CN113423796B - Adhesive composition - Google Patents
Adhesive composition Download PDFInfo
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- CN113423796B CN113423796B CN201980091780.6A CN201980091780A CN113423796B CN 113423796 B CN113423796 B CN 113423796B CN 201980091780 A CN201980091780 A CN 201980091780A CN 113423796 B CN113423796 B CN 113423796B
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- 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
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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
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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
- 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
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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
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/10—Vinyl esters of monocarboxylic acids containing three or more carbon atoms
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- 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
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- 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
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- 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
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- 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
Abstract
The present invention relates to a composition comprising an ethylene-vinyl ester copolymer and a filler. The composition can be used in the field of wood bonding.
Description
Technical Field
The invention relates to the technical field of binders suitable for wood bonding.
Background
DE-B2214410 (U.S. Pat. No. 6,142,222) and DE-B2614261 (BG-A1569637) relate to a process for the preparation of redispersible vinyl acetate/ethylene copolymer dispersion powders which are obtained in such a way that: the monomers are emulsion polymerized in the presence of partially hydrolyzed polyvinyl alcohol as protective colloid and the resulting aqueous dispersion is then spray dried. The powder is suitable as a binder for adhesives and coating compositions. Because ethylene is contained in the polymer, no film forming auxiliary agent is required to be added; however, to improve the caking stability, up to 30% by weight of an antiblocking agent is added to the powder, which greatly reduces the cohesive strength. In addition, the ethylene content of the copolymer is relatively high in order to lower the minimum film forming temperature, with the result that the thermal stability of the ethylene-containing vinyl acetate copolymer is very poor.
CN1084371C discloses a wood glue powder which is redispersible in water, has good caking stability and a Minimum Film Forming Temperature (MFFT) of 0-5 ℃. The wood glue powder comprises 70-90wt% of homo-or copolymer of vinyl ester and 10-30wt% of one or more fully hydrolyzed (i.e. degree of hydrolysis 96-100%) homo-or copolymer of vinyl alcohol. CN1084371C shows through experiments that if the rubber powder contains a vinyl alcohol homopolymer or copolymer with a hydrolysis degree of 96-100%, the adhesive strength is better than that of the rubber powder containing a vinyl alcohol homopolymer or copolymer with a hydrolysis degree of 85%. CN1084371C discloses that small amounts of anti-caking agents (e.g. calcium carbonate) may be added to the wood glue powder, but the amount of anti-caking agent should not exceed 40wt% of the total weight of the polymer. CN1084371C also discloses that in order to meet the requirement of high hot water resistant bonding, a hardness enhancer (e.g. AlCl) may be added to the wood glue powder 3 Such acidic metal salts) and a crosslinking agent (polyisocyanate). Since the above prior art clearly indicates that the ethylene-containing vinyl acetate copolymers have very poor thermal stability, CN1084371C did not attempt to contain ethylene-vinyl acetateWood glue powder protocol of copolymer.
Disclosure of Invention
The invention discloses a powder adhesive composition without water, which can be blended into a flowing state by adding water or polyvinyl alcohol aqueous solution before use. Is very easy to disperse and is especially suitable for adhesion between wood. This composition achieves higher water and heat resistance adhesion than the D4 performance group requirements in DIN standard EN 204. It also has the advantages of no volatile components, no film forming aids, no plasticizers, and a lower minimum film forming temperature MFFT. The powder adhesive composition of the present invention is free of water, and thus is convenient for long-distance transportation and long-time storage. And which also requires far lower storage temperature conditions than liquid adhesive products.
