resin. It has good paste-forming properties and good dispersibility. It is mainly used in soft material products such as artificial leather, floor plastics, wallpaper, impregnated plastics, adhesives, coatings, etc.
  • polyvinyl chloride paste resin can also be copolymerized with other monomers to obtain paste resin products of vinyl chloride copolymers.
  • soap-free emulsion polymerization includes soap-free emulsion polymerization with an emulsifier concentration lower than the CMC value and soap-free emulsion polymerization based on reactive emulsifiers.
  • the former often requires a very low monomer concentration in the emulsion polymerization system, which is not conducive to industrial production.
  • Patent Document 1 discloses a method for preparing a hyperbranched aqueous vinyl chloride copolymer emulsion by reacting vinyl chloride, vinyl acetate, a hyperbranched monomer, an initiator, an emulsifier, and a neutralizer in water, wherein the hyperbranched monomer is prepared by reacting pentaerythritol with maleic anhydride or fumaric anhydride.
  • the emulsion prepared by this method can be used to modify polyurethane adhesives and has good adhesion, but an emulsifier must still be used.
  • Non-Patent Document 1 discloses a method for emulsion copolymerization of vinyl chloride, vinyl acetate, and maleic anhydride, in which a combination of SDS and reactive emulsifier HS-10 is used as an emulsifier.
  • the paste resin of the vinyl chloride copolymer In addition, in order to expand the application range of the paste resin of the vinyl chloride copolymer, it is sometimes desired that the paste resin has more abundant functional groups. However, for the paste resin of the vinyl chloride copolymer obtained by soap-free emulsion polymerization, there is sometimes a competition between increasing the content of functional groups and retaining the performance achieved by the vinyl chloride monomer as much as possible (i.e., the so-called "original performance of the polyvinyl chloride paste resin").
  • Patent document 1 CN201911282721.9
  • Non-patent document 1 Conversion rate and latex properties of vinyl chloride-vinyl acetate-maleic anhydride emulsion copolymerization, Xiang Hongwen et al., Chemical Reaction Engineering and Technology, Vol. 30, No. 6, December 2014, pp. 522-527.
  • the object of the present invention is also to provide a vinyl chloride copolymer latex and a liquid composition based on the latex, wherein the latex does not contain a surfactant, is easy to obtain and has excellent stability, and the vinyl chloride copolymer contained therein can ensure the performance based on vinyl chloride monomer while also having more functional groups.
  • a method for preparing a vinyl chloride copolymer comprising:
  • Vinyl chloride A, comonomer B, and functional monomer C are subjected to emulsion polymerization in an aqueous medium without a surfactant under stirring in the presence of a polymerization initiator.
  • the functional monomer C has one free radical polymerizable group and two functional groups selected from amide groups, carboxyl groups and carboxylate groups and not being amide groups or carboxyl groups at the same time in one molecule,
  • the mass ratio of the comonomer B to the functional monomer C, comonomer B/functional monomer C, is 1/12 to 12/1.
  • the alkaline compound is at least one selected from ammonia gas, ammonia water, sodium hydroxide and potassium hydroxide
  • the acid anhydride monomer is at least one selected from maleic anhydride, itaconic anhydride, citraconic anhydride, dimethylmaleic anhydride, aconitic anhydride and phenylmaleic anhydride
  • the dicarboxylic acid monomer is at least one selected from C2 to C20 olefin dicarboxylic acids.
  • a vinyl chloride copolymer latex wherein the vinyl chloride copolymer latex does not contain a surfactant
  • the vinyl chloride copolymer constituting the latex has units based on vinyl chloride A, units based on comonomer B, and units based on functional monomer C.
  • the functional monomer C has one free radical polymerizable group and two functional groups selected from amide groups, carboxyl groups, and carboxylate groups and not being amide groups at the same time in one molecule.
  • the present invention provides a paste resin of a vinyl chloride copolymer and a solid composition based on the paste resin.
  • the paste resin does not contain a surfactant, thereby avoiding problems caused by residual emulsifiers and can be easily obtained.
  • the paste resin has more functional groups while ensuring the performance based on vinyl chloride monomer.
  • the word “may” may include both performing a certain process and not performing a certain process, or may include both having a certain component and not having a certain component.
  • alkyl or “alkylene” means a linear, branched or cyclic unsubstituted “alkyl” or “alkylene”
  • aryl or “arylene” means an “aryl” or “arylene” having no substituents other than the alkyl group on the aromatic ring (benzene ring, naphthalene ring, etc.).
