[go: up one dir, main page]

WO2020163989A1 - Composition adhésive - Google Patents

Composition adhésive Download PDF

Info

Publication number
WO2020163989A1
WO2020163989A1 PCT/CN2019/074830 CN2019074830W WO2020163989A1 WO 2020163989 A1 WO2020163989 A1 WO 2020163989A1 CN 2019074830 W CN2019074830 W CN 2019074830W WO 2020163989 A1 WO2020163989 A1 WO 2020163989A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
dpp
ethylene
vinyl
composition
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.)
Ceased
Application number
PCT/CN2019/074830
Other languages
English (en)
Inventor
Yipeng WEI
Hoai Thi TRAN THI
Ping 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/CN2019/074830 priority Critical patent/WO2020163989A1/fr
Priority to CN201980091780.6A priority patent/CN113423796B/zh
Publication of WO2020163989A1 publication Critical patent/WO2020163989A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00—Adhesives based on 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • C09J131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09J131/04—Homopolymers or copolymers of 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
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/04—Adhesives based on 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09J127/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the present invention relates to the field of adhesive technology suitable for wood bonding.
  • DE-B2214410 (US-A3883489) and DE-B2614261 (BG-A1569637) relates to a method for preparing redispersible vinyl acetate /ethylene copolymer dispersible powders, the dispersible powder is obtained: as monomer partially hydrolyzed polyvinyl alcohol protective colloid for emulsion polymerization in the presence of, and then spray-drying the resulting dispersion.
  • the powder suitable as a binder in adhesives and coating compositions. Because in this polymer containing ethylene, it is not necessary to add a coalescent; but in order to improve the stability of blocking, the powder must be added up to 30% (by weight) of the anti-caking agent, thus greatly reducing the Bond strength. In order to reduce the minimum film forming temperature, the ethylene content of the copolymer is relatively high, with the result that the thermal stability of such comprising an ethylene vinyl acetate copolymer is very poor.
  • CN1084371C discloses water-redispersible, blocking-resistant wood glue powder having a minimum film forming temperature (MFFT) of 0 to 5°C.
  • the wood glue powder contains 70-90 wt%vinyl ester homopolymers or vinyl ester copolymers, 10-30 wt%one or more fully hydrolyzed vinyl alcohol homopolymers or vinyl alcohol copolymers with a degree of hydrolysis of 96-100 mol%.
  • CN1084371C experimentally proves that if a glue powder contains vinyl alcohol homopolymers or copolymers having a degree of hydrolysis of 96-100 mol%, its adhesive strength is better than that of vinyl alcohol homopolymers or copolymers having a degree of hydrolysis of 85 mol%.
  • CN1084371C discloses that an antiblocking agent (e.g., calcium carbonate) can be added to the wood powder in a small amount of not more than 40 wt%, based on the total weight of the polymer.
  • an antiblocking agent e.g., calcium carbonate
  • CN1084371C also discloses that if high hot water resistance is required, hardeners (e.g. acid metal salts such as AlCl 3 ) or crosslinking agents (e.g. polyisocyanate) can be added. Since the aforementioned prior art clearly suggests that the ethylene-containing vinyl acetate copolymers have very low thermal stability, CN1084371C does not work on a wood glue powder based on ethylene vinyl acetate copolymers.
  • the present invention discloses a water-free powder adhesive composition which can be turned into flowing state by adding water or an aqueous solution of polyvinyl alcohol prior to use.
  • the composition is very easy to disperse, making it especially suitable for wood-wood bonding. Compared to the requirements of class D4 according to DIN EN 204, this composition can offer better bonding properties and higher water and heat resistance. It also has the advantages of being free of volatile components, film-forming agents and plasticizer, and having a lower minimum film forming temperature (MFFT) .
  • MFFT film forming temperature
  • the absence of water in the powder adhesive composition of the present invention allows for easier long-distance transportation and long-term storage. Furthermore, its storage temperature requirement is also far lower than that of liquid adhesive products.
