WO2024087983A1 - Polymère contenant du silicium, agent de traitement, leur procédé de préparation et leur application - Google Patents

Polymère contenant du silicium, agent de traitement, leur procédé de préparation et leur application Download PDF

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WO2024087983A1
WO2024087983A1 PCT/CN2023/121145 CN2023121145W WO2024087983A1 WO 2024087983 A1 WO2024087983 A1 WO 2024087983A1 CN 2023121145 W CN2023121145 W CN 2023121145W WO 2024087983 A1 WO2024087983 A1 WO 2024087983A1
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group
silicon
alkyl
independently
aryl
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PCT/CN2023/121145
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English (en)
Chinese (zh)
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蒋凌飞
孔祥晶
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北京马普新材料有限公司
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Publication of WO2024087983A1 publication Critical patent/WO2024087983A1/fr

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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
    • 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • the present application relates to a silicon-containing polymer, a treatment agent containing the polymer, and a preparation method and application thereof, which can be used for surface and internal addition treatment of various articles, such as paper products, natural stone, concrete, fiber fabrics, synthetic leather, non-woven fabrics, asbestos, fur or plastic, and impart oil and water repellency to the surface of the articles.
  • Polymers have been widely used in surface and internal addition treatments of paper, textiles, leather, stone, etc. They can give the surface of objects multiple functions, thereby improving the durability of the objects. For example, after paper is treated, it can withstand oil-rich foods; after textile treatment, it can improve the ability to withstand various stains; after stone treatment, the original appearance of the stone can be maintained for a long time.
  • CN103975107B proposes a solution of using barrier coating.
  • This patent mainly adopts emulsion polymerization to produce a polymer emulsion by adding starch and emulsifier, and then applies it to paper by coating. Although this method can also block grease, it will bring two problems. First, a large amount of coating is required to have an oil-proof effect. Second, it is only applicable to paper machines with coating equipment. It cannot be directly completed on general paper machines. The process applicability is not strong and the cost is also high.
  • CN100360612C proposes to use polysiloxane and polyvinyl alcohol to cross-link under the action of a catalyst and disperse them through a surfactant.
  • CN112513370A proposes a method of using a long-chain acrylic ester copolymer to achieve paper treatment, thereby achieving the effect of repelling oil and water, but this method is found to have a poor barrier effect on hot oils with a temperature above 80°C.
  • CN107849187A proposes a method of using a copolymer of acrylic ester and vinyl chloride and the resulting polymer to finish textiles, which has a good water-repellent effect.
  • CN110114435A proposes a method of using a copolymer of acrylic ester and then compounding it with a wax emulsion to finish textiles, which has a good water-repellent effect.
  • CN105377935B uses a polyurethane aqueous dispersion to finish textiles, which has a good water-repellent effect.
  • these polymers have poor oil-repellent effects and limited protective properties.
  • CN105764980B proposes to use long-chain acrylate to form an emulsion under the action of a cationic emulsifier, which can be used for physical treatment of porous objects such as fiber, stone, leather, etc., so as to have the effect of repelling water and spreading oil.
  • a cationic emulsifier which can be used for physical treatment of porous objects such as fiber, stone, leather, etc.
  • repelling water and spreading oil a cationic emulsifier
  • the purpose of the present application is to provide a silicon-containing polymer and a treatment agent containing the polymer, wherein the silicon-containing polymer and the treatment agent can be used to treat a variety of articles, thereby imparting oil and water repellency to the surfaces of the articles.
  • the present application also provides a method for preparing the treatment agent as described above.