  • the "unit" in a polymer refers to a polymerized unit derived from a monomer formed by polymerizing the monomer, and a polymerized unit obtained by converting a part of the polymerized unit into another structure by treating the polymer.
  • the temperature when “normal temperature” or “room temperature” is used, the temperature may be 10 to 40°C.
  • references to “some specific/preferred embodiments”, “other specific/preferred embodiments”, “embodiments”, etc. mean that the specific elements (e.g., features, structures, properties and/or characteristics) described in connection with the embodiment are included in at least one embodiment described herein, and may or may not exist in other embodiments.
  • the elements may be combined in various embodiments in any suitable manner.
  • the mass ratio of the comonomer B to the functional monomer C is 1/15 to 15/1.
  • the mass ratio of the comonomer B to the functional monomer C is preferably 1/10 to 10/1, more preferably 1/6 to 6/1, and further preferably 1/2 to 4/1.
  • the term “not both amide groups and carboxyl groups” means that the two functional groups are not both amide groups and carboxyl groups.
  • the term “carboxylate group” refers to a group comprising a carboxylate anion and a counter cation. There is no particular limitation on the type of the counter cation, for example, it can be
  • surfactant refers to a substance that can be dissolved in water to reduce the surface tension of water, and covers not only those substances commonly referred to as emulsifiers (small molecule emulsifiers and macromolecular (polymer) emulsifiers, etc.) in the art, but also those substances commonly referred to as stabilizers in the art.
  • surfactants examples include anionic surfactants such as sodium dodecyl sulfate, sodium salt of styrene/maleic anhydride copolymers and sodium salt of acrylic acid copolymers, nonionic surfactants such as sorbitan ester compounds and polyoxyethylene ether compounds, cationic surfactants such as dodecyl trimethyl ammonium chloride, and amphoteric surfactants such as dodecyl dimethylamine oxide.
  • anionic surfactants such as sodium dodecyl sulfate, sodium salt of styrene/maleic anhydride copolymers and sodium salt of acrylic acid copolymers
  • nonionic surfactants such as sorbitan ester compounds and polyoxyethylene ether compounds
  • cationic surfactants such as dodecyl trimethyl ammonium chloride
  • amphoteric surfactants such as dodecyl dimethylamine oxide.
  • the amount of vinyl chloride used there is no particular limitation on the amount of vinyl chloride used.
  • the amount of vinyl chloride A used is preferably 70% by mass or more and 95% by mass or less, more preferably 72% by mass or more and 93% by mass or less, and further preferably 75% by mass or more and 90% by mass or less, relative to 100% by mass of the total mass of vinyl chloride A, comonomer B and functional monomer C.
  • the comonomer B there is no particular limitation on the specific structure of the comonomer B, as long as it can be copolymerized with vinyl chloride and the functional monomer C described below and has no negative impact on the stability of the emulsion polymerization.
  • the comonomer B is preferably at least one selected from monofunctional (meth)acrylate monomers, monofunctional (meth)acrylamide monomers, monofunctional vinyl ester monomers, monofunctional vinyl ether monomers, vinyl pyrrolidone monomers, vinyl pyridine monomers, and vinyl lactam monomers.
  • alkyl (meth)acrylates preferably, alkyl (meth)acrylates having an alkyl group with 1 to 8 carbon atoms
  • alkyl (meth)acrylates preferably, alkyl (meth)acrylates having an alkyl group with 1 to 8 carbon atoms
  • alkyl (meth)acrylates preferably, alkyl (meth)acrylates having an alkyl group with 1 to 8 carbon atoms
  • monofunctional (meth)acrylamide-based monomers there is no particular limitation on the monofunctional (meth)acrylamide-based monomers, and examples thereof include, but are not limited to, (meth)acrylamide, etc. These monofunctional (meth)acrylamide-based monomers may be used alone or in combination of any two or more.
  • monofunctional vinyl ester monomer there is no particular limitation on the monofunctional vinyl ester monomer, and examples thereof include, but are not limited to, vinyl acetate, vinyl propionate, vinyl butyrate, allyl acetate, etc. These monofunctional vinyl ester monomers may be used alone or in combination of any two or more.
  • monofunctional vinyl ether monomers there is no particular limitation on the monofunctional vinyl ether monomers, and examples thereof include, but are not limited to, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, etc. These monofunctional vinyl ether monomers may be used alone or in combination of any two or more.
  • vinyl pyrrolidone-based monomers there is no particular limitation on the vinyl pyrrolidone-based monomers, and examples thereof include, but are not limited to, N-vinyl pyrrolidone, etc. These vinyl pyrrolidone-based monomers may be used alone or in combination of any two or more.