  • the aqueous solution of partially hydrolyzed vinyl alcohol homopolymers or copolymers may appear in the following three situations:
  • the wood glue powder composition /adhesive is mixed with an aqueous solution of partially hydrolyzed vinyl alcohol homopolymers or copolymers (Component (b3) ) .
  • composition comprising
  • Component (a+b1+b2) 100 wt%of Component (a+b1+b2) , a dispersible polymer powder (DPP) , and Component (c) , a filler, present in an amount of greater than or equal to 55 wt%, preferably 80-200 wt%, more preferably 90-180 wt%, and most preferably 100-160 wt%, based on the total weight, as 100wt%, of Component (a+b1+b2) , wherein Component (a+b1+b2) contains ethylene comonomers.
  • the Dispersible polymer powders (DPP) in present invention are polymer emulsions which have been converted by a series of process such as high temperatures and pressures, spray drying and surface treatment to powdered thermoplastic resin materials. When mixed with water, these powdered organic binders can redisperse in water back into new emulsions with essentially identical properties to the original copolymer emulsions.
  • Component (a+b1+b2) DPP contains:
  • Component (a) ethylene-vinyl ester copolymers
  • Component (b1+b2) one or more partially hydrolyzed vinyl alcohol homopolymers or copolymers.
  • ethylene monomers is present in Component (a) ethylene-vinyl ester copolymers in an amount of 1-20wt%, preferably 8-17 wt%, preferably 8-15wt%, more preferably 10-15wt%based on the total weight, as 100wt%, of all comonomers.
  • Component (a+b1+b2) DPP contains:
  • Component (b1+b2) partially hydrolyzed vinyl alcohol homopolymers or copolymers, present in an amount of 0.1-5 wt%, preferably 0.5-3 wt%, more preferably 1-3 wt%, based on the 100wt%weight of Component (a+b1+b2) DPP.
  • Component (a) are ethylene-vinyl acetate copolymers; preferably in Component (a) the amount of comonomer other than ethylene and vinyl acetate is less than 0.03 wt%, more preferably less than 0.01 wt%, calculated by using 100wt%of total comonomer.
  • Component (a) are ethylene-vinyl ester copolymers; preferably ethylene-vinyl ester-vinyl chloride copolymers, the amount of vinyl chloride is 20-30wt%or 65-75wt%; more preferably in Component (a) the amount of comonomer other than ethylene, vinyl ester and vinyl chloride is less than 0.03 wt%, more preferably less than 0.01 wt%, calculated by using 100wt%of total comonomer.
  • the glass transition temperature (Tg, mid-point) of Component (a+b1+b2) DPP is between -5 and 20°C, preferably between -5 and 18°C, measured using a differential scanning calorimeter, according to ISO 11357-5, at a heating rate of 10 °C/min within a temperature range of from -20 to 120 °C.
  • the Tg (mid point) of the composition is between -5 and 20°C, preferably between -5 and 18°C, more preferably between 10-18°C.
  • the minimum film forming temperature (MFFT) of Component (a+b1+b2) DPP is greater than or equal to 0°C, preferably greater than or equal to 3 °C, more preferably greater than 4°C, measured according to standard ISO 2115-1996, within a temperature range of from -10 to 50°C.
  • composition mentioned above is a solid, preferably in a powder form, and more preferably containing less than or equal to 4 wt%of powder particles having a diameter of greater than or equal to 400 ⁇ m.
  • composition mentioned above has a water content of less than 1 wt%, preferably less than 0.1 wt%, based on the total weight, as 100wt%, of Component (a+b1+b2) DPP.
  • composition mentioned above contains plasticizers in an amount of less than 1 wt%, preferably less than 0.1 wt%, based on the total weight, as 100wt%, of Component (a+b1+b2) DPP, wherein the plasticizers are phthalates, including dioctyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, butyl benzyl phthalate, dimethyl phthalate, Diethyl phthalate, dibutyl phthalate, diisononyl phthalate, di-octyl phthalate, dicyclohexyl phthalate.
  • plasticizers are phthalates, including dioctyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, butyl benzyl phthalate, dimethyl phthalate, Diethyl phthalate, dibutyl phthalate, diisononyl
  • composition mentioned above contains volatile film-forming agents in an amount of less than 1 wt%, preferably less than 0.1 wt%, based on the total weight, as 100wt%, of Component (a+b1+b2) DPP, wherein the volatile film-forming agents are alcohols, including benzyl alcohol, ethylene glycol, propylene glycol, hexanediol, etc., and esters including alcohol ester-12, and alcohol ethers including ethylene glycol butyl ether, propylene glycol methyl, propylene glycol ethyl ether, propylene glycol butyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether.