  • the present application provides a silicon-containing polymer, which includes repeating units generated by silicon-containing monomer I and repeating units generated by monomer II, wherein silicon-containing monomer I includes silicon-containing monomer I-1a and/or silicon-containing monomer I-1b,
  • R 1 is selected from a hydrogen atom or a C 1 -C 20 alkyl group
  • W is selected from the group represented by W-1, W-2, W-3 and W-4, -OC(O)-N(R 2 )- W-2 -OC(O)-O- W-3 -OC(O)-ODN(R 2 )- W-4
  • R2 is selected from a hydrogen atom or a C1 - C20 alkyl group, and D is a C1 - C20 alkylene group; when W is selected from W-1, B is absent or is a C1 - C20 alkylene group, and when W is selected from W-2, W-3, or W-4, B is a C1 - C20 alkylene group;
  • R 1 is selected from a hydrogen atom or a C 1 -C 20 alkyl group;
  • B is a C 1 -C 20 alkylene group;
  • Z is independently selected from the following structures:
  • R 4 is independently a C 1 -C 20 alkyl group, a C 6 -C 20 aryl group, a C 7 -C 12 aralkyl group, a C 7 -C 12 alkaryl group or an R 5 -OR 6 - group
  • R 5 is a C 1 -C 10 alkyl group, a C 6 -C 20 aryl group, a C 7 -C 12 aralkyl group or a C 7 -C 12 alkaryl group
  • R 6 is a C 1 -C 10 alkylene group, and 1 ⁇ a ⁇ 200;
  • Y1 and Y2 are the same or different, and are independently selected from C1 - C20 alkyl, C6 - C20 aryl, C7 - C12 aralkyl or C7 - C12 alkaryl, and the structure of formula (I):
  • R7 is each independently a C1 - C20 alkyl group, a C6 - C20 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group
  • R8 is each independently a C1 - C20 alkyl group, a C6 - C20 aryl group, a C7 - C12 aralkyl group, a C7 - C12 alkaryl group or a R9 - OR10 -group, wherein R9 is a C1 - C10 alkyl group, a C6 - C20 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group, R10 is a C1 - C10 alkylene group, and 0 ⁇ b ⁇ 200;
  • P is selected from the groups represented by P-1 and P-2, -C(O)-O- P-1 -C(O)-N(R 2 )- P-2
  • B is a C 1 -C 20 alkylene group
  • R 1 and R 2 are each independently a hydrogen atom or a C 1 -C 20 alkyl group
  • R 3 and R 4 are each independently a hydrogen atom, a C 1 -C 18 alkyl group, a hydroxyethyl group or a benzyl group, or R 3 and R 4 are combined with a nitrogen atom to form a morpholino group, a piperidino group or a pyrrolidinyl group.
  • the silicon-containing monomer I further includes a silicon-containing monomer I-2,
  • R 1 is selected from a hydrogen atom or a C 1 -C 20 alkyl group;
  • B is a C 1 -C 20 alkylene group;
  • X is selected from the group represented by X-1 and X-2, -C(O)-O- X-1 -C(O)-N(R 2 )- X-2
  • R 2 is selected from a hydrogen atom or a C 1 -C 20 alkyl group
  • Z is selected from the following structures:
  • R 4 is independently a C 1 -C 20 alkyl group, a C 6 -C 20 aryl group, a C 7 -C 12 aralkyl group, a C 7 -C 12 alkaryl group or an R 5 -OR 6 - group
  • R 5 is a C 1 -C 10 alkyl group, a C 6 -C 20 aryl group, a C 7 -C 12 aralkyl group or a C 7 -C 12 alkaryl group
  • R 6 is a C 1 -C 10 alkylene group, and 1 ⁇ a ⁇ 200;
  • Y1 and Y2 are the same or different, and are independently selected from C1 - C20 alkyl, C6 - C20 aryl, C7 - C12 aralkyl or C7 - C12 alkaryl, and the structure of formula (I):
  • R7 is each independently a C1 - C20 alkyl group, a C6 - C20 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group;
  • R8 is each independently a C1 - C20 alkyl group, a C6 - C20 aryl group, a C7 - C12 aralkyl group, a C7 - C12 alkaryl group or an R9 - OR10- group, wherein R9 is a C1 - C10 alkyl group, a C6 - C20 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group, R10 is a C1 - C10 alkylene group, and 0 ⁇ b ⁇ 200.