  • vinylpyridine monomer examples thereof include, but are not limited to, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, etc. These vinylpyridine monomers may be used alone or in combination of any two or more.
  • vinyl lactam monomer examples thereof include, but are not limited to, vinyl caprolactam, vinyl enantholactam, vinyl hexadecanoic acid amide, etc. These vinyl lactam monomers may be used alone or in combination of any two or more.
  • comonomer B is more preferably at least one selected from monofunctional (meth)acrylate monomers, monofunctional (meth)acrylamide monomers, monofunctional vinyl ester monomers, and monofunctional vinyl ether monomers, and particularly preferably a monofunctional vinyl ester monomer, for example, vinyl acetate and/or vinyl propionate.
  • the functional monomer C has one free radical polymerizable group and two functional groups selected from an amide group, a carboxyl group, and a carboxylate group and not being an amide group or a carboxyl group at the same time in one molecule, there is no particular limitation on the specific structure of the functional monomer C.
  • the functional monomer C can be used alone or in any combination of two or more.
  • the radical polymerizable group is preferably an alkenyl group.
  • the structure of the functional monomer C is shown in the following formula (1):
  • R3 , R6 , R7 , R8 each independently represent a direct bond or a C1-C20 substituted or unsubstituted alkylene group
  • R4 , R5 , R9 , R10 each independently represent hydrogen or a C1-C20 substituted or unsubstituted alkyl group.
  • the substituent on the alkylene group or the alkyl group may include a hydroxyl group, an amine group, a halogen atom (e.g., fluorine, chlorine, bromine, iodine, etc.), etc.
  • the obtained latex had no demulsification such as floccules and precipitation.
  • the paste resin obtained after drying the latex is mixed evenly with paste resin (100phr), plasticizer (DOP, 20phr) and heat stabilizer (Ca-Zn, 2phr), hot pressed into film at 150°C, and cut into 20mm ⁇ 20mm films to determine the water absorption rate.
  • the mass of the resin film is recorded as m3 grams .
  • the resin film is placed in deionized water at room temperature of 25°C for 24 hours. After being taken out, the surface moisture is absorbed with filter paper. At this time, the mass of the resin film is recorded as m4 grams. Then [( m4 - m3 )/ m3 ] ⁇ 100% is the water absorption rate of the resin film.
  • the alkaline mixed solution containing the functional monomers is added, and a redox initiator (2.0 g potassium persulfate and 1.2 g sodium bisulfite) is added, and 15 g vinyl propionate (the mass ratio of vinyl propionate/functional monomer C1 is 3/1) is added.
  • a redox initiator 2.0 g potassium persulfate and 1.2 g sodium bisulfite
  • 15 g vinyl propionate the mass ratio of vinyl propionate/functional monomer C1 is 3/1 is added.
  • 80.0 g vinyl chloride is added (the pH of the system before polymerization is about 9.6 at this time).
  • Pre-emulsification is carried out for half an hour, and then the temperature is raised to 45°C, and the reaction is carried out under mechanical stirring at 400 rpm.
  • the initial reaction pressure is 0.56 MPa, and the reaction is carried out for 10 hours until the pressure in the kettle drops to 0.20 MPa. It is determined that the reaction end point has been reached and the reaction is stopped. After the reaction is completed, the latex of the vinyl chloride copolymer E1 is obtained from the reactor.
  • the latex was dried to remove water to constant weight, and the dried product was washed with water, and the process was repeated three times. After washing, the latex was dried again to constant weight, and then crushed to obtain a paste resin of a vinyl chloride copolymer.
  • Table 1 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 1 Except that the pH in Example 1 was controlled to 7.0 (so that the pH of the system before polymerization was about 7.2) to obtain the functional monomer C1 (the two functional groups were ammonium carboxylate and ammonium carboxylate), a latex of a vinyl chloride copolymer with a solid content of 13.4% was obtained in a similar manner to Example 1.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 1 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 1 Except that the pH in Example 1 was controlled to 10.5 (so that the pH of the system before polymerization was about 10.8) to obtain the functional monomer C1 (the two functional groups were ammonium carboxylate and ammonium carboxylate), a latex of a vinyl chloride copolymer with a solid content of 17.9% was obtained in a similar manner to Example 1.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 1 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 1 Except for changing the amount of functional monomer C1 and vinyl propionate in Example 1 (the mass ratio of vinyl propionate/functional monomer C1 is 1/1), a latex of a vinyl chloride copolymer with a solid content of 22.1% is obtained by a method similar to Example 1.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 1 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 4 Except that 17.6g of ammonia water, the alkaline compound in Example 4, is replaced by 3.5g of sodium hydroxide, the total amount of deionized water is 300.0g to obtain functional monomer C2 (the two functional groups are sodium carboxylate and sodium carboxylate, respectively), and the reaction is carried out in a mass ratio of propylene vinyl ester/functional monomer C2 of 1/1.