  • the volatile film-forming agents are alcohols, including benzyl alcohol, ethylene glycol, propylene glycol,
  • Component (a+b1) is obtained by the emulsion polymerization of ethylene and vinyl esters in the presence of a surfactant and/or an aqueous solution of Component (b1) .
  • Component (a+b1+b2) DPP is obtained by spay-drying an aqueous dispersion containing Component (a+b1) and an aqueous solution containing Component (b2) .
  • Component (c) is a neutral or slightly acidic inorganic filler having a particle size of from 500 to 2,500 mesh, preferably from 700 to 1250 mesh, preferably one or more selected from the group consisting of aluminum silicate powders, diatomaceous earth, colloidal silica gels, fumed silica, precipitated silica, silica powders, light spar, kaolin, talc, cement, calcium carbonate and magnesium hydride. Preference is given to calcium carbonate having a particle size of 700-1250 mesh.
  • composition mentioned above is prepared by first spray drying the mixture of an aqueous dispersion containing Component (a+b1) and an aqueous solution containing Component (b2) to obtain a dispersible polymer powder (DPP) , Component (a+b1+b2) , which is then mixed with Component (c) .
  • DPP dispersible polymer powder
  • an additive may be added to the mixture of an aqueous dispersion containing Component (a+b1) and an aqueous solution containing Component (b2) , followed by a spray-drying process.
  • composition mentioned above can be used to prepare wood adhesives.
  • the above-mentioned composition is used for the bonding of non-load-bearing wood parts or load-bearing wood parts.
  • the above-mentioned composition is used for two-component EPI wood glue for wood to wood bonding.
  • the use described above includes a step that the above-mentioned composition is mixed with water prior to use.
  • the use described above includes a step that the above-mentioned composition is mixed with an aqueous solution of polyvinyl alcohol prior to use.
  • a two-component composition comprising
  • Component A containing Component (a+b1+b2) DPP and Component (c) filler
  • Component D containing Component (d) a crosslinker, which including MDI, based on the 100wt%weight of Component (a+b1+b2) DPP.
  • the weight ratio of Component (a+b1+b2) DPP to Component (d) crosslinker ranges from 0.5 to 2.5, preferably from 0.8 to 2.3, more preferably from 1.4 to 2.0.
  • a three-component composition comprising
  • Component A containing Component (a+b1+b2) DPP and Component (c) filler, and
  • Component D containing Component (d) crosslinker, which containing MDI,
  • Component C containing Component (e) water, and/or an aqueous solution of
  • the weight ratio of water contained in Component C to Component D ranges from 0.5 to 4, preferably from 0.8 to 3, more preferably 1.2-2.9.
  • the aqueous dispersion of adhesive obtained by mixing Component A and Component C has a solid content of 45-75wt%, preferably 50-75 wt%.
  • the mixture obtained in the step (ii) should be used within 20-120 min, preferably within 30-90 min, more preferably within 30-60 min.
  • vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl trimethyl acetate, vinyl acetate, carbon atoms most ⁇ -branched monocarboxylic acid vinyl esters 10 as VeoVa9 or VeoVa10. Vinyl acetate is particularly preferred.
  • copolymer comprising a vinyl aromatic hydrocarbon compounds such as styrene, and /or vinyl halides such as vinyl chloride, and /or acrylic acid and /or methacrylic acid with an alcohol having a carbon number of 1 to 10 formed by esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate n-butyl acrylate, t-butyl acrylate, n-butyl methacrylate, t-butyl methacrylate, ethyl acrylate, ethyl acrylate and /or ethylenically unsaturated dicarboxylic acid ester and /or a derivative thereof thereof, such as diisopropyl fumarate, maleate, or dimethyl
  • Preferably containing other comonomers can increase the hardness, even if the copolymer has polymerized comonomer of higher Tg value.
  • comonomers are vinyl chloride and VeoVa9.