  • Y 1 and/or Y 2 is a structure of formula (I); when a is greater than 1 and ⁇ 200, at least one Y 1 is a structure of formula (I) and/or at least one Y 2 is a structure of formula (I):
  • R7 is each independently a C1 - C20 alkyl group, a C6 - C20 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group;
  • R8 is each independently a C1 - C20 alkyl group, a C6 - C20 aryl group, a C7 - C12 aralkyl group, a C7 - C12 alkaryl group or an R9 - OR10- group, wherein R9 is a C1 - C10 alkyl group, a C6 - C20 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group, R10 is a C1 - C10 alkylene group, and 0 ⁇ b ⁇ 200.
  • R7 is each independently a C1 - C10 alkyl group, a C6 - C10 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group;
  • R8 is each independently a C1 - C10 alkyl group, a C6 - C10 aryl group, a C7 - C12 aralkyl group, a C7 - C12 alkaryl group or an R9 - OR10 -group, wherein R9 is a C1 - C10 alkyl group, a C6 - C10 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group, and R10 is a C1 - C10 alkylene group.
  • R7 is each independently a C1 - C6 alkyl group, a C6 - C10 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group;
  • R8 is each independently a C1 - C6 alkyl group, a C6 - C10 aryl group, a C7 - C12 aralkyl group, a C7 - C12 alkaryl group or an R9 - OR10 -group, wherein R9 is a C1 - C6 alkyl group, a C6 - C10 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group, and R10 is a C1 - C6 alkylene group.
  • R1 represents a hydrogen atom or a methyl group
  • R2 is each independently a C1 - C6 alkylene group, preferably a C2 - C4 alkylene group
  • q is an integer of 1-50, preferably an integer of 1-20
  • R3 represents a hydrogen atom or a C1 - C20 alkyl group, preferably a hydrogen atom or a C1 - C10 alkyl group, more preferably a hydrogen atom or a C1 - C3 alkyl group;
  • G is selected from the group represented by G-1 and G-2, -C(O)-O-(CH 2 ) n - G-1 -C(O)-N(R 4 )-(CH 2 ) n - G-2
  • R4 represents a hydrogen atom or a methyl group, and n is an integer of 0-10, preferably an integer of 0-5.
  • the proportion of the repeating units generated by silicon-containing monomers I-1a and/or silicon-containing monomers I-1b in the repeating units generated by silicon-containing monomers I is 1% to 100%, 5% to 100%, 10% to 100% or 50% to 100%, for example, 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or any two of them.
  • the total amount of the repeating units generated by silicon-containing monomers I-1a and I-1b and the repeating units generated by silicon-containing monomers I-2 is the total amount of repeating units generated by silicon-containing monomers I.
  • the mass content of the repeating units produced by the silicon-containing monomer I is 30%-90%, preferably 40%-85%, and more preferably 50%-80%, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or a range consisting of any two of them.
  • the mass content of the repeating unit produced by monomer II is 5%-65%, preferably 10%-50%, more preferably 15%-45%, for example 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or the range of any two thereof.
  • the mass content of the repeating unit produced by monomer III is 1%-40%, preferably 5%-30%, and more preferably 10%-25%, for example, 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or a range composed of any two of them.
  • the silicon-containing polymer of the present application is formed by polymerization of monomers, and the monomers used for polymerization include the silicon-containing monomer I and the monomer II, and the silicon-containing monomer I includes the silicon-containing monomer I-1a and/or the silicon-containing monomer I-1b.
  • the monomer may also include the monomer III.
  • the proportion of silicon-containing monomer I-1a and/or silicon-containing monomer I-1b in silicon-containing monomer I is 1% to 100%, 5% to 100%, 10% to 100% or 50% to 100%, for example, 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or a range consisting of any two of them.
  • the proportion of silicon-containing monomer I in the total amount of monomers is 30%-90% by mass, preferably 40%-85%, more preferably 50%-80%, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or a range consisting of any two of them.
  • the proportion of monomer II in the total amount of monomers is 5%-65% by mass, preferably 10%-50%, more preferably 15%-45%, for example 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or a range consisting of any two of them.
  • the proportion of monomer III in the total amount of monomers is 1%-40% by mass, preferably 5%-30%, more preferably 10%-25%, for example 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or a range consisting of any two of them.
  • R 1 is selected from a hydrogen atom or a methyl group.