In the present invention, an aqueous solution of a partially hydrolyzed vinyl alcohol homopolymer or copolymer may occur in three cases:
case one: in the emulsion polymerization of ethylene-vinyl esters, aqueous solutions of partially hydrolyzed vinyl alcohol homo-or copolymers (b 1) are used as protective colloids;
and a second case: mixing the ethylene-vinyl ester aqueous dispersion of which the emulsion polymerization is completed with an aqueous solution of a partially hydrolyzed vinyl alcohol homo-or copolymer (b 2), and spray-drying to obtain a redispersible rubber powder;
and a third case: optionally, the wood glue powder composition/binder is mixed with an aqueous solution of the partially hydrolysed vinyl alcohol homo-or copolymer (b 3) before use.
A composition comprising:
100% by weight of a redispersible powder of component (a+b1+b2) (i.e. Dispersible polymer powders) and greater than or equal to 55% by weight of a filler of component (c), preferably in an amount of between 80% and 200% by weight, more preferably between 90 and 180% by weight, still more preferably between 100 and 160% by weight,
wherein the weight of the component (a+b1+b2) is 100wt%
Wherein the component (a+b1+b2) is a redispersible powder comprising ethylene comonomer.
In the present invention, redispersible powders (i.e., dispersible polymer powders) are: the powdered thermoplastic resinous material is converted from the polymer emulsion by a series of processes such as high temperature and pressure, spray drying and surface treatment. When mixed with water, these powdered organic binders can be redispersed in water to form new emulsions, which have substantially the same properties as the original copolymer emulsion.
The composition as described above, component (a+b1+b2) comprises:
component (a) an ethylene-vinyl ester copolymer,
component (b1+b2) is one or more partially hydrolyzed vinyl alcohol homopolymers or copolymers.
In the composition described above, the ethylene monomer is used in an amount of 1 to 20% by weight, preferably between 8 and 17% by weight, more preferably between 8 and 15% by weight, preferably between 10 and 15% by weight, based on 100% by weight of the total amount of all the comonomers, of the copolymer of ethylene-vinyl ester of component (a).
The composition as described above, component (a+b1+b2) comprises:
100% by weight of component (a) ethylene-vinyl ester copolymer,
0.1 to 5% by weight of one or more partially hydrolysed vinyl alcohol homo-or copolymers of component (b1+b2), preferably in an amount of between 0.5 and 3% by weight, more preferably between 1 and 3% by weight,
wherein the redispersible powders are present in an amount of 100% by weight based on the weight of the component (a+b1+b2).
A composition as described above wherein component (a) is an ethylene-vinyl acetate copolymer; preferably, the amount of comonomer other than ethylene and vinyl acetate in component (a) is less than 0.03wt%, more preferably less than 0.01wt%, calculated as 100wt% of the total amount of all comonomers.
The composition as described above, wherein component (a) is a copolymer of ethylene-vinyl ester, preferably an ethylene-vinyl ester-vinyl chloride copolymer, wherein vinyl chloride is used in an amount of between 20 and 30wt% or between 65 and 75wt%, more preferably the amount of other comonomers in component (a) than ethylene, vinyl ester, vinyl chloride is less than 0.03wt%, more preferably less than 0.01wt%, calculated as 100wt% of the total amount of all comonomers.
The composition as described above, component (a+b1+b2) redispersible powders have a glass transition temperature Tg (median mid point) of between-5 and 20℃and preferably between-5 and 18 ℃.
The Tg test method is carried out according to the standard ISO11357-5 by using a differential scanning calorimeter, the temperature test range is-20-120 ℃, and the temperature rising rate is 10 ℃/min.
The composition as described above has a glass transition temperature Tg (median mid point) of between-5 and 20 ℃, preferably between-5 and 18 ℃, more preferably between 10 and 18 ℃.
In the composition as described above, the minimum film-forming temperature MFFT of the redispersible powders of the component (a+b1+b2) is 0 ℃ or higher, preferably 3 ℃ or higher, more preferably 4 ℃ or higher.
The test method of the minimum film forming temperature MFFT is carried out according to the standard ISO 2115-1996, and the temperature test range is-10 ℃ to 50 ℃.
The composition as described above, is a solid composition; preferably a solid powder composition; more preferably, the particle size of the powder is not more than 4% by weight and not less than 400. Mu.m.