  • a latex of a vinyl chloride copolymer with a solid content of 20.8% is obtained in a similar manner to Example 4.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 1 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • a latex of a vinyl chloride copolymer having a solid content of 22.3% was obtained in a similar manner to that in Example 4, except that the comonomer B in Example 4 was replaced with vinyl acetate and the reaction was carried out in a vinyl acetate/functional monomer C1 mass ratio of 1/1.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 1 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 4 Except that the reaction temperature in Example 4 is increased to 48°C, a latex of a vinyl chloride copolymer with a solid content of 21.5% is obtained in a similar manner to Example 4.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 1 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 6 Except that the maleic acid monomer in Example 6 is replaced by maleic anhydride to obtain functional unit C3 (the two functional groups are amide group and ammonium carboxylate, respectively), and the reaction is carried out in a manner with a mass ratio of vinyl acetate/functional monomer C3 of 1/1, a latex of a vinyl chloride copolymer with a solid content of 22.6% is obtained in a similar manner to Example 6.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 1 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 4 Except that the initiator in Example 4 is replaced by azobisisobutylamidine hydrochloride and the reaction temperature is 56°C, a latex of a vinyl chloride copolymer with a solid content of 22.4% is obtained in a similar manner to Example 4.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 1 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 4 Except that the pH in Example 4 is controlled to 6.2 (so that the pH of the system before polymerization is about 6.5) to obtain functional monomer C4 (the two functional groups are carboxylic acid group and ammonium carboxylate, respectively), and the initiator in Example 4 is replaced by azobisisobutylamidine hydrochloride, and the reaction temperature is 56°C, a latex of a vinyl chloride copolymer with a solid content of 18.6% is obtained by a method similar to that in Example 4.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 1 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 1 Except for changing the amount of functional monomer C1 and vinyl propionate in Example 1 (the mass ratio of vinyl propionate/functional monomer C1 is 10/1), a latex of a vinyl chloride copolymer with a solid content of 13.6% is obtained by a method similar to Example 1.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 2 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 1 Except for changing the amount of functional monomer C1 and vinyl propionate in Example 1 (the mass ratio of vinyl propionate/functional monomer C1 is 5/1), a latex of a vinyl chloride copolymer with a solid content of 15.5% is obtained by a method similar to Example 1.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 2 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • Example 1 Except for changing the amount of functional monomer C1 and vinyl propionate in Example 1 (the mass ratio of vinyl propionate/functional monomer C1 is 1/5), a latex of a vinyl chloride copolymer with a solid content of 14.6% is obtained by a method similar to Example 1.
  • Example 2 In addition, in a similar manner to that in Example 1, a paste resin of a vinyl chloride-based copolymer was obtained.
  • Table 2 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • a latex of a vinyl chloride copolymer with a solid content of 9.6% is obtained by a method similar to Example 1.
  • Table 2 shows the physical properties and stability evaluation results of the latex and the paste resin.
  • the latex is dried to remove water to constant weight, and the dried product is washed with water, and the process is repeated three times. After washing, the latex is dried again to constant weight, and the homopolymerized polyvinyl chloride paste resin is obtained after crushing.
  • Example 1 Except that the maleic acid in Example 1 was replaced by acrylic acid to obtain the functional monomer CC1 (having only one functional group in the molecule), polymerization was carried out in a similar manner as in Example 1.
  • the initial reaction pressure was 0.56 MPa, and the pressure in the reactor dropped to 0.15 MPa after 10 hours of reaction, and the reaction was stopped. No latex was obtained, and the product agglomerated and demulsified.
  • the polymerization was carried out in a similar manner to Example 4 except that maleic acid was directly used as the functional monomer CC2 (both functional groups of the functional monomer were carboxyl groups). After 10 hours of reaction, the pressure in the reactor did not decrease, and the reaction was stopped. No latex was obtained, and a small amount of white insoluble matter was present in the solution.