  • B is selected from C 1 -C 10 alkylene groups, preferably C 1 -C 6 alkylene groups.
  • D is selected from a C 1 -C 10 alkylene group, preferably a C 1 -C 6 alkylene group.
  • R 2 is selected from a hydrogen atom or a methyl group.
  • R 4 is each independently a C 1 -C 10 alkyl group, a C 6 -C 10 aryl group, a C 7 -C 12 aralkyl group, a C 7 -C 12 alkaryl group, or an R 5 -OR 6 - group
  • R 5 is a C 1 -C 10 alkyl group, a C 6 -C 10 aryl group, a C 7 -C 12 aralkyl group, or a C 7 -C 12 alkaryl group
  • R 6 is a C 1 -C 10 alkylene group, and/or 1 ⁇ a ⁇ 80;
  • R7 is each independently a C1 - C10 alkyl group, a C6 - C10 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group;
  • R8 is each independently a C1 - C10 alkyl group, a C6 - C10 aryl group, a C7 - C12 aralkyl group, a C7 - C12 alkaryl group or an R9 - OR10- group, wherein R9 is a C1 - C10 alkyl group, a C6 - C10 aryl group, a C7 - C12 aralkyl group or a C7 - C12 alkaryl group, R10 is a C1 - C10 alkylene group, and/or 0 ⁇ b ⁇ 80.
  • R 4 is each independently a C 1 -C 6 alkyl group, a C 6 -C 10 aryl group, a C 7 -C 10 aralkyl group, a C 7 -C 10 alkaryl group, or an R 5 -OR 6 - group
  • R 5 is a C 1 -C 6 alkyl group, a C 6 -C 10 aryl group, a C 7 -C 10 aralkyl group, or a C 7 -C 10 alkaryl group
  • R 6 is a C 1 -C 6 alkylene group, and 1 ⁇ a ⁇ 30;
  • R7 is each independently a C1 - C6 alkyl group, a C6 - C10 aryl group, a C7 - C10 aralkyl group or a C7 - C10 alkaryl group;
  • R8 is each independently a C1 - C6 alkyl group, a C6 - C10 aryl group, a C7 - C10 aralkyl group, a C7 - C10 alkaryl group or an R9 - OR10- group, wherein R9 is a C1 - C6 alkyl group, a C6 - C10 aryl group, a C7 - C10 aralkyl group or a C7 - C10 alkaryl group, R10 is a C1 - C6 alkylene group, and 0 ⁇ b ⁇ 30.
  • a is an integer from 1-80, an integer from 1-30, an integer from 1-20, or an integer from 1-10.
  • b is 0. In some embodiments, b is an integer from 1 to 30, an integer from 1 to 20, an integer from 1 to 10, or an integer from 1 to 5.
  • Z is independently selected from one or more of the following structures i-1 to i-6:
  • R is each independently selected from a C 1 -C 10 alkyl group, a C 6 -C 10 aryl group, a C 7 -C 12 aralkyl group or a C 7 -C 12 alkaryl group;
  • 1 ⁇ m+1 ⁇ 60 preferably 1 ⁇ m+1 ⁇ 30; 0 ⁇ p ⁇ 60, preferably 0 ⁇ p ⁇ 30; 0 ⁇ q ⁇ 60, preferably 0 ⁇ q ⁇ 30; 1 ⁇ x ⁇ 9, preferably 1 ⁇ x ⁇ 7.
  • R is a C 1 -C 3 alkyl group, such as methyl.
  • Z is selected from the following structures:
  • Me represents a methyl group
  • ph represents a phenyl group
  • 1 ⁇ m+1 ⁇ 60 preferably 1 ⁇ m+1 ⁇ 30
  • 0 ⁇ p ⁇ 60 preferably 0 ⁇ p ⁇ 30
  • 0 ⁇ q ⁇ 60 preferably 0 ⁇ q ⁇ 30
  • 1 ⁇ x ⁇ 9 preferably 1 ⁇ x ⁇ 7.
  • m is 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9.
  • x is 1, 2, 3, 4, 5, 6, or 7.