  • ethylene-vinyl ester copolymers can also comprise from 0.05 to 10% (by weight) of the total weight of the comonomer auxiliary monomers, these auxiliary monomers selected from ethylenically unsaturated carboxylic acid, preferably acrylic acid and methacrylic acid; ethylenically unsaturated amides, preferably acrylamide; ethylenically unsaturated sulfonic acids and salts thereof, preferably vinylsulfonic acid, acrylamido-2-methylpropyl alpha] acid; and /or more ethylenically unsaturated comonomers such as divinyl adipate, diallyl maleate, allyl methacrylate or triallyl esters of cyanuric acid.
  • auxiliary monomers selected from ethylenically unsaturated carboxylic acid, preferably acrylic acid and methacrylic acid; ethylenically unsaturated amides, preferably acrylamide; ethyl
  • auxiliary monomers as crosslinking monomers such as acrylamide glycolic acid (AGA) , methyl-ethanol methacrylamide (MAGME) , N-methylolacrylamide (NMAA) , N-methylol acrylamide, N-methylol allylcarbamate; alkyl ethers such as isobutoxy ether, or N-methylol acrylamide ester, N-methylol methacrylamide ester, or N-methylol allylcarbamate.
  • AGA acrylamide glycolic acid
  • MAGME methyl-ethanol methacrylamide
  • NMAA N-methylolacrylamide
  • alkyl ethers such as isobutoxy ether, or N-methylol acrylamide ester, N-methylol methacrylamide ester, or N-methylol allylcarbamate.
  • preferred ethylene-vinyl ester copolymers include: ethylene-vinyl acetate copolymers having an ethylene content of 8-13 wt%, preferably 9-12wt%,
  • ethylene-vinyl acetate-vinyl chloride copolymers having a vinyl chloride content of 10-40 wt% preferably 15-30 wt%, more preferably 20-30wt%, more preferably 22-28wt%and ethylene-vinyl laurate-vinyl chloride copolymers having a vinyl chloride content of 50-85 wt%, preferably 60-70wt%, more preferably 65-78wt%, more preferably 70-75wt%, wherein all figures in wt%are based on the total weight, as 100wt%, of all comonomers in this paragraph.
  • Ethylene-Vinyl ester copolymers prepared by emulsion polymerization employed.
  • the polymerization reaction can be a batch type or continuous type, with or without a mother liquor feeding the starting component may comprise all or individual components of the reaction mixture, certain components can be put into the first or the individual components, subsequently metered into other components, or method without using metered initially charged. Preferably constant for all metered.
  • the reaction pressure is preferably 20 to 40 bar.
  • the polymerization is preferably carried out at a temperature of 40-80 °C, and emulsion polymerization initiated by the usual manner.
  • Conventional water-soluble initiators can be used free-radical initiators, preferably in an amount (by weight) 0.01 to 1.0%of the total weight of the monomers. Examples of such initiators are potassium persulfate and ammonium persulfate; peroxides such as tert-butyl hydroperoxide; hydrogen peroxide.
  • the radical initiator and may also be used in an amount of from 0.01 to 0.5% (by weight) of the total monomer weight of a reducing agent in combination. Suitable reducing agents include formaldehyde sulfoxylate, sodium bisulfite or ascorbic acid.
  • Useful dispersants include all emulsifiers commonly used in emulsion polymerization.
  • the amount of emulsifier is preferably from 1 to 4%of the total weight of the monomer (by weight) .
  • suitable emulsifiers are cationic surfactants such as carbon atoms, alkyl sulfates of 8 to 18; the number of carbon atoms in the hydrophobic group of 8 to 18 and the number of ethylene oxide or propylene oxide units up 40 is alkyl and alkylaryl ether sulfates; carbon atoms 8-18 alkyl or alkaryl sulfonate; full ester or thio acid mono formed with monohydric alcohols or alkylphenols ester.
  • suitable anionic surfactants are those containing 8 to 40 ethylene oxide units, alkyl polyglycol ethers or alkylaryl polyglycol ethers.
  • the protective colloid may be used, which is most preferably used in an amount (by weight) 4%of the total weight of the monomers.
  • examples of such compounds include: vinyl alcohol monomer comprises 75 to 85% (molar) vinyl alcohol -vinyl acetate copolymer; molecular weight of 5,000 to 400,000 polyvinylpyrrolidone, and degree of substitution of hydroxyethyl of 1.5 to 3 cellulose.
  • the pH value required for the polymerization reaction is generally in the range of 3 to 7 may be employed in a conventional manner with an acid, base or buffer such as alkali metal phosphates or alkali metal carbonates adjusted.
  • an acid, base or buffer such as alkali metal phosphates or alkali metal carbonates adjusted.
  • the polymerization reaction may be added in conventional regulators, such as mercaptans, aldehydes and chlorinated hydrocarbons.