  • Example 1 Except for changing the amount of vinyl propionate and functional monomer C1 in Example 1 (the mass ratio of vinyl propionate/functional monomer C1 is 15/1), polymerization was carried out in a similar manner as in Example 1. After 10 hours of reaction, the pressure in the reactor did not decrease, and the reaction was stopped. No latex was obtained, and a very small amount of white insoluble matter existed in the solution.
  • Example 1 Except for changing the amount of functional monomer C1 and vinyl propionate in Example 1 (the mass ratio of vinyl propionate/functional monomer C1 is 1/15), polymerization was carried out in a similar manner as in Example 1. After 10 hours of reaction, the pressure in the reactor did not decrease, and the reaction was stopped. No latex was obtained, and a very small amount of white insoluble matter existed in the solution.
  • the polymerization was carried out in a similar manner to Example 1 except that vinyl propionate was not used. After 10 hours of reaction, the pressure in the reactor did not decrease, so the reaction was stopped. No latex was obtained, and the solution was slightly yellow and unreacted.

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Abstract

La présente invention concerne un procédé de préparation d'un copolymère de série de chlorure de vinyle, et un latex de copolymère de série de chlorure de vinyle, une résine en pâte, une composition liquide et une composition solide. Le procédé de préparation du copolymère de série de chlorure de vinyle consiste, dans un milieu aqueux qui ne contient pas de tensioactif, à réaliser une polymérisation en émulsion sur le chlorure de vinyle A, un monomère de copolymérisation B, et un monomère fonctionnel C en présence d'un initiateur de polymérisation sous agitation, chaque molécule du monomère fonctionnel C contenant un groupe polymérisable par voie radicalaire et deux groupes fonctionnels qui sont choisis parmi un groupe amide, un groupe carboxyle et un groupe carboxylate et qui ne sont pas un groupe amide ou un groupe carboxyle en même temps, et le rapport massique du monomère de copolymérisation B au monomère fonctionnel C étant de 1/12 à 12/1. Le latex de copolymère de série de chlorure de vinyle de la présente invention ne contient pas de tensioactif ; et le copolymère de série de chlorure de vinyle constituant le latex a un motif à base de chlorure de vinyle A, un motif à base de monomère de copolymérisation B, et un motif à base de monomère fonctionnel C.
PCT/CN2025/070325 2024-01-05 2025-01-03 Procédé de préparation d'un copolymère de série de chlorure de vinyle, et latex de copolymère de série de chlorure de vinyle, résine en pâte, composition liquide et composition solide Pending WO2025146113A1 (fr)

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CN118126229A (zh) * 2024-01-05 2024-06-04 北京化工大学 氯乙烯系共聚物的制备方法与氯乙烯系共聚物胶乳、糊树脂、液态组合物、固态组合物

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JP2002348318A (ja) * 2001-03-23 2002-12-04 Kanegafuchi Chem Ind Co Ltd 塩化ビニル系ペースト樹脂
JP2010031234A (ja) * 2008-06-26 2010-02-12 Tosoh Corp 塩化ビニル系樹脂ラテックス及びその製造方法
CN102652144A (zh) * 2009-12-10 2012-08-29 东曹株式会社 氯乙烯类树脂胶乳、其制备方法以及使用该氯乙烯类树脂胶乳的热敏转印图像接受片材
CN104403042A (zh) * 2014-12-29 2015-03-11 周大胜 一种耐盐雾性的偏氯乙烯共聚物胶乳及其制备方法
CN118126229A (zh) * 2024-01-05 2024-06-04 北京化工大学 氯乙烯系共聚物的制备方法与氯乙烯系共聚物胶乳、糊树脂、液态组合物、固态组合物

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Publication number Priority date Publication date Assignee Title
JP2002348318A (ja) * 2001-03-23 2002-12-04 Kanegafuchi Chem Ind Co Ltd 塩化ビニル系ペースト樹脂
JP2010031234A (ja) * 2008-06-26 2010-02-12 Tosoh Corp 塩化ビニル系樹脂ラテックス及びその製造方法
CN102652144A (zh) * 2009-12-10 2012-08-29 东曹株式会社 氯乙烯类树脂胶乳、其制备方法以及使用该氯乙烯类树脂胶乳的热敏转印图像接受片材
CN104403042A (zh) * 2014-12-29 2015-03-11 周大胜 一种耐盐雾性的偏氯乙烯共聚物胶乳及其制备方法
CN118126229A (zh) * 2024-01-05 2024-06-04 北京化工大学 氯乙烯系共聚物的制备方法与氯乙烯系共聚物胶乳、糊树脂、液态组合物、固态组合物

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