  • R1 and R2 are selected from hydrogen atoms or methyl groups;
  • B is a C1 - C6 alkylene group;
  • R3 and R4 are independently C1 - C3 alkyl groups, hydroxyethyl groups or benzyl groups, or R3 and R4 are combined with the nitrogen atom to form a morpholino group, a piperidino group or a pyrrolidinyl group.
  • the silicon-containing monomer I-1a is selected from
  • CH 2 CH-ph-Si(OSi(CH 3 ) 3 ) 3 (ph represents ),
  • CH 2 CH-ph-(CH 2 ) 2 Si(OSi(CH 3 ) 3 ) 3 (ph represents ),
  • CH 2 CH-ph-(CH 2 ) 3 [Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 represents a butyl group, ph represents )(1 ⁇ n ⁇ 25)
  • CH 2 CH—OC(O)—NH—(CH 2 ) 3 Si(OSi(CH 3 ) 3 ) 3 ,
  • CH 2 CH-OC(O)-NH-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 represents a butyl group) (1 ⁇ n ⁇ 25),
  • CH2 CH-OC(O)-O-( CH2 ) 3 -Si(OSi( CH3 ) 3 ) 3 ,
  • CH 2 CH-OC(O)-O-(CH 2 ) 3 -[Si(CH 3 ) 2 O]n-Si(CH 3 ) 2 C 4 H 9 (C 4 H 9 represents a butyl group) (1 ⁇ n ⁇ 25),
  • CH2 CH-OC(O)-O-( CH2 ) 2- NH-( CH2 ) 3Si (OSi( CH3 ) 3 ) 3 , and
  • CH2 CH-OC(O)-O-( CH2 ) 2 -NH-( CH2 ) 3 [Si( CH3 ) 2O ]n-Si( CH3 ) 2C4H9 ( C4H9 represents a butyl group) ( 1 ⁇ n ⁇ 25 ).
  • the silicon-containing monomer I-1b is selected from
  • CH2 CH-C(O)-N[-( CH2 ) 3 -Si(OSi( CH3 ) 3 ) 3 ] 2 ,
  • CH 2 CH—C(O)—N[—(CH 2 ) 3 —Si(CH 3 )(OSi(CH 3 ) 3 ) 2 ] 2 ,
  • CH2 CH-C(O)-N[-( CH2 ) 3- (Si( CH3 ) 2O ) n -Si( CH3 ) 2C4H9 ] 2 ( C4H9 represents a butyl group) ( 1 ⁇ n ⁇ 25 ) and
  • CH 2 C(CH 3 )-C(O)-N[-(CH 2 ) 3 -(Si(CH 3 ) 2 O) n -Si(CH 3 ) 2 C 4 H 9 ] 2 (C 4 H 9 represents a butyl group) (1 ⁇ n ⁇ 25).
  • the silicon-containing monomer I-2 is selected from
  • CH2 C( CH3 )-C(O)-O-( CH2 ) 3Si (OSi( CH3 ) 3 ) 3 ,
  • CH2 C( CH3 )C(O)-NH-( CH2 ) 3Si (OSi( CH3 ) 3 ) 3 , and
  • CH2 C( CH3 )C(O)-NH-( CH2 ) 3- [Si( CH3 ) 2O ]n-Si( CH3 ) 2C4H9 ( C4H9 represents a butyl group ) (1 ⁇ n ⁇ 25).
  • monomer II is selected from one or more of dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, N-tert-butylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, dipropylaminoethyl (meth)acrylamide, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, and dipropylaminopropyl (meth)acrylamide.
  • monomer III is selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxypolyethylene glycol (meth)acrylate, preferably hydroxyethyl methacrylate and 4-hydroxybutyl acrylate.
  • the weight average molecular weight of the polymer is 8-2 million, preferably 2-1.5 million.
  • the polymer is in the form of an ammonium salt or a nitrogen oxide.
  • the present application further provides a treating agent, comprising the silicon-containing polymer described above and a solvent, wherein the solvent comprises water and/or an organic solvent.