The composition as described above has a water content of less than 1% by weight, preferably less than 0.1% by weight, calculated as 100% by weight of component (a+b1+b2).
The composition as described above, wherein the plasticizer is used in an amount of less than 1wt%, preferably less than 0.1wt%, calculated as 100wt% of the weight of component (a+b1+b2). Wherein the plasticizer is phthalate, including dioctyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, butyl benzyl phthalate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisodecyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate.
The composition as described above wherein the amount of volatile coalescents is less than 1wt%, preferably less than 0.1wt%, calculated as 100wt% of the weight of component (a+b1+b2). Volatile coalescents refer to alcohols, including benzyl alcohol, ethylene glycol, propylene glycol, hexylene glycol, and the like, 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, and propylene glycol phenyl ether.
The composition as described above, wherein component (a+b1) is obtained by emulsion polymerization of ethylene-vinyl ester in the presence of a surfactant and/or (b 1) an aqueous solution of a vinyl alcohol homo-or copolymer.
The composition as described above, wherein the redispersible powders of the component (a+b1+b2) are obtained by spray-drying an aqueous dispersion containing an ethylene-vinyl ester copolymer of the component (a+b1) and an aqueous solution containing a homo-or copolymer of vinyl alcohol of the component (b 2).
A composition as described above wherein the filler of component (c) is a neutral or weakly acidic inorganic filler having a particle size of 500 to 2500 mesh, preferably 700 to 1250 mesh, preferably selected from the group consisting of aluminum silicate powder, diatomaceous earth, colloidal silica gel, fumed silicic acid, precipitated silicic acid, silica fume, light spar, kaolin, talc, cement, diatomaceous earth, calcium carbonate, or hydrogenated magnesium silicate; preferably, the calcium carbonate has a particle size between 700 and 1250 mesh.
A process for preparing the composition as described above, which comprises spray-drying a mixture of an aqueous dispersion of an ethylene-vinyl ester copolymer containing component (a+b1) and an aqueous solution of a homo-or copolymer of vinyl alcohol containing component (b 2) to give a redispersible powder (a+b1+b2) and mixing with component (c).
If necessary, an additive may be mixed into an aqueous dispersion containing the ethylene-vinyl ester copolymer of the component (a+b1) and an aqueous solution containing the partially hydrolyzed vinyl alcohol homopolymer or copolymer of the component (b 2), and then the mixture may be dried by spray drying.
Use of a composition as described above in the preparation of a woodworking glue.
The use as described above, wherein the above composition is used for the bonding of structural and non-structural wood parts.
The use as described above, wherein the composition is used in a two-component EPI panel glue.
The use of the composition as described above, comprising mixing it with water under agitation prior to use.
The use of the composition as described above comprises mixing it with an aqueous solution of polyvinyl alcohol with stirring prior to use.
A two-component composition comprising
Component A, comprising a redispersible powder of component (a+b1+b2) and a filler of component (c),
component D, comprising (D) a crosslinker comprising MDI,
wherein the redispersible powders are present in an amount of 100% by weight based on the weight of the component (a+b1+b2).
A two-component composition as described above, wherein the weight ratio of the redispersible powders of component (a+b1+b2) to the crosslinking agent of component (d) is between 0.5 and 2.5, preferably between 0.8 and 2.3, more preferably between 1.4 and 2.0,
a three-component composition comprises
Component A, comprising a redispersible powder of component (a+b1+b2) and a filler of component (c),
component D, comprising (D) a crosslinker comprising MDI,
component C, comprising (e) water and/or (b 3) an aqueous solution of a homo-or copolymer of vinyl alcohol,
wherein the redispersible powders are present in an amount of 100% by weight based on the weight of the component (a+b1+b2).
The three-component composition as described above, wherein the weight ratio of water contained in component C to component D is between 0.5 and 4, preferably between 0.8 and 3, more preferably between 1.2 and 2.9.