  • the aqueous dispersion has a solid content of preferably from 30 to 65 wt%.
  • the partially hydrolyzed vinyl alcohol homopolymers or copolymers in Component (b1) or (b2) or (b3) refer to those homopolymers or copolymers having a degree of hydrolysis of 75-90 mol%, preferably 85-90 mol%.
  • vinyl alcohol homopolymers or copolymers having a degree of hydrolysis of 85-90 mol%and a viscosity, in 4 wt%aqueous solution, of 15-20 mPa.s.
  • Preferred vinyl alcohol copolymer such as a copolymer, i.e. containing vinyl alcohol units in addition, also comprises from 0.5 to 10%of the total weight of copolymer (by weight) , preferably from 1 to 5% (by weight) of 1-methyl a copolymer of vinyl alcohol units.
  • a vinyl alcohol copolymer as a degree of hydrolysis (molar) 98-100%of vinyl alcohol, 1-methyl-vinyl alcohol copolymer.
  • Vinyl alcohol homo-or copolymer commercially available as a commodity, and /or using well-known methods from the corresponding homopolymer or copolymer of vinyl acetate hydrolysis or alcoholysis prepared.
  • ethylene-vinyl ester polymers to a solid content of 30 to 60% (by weight) is used, the vinyl alcohol polymer in form of a solid or an aqueous solution and this dispersion was mixed, preferably mixed in the form of an aqueous solution.
  • Mixing operation may be carried out in a conventional manner in any mixing device.
  • the mixing ratio should be chosen such that in the DPP, ethylene-vinyl ester polymer in an amount of 70 to 90% (by weight) , preferably 80-90% (wt) ; vinyl alcohol polymer in an amount of 10 to 30 % (by weight) , preferably 10-20% (by weight) , based on the total weight, as 100wt%, of the DPP.
  • spray-drying nozzle can be a single structure or multiple structures in the nozzle plate or drying or preheating without preheating the drying gas stream.
  • the drying temperature should not exceed 250 °C.
  • the optimum temperature of the drying gas may be experimentally determined, in most cases, the drying temperature above 60 °C proved to be particularly suitable.
  • PVA 17/88 vinyl alcohol homopolymers or copolymers having a degree of hydrolysis of about 88 mol%, and a viscosity, in a 4wt%aqueous solution, of about 17 mPa ⁇ s, commercially available
  • MDI diphenylmethane-diisocyanate
  • CaCO 3 calcium carbonate (700 mesh) , Commercially available
  • Component (e) water, and/or an aqueous solution of Component (b3) vinyl alcohol homopolymers or copolymers,
  • Component C has a solids content of 45-75wt%, preferably 50-75%wt%;
  • step (ii) adding Component D (including MDI) to the mixture obtained in step (i) , mixing well and using immediately.
  • the test was conducted according to the European standard EN-204.
  • the test sample was beech, measuring 70 mm x 20 mm x 5 mm, with a density of 700kg/m 3 , and a water content of 12wt%.
  • the bond line at the joint was 20 mm long and 10 mm wide, with a thickness of 0.1 mm. After application, the joint was pressed at a pressure of 0.8 MPa for 2 hours After the pressure was removed, it was stored for more than 7 days at 23°C and 55%relative humidity.
  • test sample was boiled in water for 6 hours and then immersed in 20 °C water for 2 hours. After that, the wet sample was immediately tested for shear strength.
  • the sample was tested for tensile shear strength using a universal material experiment machine at an elongation rate of 50 mm/min. When the joint was broken, read the pressure value, i.e. the shear strength of the final sample. Each sample was tested 4 to 5 times before calculating the average.
  • Table 2 shows that when the weight ratio of Component (a+b1+b2) DPP to Component (d) crosslinker MDI ranges from 1.4 to 2.0, and the weight ratio of water contained in Component C to Component D ranges from 1.2 to 2.9, the composition of the present invention can offer better bonding properties and higher water and heat resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition comprenant un copolymère éthylène-ester vinylique et une charge. Ladite composition peut être utilisée dans le domaine du collage du bois.
PCT/CN2019/074830 2019-02-12 2019-02-12 Composition adhésive Ceased WO2020163989A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2019/074830 WO2020163989A1 (fr) 2019-02-12 2019-02-12 Composition adhésive
CN201980091780.6A CN113423796B (zh) 2019-02-12 2019-02-12 一种粘合剂组合物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/074830 WO2020163989A1 (fr) 2019-02-12 2019-02-12 Composition adhésive