  • the organic solvent is one or more of acetone, methyl ethyl ketone, 4-methyl-2-pentanone, ethyl acetate, butyl acetate, N-methyl-2-pyrrolidone, N,N-dimethylformamide, ethanol, isopropanol, n-propanol, butyl carbitol, and dipropylene glycol methyl ether.
  • the present application also relates to a method for producing the above-mentioned treatment agent, which comprises the following steps:
  • the proportion of silicon-containing monomers I-1a and/or I-1b in silicon-containing monomers I is 1% to 100%, 5% to 100%, 10% to 100%, 50% to 100%, 50% to 98%, for example, 1%, 5%, 10%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%, 101%, 102%, 103%, 104%, 105%, 106%, 107%, 108%, 109%, 110%, 111%, 112%, 113%, 114%, 115%, 116%, 117%, 118%, 119%, 120%, 121%, 122%, 123%, 124%, 125%, 126%, 127%, 128%, 129%, 130%, 131%, 132%, 133%, 134%, 135%, 136%,
  • the amount of silicon-containing monomer I in the total amount of monomers is 30%-90% by mass, preferably 40%-85%, more preferably 50%-80%, for example, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or a range consisting of any two of them.
  • the amount of monomer II is 5%-65% of the total monomer amount, preferably 10%-50%, more preferably 15%-45%, for example 5%, 10%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or any two thereof.
  • the amount of monomer III in the total amount of monomers is 0-40%, preferably 1%-40%, more preferably 5%-30%, and further preferably 10-25%, for example 1%, 3%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or the range composed of any two of them.
  • the manufacturing method may further include any one or more of the following steps (2), (3), and (4):
  • the present application also provides the use of the above silicon-containing polymer or the above treatment agent or the treatment agent prepared by the above method in fiber fabrics, leather, non-woven fabrics, asbestos, fur, concrete, natural stone, paper products or plastics.
  • the present application also provides a product treated with the above silicon-containing polymer or the above treatment agent or the treatment agent prepared by the above method, and the product can be fiber fabric, leather, non-woven fabric, asbestos, fur, concrete, natural stone, paper products or plastics.
  • the present application also provides a method for treating a product, which comprises contacting the product with the above-mentioned silicon-containing polymer or the above-mentioned treating agent or the treating agent prepared by the above-mentioned method, wherein the product is a paper product, natural stone, concrete, fiber fabric, synthetic leather, non-woven fabric, asbestos, fur or plastic.
  • the contacting is achieved by wet-end addition, surface sizing or coating process.
  • examples of paper products include but are not limited to paper, paper carriers such as paper cups, paper bowls, paper plates, etc.
  • the silicon-containing polymer and the resulting treatment agent of the present application can be easily dispersed in solvent or water and applied to the treatment of various articles, such as paper products, natural stone, concrete, fiber fabrics, synthetic leather, non-woven fabrics, asbestos, fur or plastic.
  • the treatment methods include coating, soaking or internal addition and other treatment methods.
  • the silicon-containing polymer and the resulting treatment agent of the present application can give the surface of the article oil-repellent and water-repellent properties after treatment.
  • alkyl refers to a straight chain alkyl or a branched alkyl, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, etc.
  • alkylene refers to straight or branched chain alkylene, non-limiting examples of which include methylene, ethylene, n -propylene , n-butylene, n-pentylene, -CHCH3CH2- , -CHCH3CH2CH2- , CH2CH3CHCH2- , and the like .
  • the polymerization method of the present polymer is not particularly limited, and conventional free radical polymerization methods such as bulk polymerization, solution polymerization in an organic solvent, and emulsion polymerization in water can all be used.
  • the initiator of the polymer peroxide, azo compound or persulfate compound can be used.
  • the polymerization initiator can be an oil-soluble or water-soluble initiator according to the polymerization system.
  • oil-soluble polymerization initiators preferably include 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), dimethyl-2,2'-azobis(2-methylpropionate), benzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, and the like.
  • water-soluble polymerization initiators preferably include 2,2'-azobisisobutylamidine dihydrochloride, 2,2'-azobis(2-methylpropionamidine) hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate, 2,2'-azobis[2-(5-methyl-imidazolin-2-yl)propane] hydrochloride, potassium persulfate, barium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide, and the like.