The three-component composition as described above, wherein the solid content of the aqueous binder dispersion obtained after mixing component A with component C is between 45 and 75% by weight, preferably between 50 and 75% by weight.
The use of a composition as described above, comprising, prior to use
(i) Component A and component C (comprising (e) water and/or (b 3) an aqueous solution of a vinyl alcohol homopolymer or copolymer) are first stirred and mixed,
(ii) And then stirring and mixing the component D crosslinking agent and the mixture obtained in the step (i) uniformly.
Wherein the mixture obtained in step (ii) should be used within 20-120 minutes, preferably within 30-90 minutes, more preferably within 30-60 minutes.
Preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl esters of alpha-branched monocarboxylic acids having up to 10 carbon atoms, such as VeoVa 9 or VeoVa 10. Vinyl acetate is particularly preferred.
If desired, other comonomers may be used in an amount of from 1.0 to 65% by weight, based on the total weight of the ethylene-vinyl ester copolymer of component (a), of vinyl aromatic compounds, such as styrene, and/or vinyl halides, such as vinyl chloride, and/or esters of acrylic acid and/or methacrylic acid with alcohols having from 1 to 10 carbon atoms, 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, 2-ethyl acrylate and/or ethylenically unsaturated dicarboxylic acid esters and/or derivatives thereof, such as diisopropyl fumarate, maleic acid or dimethyl fumarate, methyl t-butyl ester, di-n-butyl ester, di-t-butyl ester and ethyl ester, or maleic anhydride.
It is preferred to use other comonomers which increase the hardness of the polymer, even if polymerized with a higher Tg value. Examples of such comonomers are VeoVa 9 and vinyl chloride.
If desired, the ethylene-vinyl ester copolymer may also comprise from 0.05 to 10% by weight, based on the total weight of the comonomers, of auxiliary monomers selected from ethylenically unsaturated carboxylic acids, preferably acrylic acid and methacrylic acid; ethylenically unsaturated amides, preferably acrylamides; ethylenically unsaturated sulphonic acids and salts thereof, preferably vinylsulphonic acid, alpha-acrylamide-2-methylpropanesulphonic acid; and/or a polyethylenically unsaturated comonomer such as divinyl adipate, diallyl maleate, allyl methacrylate or triallyl isocyanurate. Further suitable auxiliary monomers are crosslinking monomers, for example acrylamidoglycolic acid (AGA), methyl methacrylamidoglycolate (MAGME), N-methylolacrylamide (NMAA), N-methylolmethacrylamide, allyl N-methylolcarbamate; alkyl ethers such as isobutoxy ether, or esters of N-methylolacrylamide, of N-methylolmethacrylamide, or of allyl N-methylolcarbamate.
In component (a), preferred ethylene-vinyl ester copolymers are:
ethylene-vinyl acetate copolymers having an ethylene content of 8 to 13wt%, preferably 9 to 12wt%;
ethylene-vinyl acetate-vinyl chloride copolymer, wherein the vinyl chloride content is 10-40wt%, preferably 15-30wt%, more preferably 20-30wt%, more preferably 22-28wt%;
ethylene-vinyl laurate-vinyl chloride copolymer, wherein the content of vinyl chloride is 50 to 85wt%, preferably 60 to 70wt%, more preferably 65 to 78wt%, more preferably 70 to 75wt%;
this stage is calculated as 100% by weight of the total amount of all comonomers.
The ethylene-vinyl ester copolymer is prepared by an emulsion polymerization method. The polymerization may be carried out batchwise or continuously, with or without mother liquor, and the initial charge may comprise all or individual components of the reaction mixture, with the addition of certain components or individual components being carried out first and then of the other components being metered in, or else by metering in without the initial charge. All metering is preferably carried out at constant speed. The copolymerization of ethylene is used, preferably at a reaction pressure of from 20 to 40bar.