Publications (1)

Publication Number Publication Date
WO2020163989A1 true WO2020163989A1 (fr) 2020-08-20

Family

ID=72044512

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/074830 Ceased WO2020163989A1 (fr) 2019-02-12 2019-02-12 Composition adhésive

Country Status (2)

Country Link
CN (1) CN113423796B (fr)
WO (1) WO2020163989A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932647A (en) * 1994-12-08 1999-08-03 Wacker - Chemie Gmbh Wood glue powder
US20020165341A1 (en) * 2000-12-14 2002-11-07 Wacker Polymer Systems Gmbh & Co. Kg Process for the preparation of polymers having a reduced content of volatile components
EP2138548B1 (fr) * 2008-06-23 2011-03-30 Wacker Chemie AG Dispersion de polymère à émulsion thermorésistante
US20150274850A1 (en) * 2012-12-14 2015-10-01 Henkel Ag & Co. Kgaa Method for producing a polyvinyl acetate dispersion

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1801154B1 (fr) * 2004-09-28 2011-08-31 The Nippon Synthetic Chemical Industry Co., Ltd. Formulation de copolymere ethylene/alcool vinylique et structure multicouche comprenant ledit copolymere

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932647A (en) * 1994-12-08 1999-08-03 Wacker - Chemie Gmbh Wood glue powder
US20020165341A1 (en) * 2000-12-14 2002-11-07 Wacker Polymer Systems Gmbh & Co. Kg Process for the preparation of polymers having a reduced content of volatile components
EP2138548B1 (fr) * 2008-06-23 2011-03-30 Wacker Chemie AG Dispersion de polymère à émulsion thermorésistante
US20150274850A1 (en) * 2012-12-14 2015-10-01 Henkel Ag & Co. Kgaa Method for producing a polyvinyl acetate dispersion

Also Published As

Publication number Publication date
CN113423796A (zh) 2021-09-21
CN113423796B (zh) 2023-08-04

Similar Documents

Publication Publication Date Title
EP0153728B1 (fr) Procédé pour la production d'une émulsion d'un copolymère d'acetate de vinyl et d'éthylène utilisant deux alcohols de polyvinyle comme système de stabilisation et une composition adhésive contenant l'émulsion
US4073779A (en) Hydrolysis-resistant, film-forming copolymer dispersions
KR100961241B1 (ko) 양이온 안정성 및 수재분산성 중합체 분말 조성물의 제조방법
US5907011A (en) Heterogeneous polyvinyl ester dispersions and powders
CA2202383C (fr) Poudre de colle a bois
EP0484822B1 (fr) Emulsions de copolymères acétate de vinyle/ethylène avec des propriétés adhérantes en humidité améliorés
US5633334A (en) Ethylene-vinyl acetate emulsions with an improved balance of adhesive properties
EP1067147B1 (fr) Emulsions d'acetate de vinyle/éthylène à taux en matières solides élevées
US6710113B2 (en) Process for preparing two-phase polymers in the form of their aqueous dispersions and water-redispersible powders
US5296532A (en) Adhesive compositions containing aqueous copolymer dispersions and acid metal salts or free acids
JP2002167403A (ja) ビニルエステル系樹脂エマルジョンの製法
KR20070083672A (ko) 소수성 단량체의 유화 중합
US6616798B2 (en) Process for preparing adhesives having improved adhesion
JPWO2007074674A1 (ja) 接着性組成物
US6093766A (en) Process for preparing polyvinyl alcohol stabilized solvent- and plastifier-free polyvinyl ester dispersions
US9926232B2 (en) Process for producing water-redispersible polymer powder compositions having cationic functionality
US6489391B1 (en) Process for preparing aqueous, protective colloid stabilized vinyl ester homopolymer and copolymer dispersions
US20050250899A1 (en) Use of copolymers stabilized with a protective colloid in cement-free or low-cement coating materials
US9650507B2 (en) Method for producing vinyl ester polymers having specifically settable dispersity and low polydispersity
WO2020163989A1 (fr) Composition adhésive
WO2007141211A1 (fr) Carreaux enduits d'une dispersion de polymÈre aInsi que procÉdÉ pour la fabrication de ceux-ci
JPH08193154A (ja) 不均質ポリビニルエステル分散物および−粉末
JP2015034197A (ja) 乳化重合用分散剤およびそれを用いて得られる酢酸ビニル系樹脂エマルジョン、ならびに接着剤
CA2069670A1 (fr) Dispersions polymeriques obtenues a partir de pivalate de vinyle, d'acetate de vinyle et d'alcene
DE102012220776A1 (de) Verfahren zur Herstellung von Polyvinylalkohol-stabilisierten Polymerisaten mittels Emulsionspolymerisation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19914703

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19914703

Country of ref document: EP

Kind code of ref document: A1