  • the polymerization initiator is preferably a peroxide or an azo compound with a half-life of 10 hours and a decomposition temperature of above 40°C, such as tert-butyl peroxypivalate, 2,2'-azobis(2-methylpropionitrile), etc.
  • the manufacturing process of the treatment agent of this application is as follows:
  • an oxidizing agent is added to the above dispersion for treatment.
  • the papers that can be processed include thin paper, thick paper, boxboard, or pulp molding, ranging from 300g carton per unit area ( m2 ), 80g kraft paper per unit area ( m2 ), 100g thin paper per unit area ( m2 ), to 200g paper-plastic products per unit area ( m2 ).
  • the raw materials of paper can be chemical bleached pulp or unbleached pulp, wood pulp, chemical mechanical pulp, mechanical pulp, etc. Resin components such as polyamide, polyolefin, polyvinyl alcohol, etc. can also be added to these pulps.
  • the methods of paper processing are as follows:
  • the sugarcane pulp board is directly subjected to pulping treatment, the deflection degree is 600 ml of Canadian freedom, the pulp concentration is 0.3%, and the sizing agent of alkyl ketene dimer (AKD) is added in sequence, the added amount is 2% of the dry paper weight, and then the synthesized treatment agent is added, the added amount is 1-15% of the dry paper weight.
  • the deflection degree is 600 ml of Canadian freedom
  • the pulp concentration is 0.3%
  • the sizing agent of alkyl ketene dimer (AKD) is added in sequence, the added amount is 2% of the dry paper weight, and then the synthesized treatment agent is added, the added amount is 1-15% of the dry paper weight.
  • test paper Paper weight 50 g/ m2
  • Chemical pulp LBKP broadleaf bleached kraft pulp
  • NBKP coniferous bleached kraft pulp
  • Cationic starch MC-2 type starch produced by Guangxi Mingyang Biochemical Company was added in an amount of 1% by weight of the pulp, and a thin sheet of paper with a weight of 50 g/ m2 was made by a fourdrinier paper machine.
  • the starch solution used for sizing is non-ion modified hydroxyethyl starch, Penford Gum 290 produced by Penford, with a concentration of 5%.
  • the starch solution is first heated to above 90°C for gelatinization, and then the synthesized treatment agent is added after the gelatinization is completed.
  • the concentration of the treatment agent in the starch solution is 1-15% by weight.
  • the temperature of the starch solution is controlled to be not less than 70°C, and the paper is first treated with surface sizing, and the liquid absorption exceeds 70%, and then dried to obtain the treated paper.
  • test paper Paper weight 230 g/ m2
  • the paper is made of five layers, of which the bottom and top layers are chemical pulp boards LBKP (bleached kraft pulp from broadleaf trees) plus NBKP (bleached kraft pulp from coniferous trees) in a ratio of 7:3.
  • the middle three layers are made of chemical mechanical pulp or mechanical pulp boards, which are compounded on the paper machine into a cardboard with a weight of 230 g/ m2 .
  • the coating starch used is cassava coating starch MS-1 produced by Guangxi Mingyang Biochemical Company.
  • the starch concentration is 20%, Add water to starch and heat to above 90°C for gelatinization. After gelatinization, add the synthesized paper treatment agent.
  • the concentration of the treatment agent in the starch solution is 1-15% (mass concentration). Control the starch temperature to not less than 50°C and apply it to the top layer of the paperboard using a paper coating machine.
  • the coating amount is 3-8 g/ m2 .
  • test is carried out according to GB/T1540-2002 or ISO 535:1991.
  • the principle is to measure the weight (g) of water absorbed by a 100 cm 2 paper supporting 10 mm of water in 1 minute, and convert the value into weight per square meter (g/m 2 ).
  • the Cobb absorbency tester usually uses a flip cylinder tester.
  • the metal cylinder is a cylinder with an inner cross-sectional area of (100 ⁇ 0.2) cm2 and a corresponding inner diameter of (112.8 ⁇ 0.2) mm. If a small cylinder is used, the recommended area should be no less than 50 cm2 . At this time, the volume of water should be reduced accordingly to ensure a water height of 10 mm.