The polymerization is preferably carried out at a temperature of from 40℃to 80℃and is initiated in the manner customary for emulsion polymerization. The initiation may be carried out using customary water-soluble free-radical initiators, preferably in an amount of from 0.01 to 1.0% by weight, based on the total weight of the monomers. Examples of such initiators are ammonium persulfate and potassium persulfate; peroxides such as t-butyl peroxide; hydrogen peroxide. If desired, the above-mentioned radical initiators may also be used in combination with reducing agents in amounts of from 0.01 to 0.5% by weight, based on the total weight of the monomers. Suitable reducing agents are formaldehydesulfoxylate, sodium bisulphite or ascorbic acid. When redox initiation is employed, it is preferred to meter in one or both of the redox catalyst components simultaneously during the polymerization.
Useful dispersants include all emulsifiers customary in emulsion polymerization. The emulsifier is preferably used in an amount of 1 to 4% by weight based on the total weight of the monomers. Examples of suitable emulsifiers are cationic surfactants, such as alkyl sulfates having 8 to 18 carbon atoms; alkyl and alkylaryl ether sulfates having 8 to 18 carbon atoms in the hydrophobic group and up to 40 ethylene oxide or propylene oxide units; alkyl or alkylaryl sulfonates having 8 to 18 carbon atoms; full or monoester esters of thiosuccinic acid with monohydric alcohols or alkylphenols. Examples of suitable anionic surfactants are alkyl polyglycol ethers or alkylaryl polyglycol ethers having from 8 to 40 ethylene oxide units.
If desired, protective colloids can be used, preferably in amounts of up to 4% by weight, based on the total weight of the monomers. Examples of such compounds are: 75 to 90 mole% of a vinyl alcohol-vinyl acetate copolymer of vinyl alcohol monomer; polyvinylpyrrolidone having a molecular weight of 5000 to 400,000 and hydroxyethylcellulose having a degree of substitution of 1.5 to 3.
The pH required to carry out the polymerization is generally in the range from 3 to 7 and can be adjusted in a conventional manner with acids, bases or buffers such as alkali metal phosphates or alkali metal carbonates. For the purpose of adjusting the molecular weight, customary regulators, such as mercaptans, aldehydes and chlorinated hydrocarbons, can be added in the polymerization.
The solids content of the aqueous dispersion is preferably from 30 to 65% by weight.
In the present invention, the partially hydrolyzed vinyl alcohol homo-or copolymer of component (b 1) or component (b 2) or component (b 3) means: those homopolymers or copolymers having a degree of hydrolysis of from 75 to 90 mol%, preferably from 85 to 90 mol%. For example: the degree of hydrolysis is preferably from 85 to 90 mol% of a homo-or copolymer of vinyl alcohol having a Hoppler viscosity of from 2 to 6 mPas, or from 15 to 20 mPas, or from 22 to 30 mPas, as measured in a 4% aqueous solution.
Among them, a homopolymer or copolymer of vinyl alcohol having a Hoppler viscosity of 15 to 20 mPas as measured with a 4% aqueous solution and a degree of hydrolysis of preferably 85 to 90 mol% is preferable.
Preferred vinyl alcohol copolymers are those which, in addition to vinyl alcohol units, contain from 0.5 to 10% by weight, preferably from 1 to 5% by weight, based on the total weight of the copolymer, of 1-methyl vinyl alcohol units. Particularly preferred vinyl alcohol copolymers are vinyl alcohol-1-methyl vinyl alcohol copolymers having a degree of hydrolysis of 98 to 100 mol%.
Vinyl alcohol homopolymers or copolymers are commercially available and/or are prepared by hydrolysis or alcoholysis of the corresponding vinyl acetate homopolymers or copolymers using well-known methods.
For the preparation of water-redispersible wood glues with good caking stability, the ethylene-vinyl ester copolymers are used in the form of aqueous dispersions having a solids content of 30 to 60% by weight, and the vinyl alcohol polymers are mixed with the dispersion in the form of solids or aqueous solutions, preferably in the form of aqueous solutions.