  • the cylinder height is 50 mm.
  • the part of the cylinder ring surface in contact with the sample should be smooth and have sufficient roundness to prevent the edge of the cylinder from damaging the sample.
  • a layer of elastic but non-absorbent rubber pad or gasket should be added to the flip cylinder cover and the flat pressing base.
  • the metal roller should have a width of (200 ⁇ 0.5) mm, a mass of (10 ⁇ 0.5) kg, and a smooth surface.
  • the treated paper sample into 10 (125 ⁇ 5) mm square or ⁇ (125 ⁇ 5) mm circular specimens (5 on the front and 5 on the back).
  • the specimen size should be slightly larger than the outer diameter of the cylinder to avoid leakage caused by too small specimens and to avoid affecting operation by too large specimens.
  • This method directly tests the ability of paper to resist hot water.
  • the test method is relatively simple. Generally, the treated paper is made into a container that can hold liquids. 100°C boiling water is poured into it and observed for 30 minutes to see if there is any leakage. If there is no leakage, it passes. This method is suitable for pulp molded products.
  • the natural stones that can be processed include: marble, granite, sandstone, slate, etc.
  • Si-ph-B3 is replaced by the following silicon-containing monomers I with different structures, namely Si-ph-B1 (Example 2), Si-N2-B2 (Example 3), Si-N2-B1 (Example 4), Si-OCN-B3 (Example 5), Si-OCO-B3 (Example 6), Si-ph0-B3 (Example 7).
  • the solution was tested by gas chromatography-mass spectrometry, and the residual mass concentration of each monomer was less than 0.1%, indicating that the monomer composition of the obtained polymer was almost the same as the added monomer composition.
  • aqueous dispersion synthesized in the examples and comparative examples was used as a treatment agent to test several articles:
  • Paper tableware test Prepare a 1wt% pulp solution, add 2wt% of AKD type sizing agent and 10wt%, 6wt%, 3wt% of dry paper weight respectively, to make a 10-inch disc weighing 20 grams. Test with 85°C salad oil for 20 minutes, and grade and score according to the penetration; test with 100°C boiling water for 30 minutes, and record whether it passes or leaks.
  • Paper test 50 g/ m2 thin paper was selected and treated by surface sizing. The concentrations of the treating agent were 5wt%, 4wt% and 3wt% respectively. The hot oil resistance and Cobb water absorption value were tested.
  • Sandstone test dilute the treatment agent with water to 3wt%, 2wt% and 1wt% liquid respectively, soak the sandstone sample in the liquid, take it out and dry it naturally for 48 hours at a temperature not lower than 25°C, then drop salad oil and coffee on the sandstone surface respectively, observe the wetting state, and grade and score it.
  • Example 8-10 The test method is the same as that of Example 1.
  • the test performance of Examples 8-10 is summarized in Table 3.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente demande concerne un polymère contenant du silicium, un agent de traitement, leur procédé de préparation et leur application. Le polymère contenant du silicium comprend des unités de répétition produites par un monomère contenant du silicium I et des unités de répétition produites par un monomère II. Le monomère contenant du silicium I comprend un monomère contenant du silicium I-1a et/ou un monomère contenant du silicium I-1b. Le polymère ou un agent de traitement contenant le polymère peut être utilisé pour traiter une variété d'articles, tels que des produits en papier, des textiles, de la pierre, etc., pour donner aux articles la fonction de répulsion de l'huile et de l'eau.
PCT/CN2023/121145 2022-10-24 2023-09-25 Polymère contenant du silicium, agent de traitement, leur procédé de préparation et leur application WO2024087983A1 (fr)

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WO2009148029A1 (fr) * 2008-06-02 2009-12-10 旭硝子株式会社 Copolymère, procédé pour produire celui-ci, composition oléofuge et article traité avec la composition oléofuge
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CN114573768A (zh) * 2022-03-10 2022-06-03 北京马普新材料有限公司 一种水分散型聚合物、包含该聚合物的组合物及其应用
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