The mixing operation can be carried out in any manner in conventional mixing devices. The mixing ratio is selected so that the content of the ethylene-vinyl ester copolymer component in the resulting redispersible powders is from 70 to 90% by weight, preferably from 80 to 90% by weight; the vinyl alcohol polymer is present in an amount of 10 to 30wt%, preferably 10 to 20wt%, calculated as 100wt% redispersible powders.
The mixture is then spray dried, which may be carried out in a preheated or unheated drying gas stream using a single or multiple structure nozzle or a drying tray. Typically, the drying temperature should not exceed 250 ℃. The optimum temperature of the drying gas can be determined experimentally, and in most cases drying temperatures above 60℃have proven to be particularly suitable.
Detailed Description
Rubber powder 2: tg=17 ℃ mfft=4 ℃ VAE redispersible powders, wherein the ethylene monomer is used in an amount of 10-15wt%, calculated as 100wt% of the total amount of all comonomers
Rubber powder 3: tg= -3 ℃ MFFT = 0 ℃ VAE redispersible rubber powder, wherein ethylene monomer is used in an amount of 10-15wt%, calculated as 100wt% of the total amount of all comonomers
Rubber powder 4: tg=12 ℃ mfft=5 ℃ VAE-VC redispersible powders, wherein the ethylene monomer amount is 8-17wt%, the vinyl chloride amount is 20-30wt%, calculated as 100wt% of the total amount of all comonomers
Rubber powder 5: tg=1deg.C mfft=0deg.C Vinyl laurate-E-VC redispersible powders, wherein the ethylene monomer amount is 8-17wt%, the Vinyl chloride amount is 65-75wt%, calculated as 100wt% of the total amount of all comonomers
Rubber powder 6: tg=1 ℃ mfft=0 ℃ Vinyl laurate-E-VC redispersible powders, wherein ethylene monomer is used in an amount of 10-15wt%, vinyl chloride is used in an amount of 65-75wt%, calculated as 100wt% total of all comonomers, the above materials are provided by the wack chemical company and TG is calculated as the median.
Rubber powder A: TG (median) =22 ℃ mfft=5 ℃, VA-Veova redispersible powders. Supplied by Shanxi three-dimensional group Inc. under the trade name SWF-04.
PVA 17/88 has a degree of hydrolysis of about 88mol% of a vinyl alcohol homo-or copolymer, which has a Hoppler viscosity of about 17 mPas as measured in a 4% aqueous solution, and is commercially available.
MDI diphenylmethane diisocyanate, commercially available.
CaCO 3 Calcium carbonate, 700 mesh particle size, is commercially available.
Preparation method
And (o) taking a certain amount of redispersible rubber powder and filling materials, stirring and mixing to obtain the component A.
(i) Uniformly mixing the component A and the component C, wherein the component C comprises (e) water and/or (b 3) an aqueous solution of a vinyl alcohol homopolymer or copolymer,
wherein the solid content of the aqueous binder dispersion obtained after mixing component A with component C is between 45 and 75% by weight, preferably between 50 and 75% by weight.
(ii) Adding component D cross-linking agent (including MDI) into the mixture obtained in step (i), stirring and mixing uniformly, and using immediately.
The testing method comprises the following steps:
spline preparation
The test method is carried out according to European standard EN-204. The test sample bar is beech, the sample bar size is 70mm, 20mm, 5mm, and the density is 700kg/m 3 The water content was 12wt%. The glue coating thickness of the joint is 0.1mm, and the glue coating area is 20mm x 10mm. After the glue is coated, the joint is arrangedMaintained at a pressure of 0.8MPa for 2 hours. After the pressure is removed, the mixture is cured for more than 7 days in an environment with 23 ℃ and 55% relative humidity.
Intensity test
The test conditions for the D4 performance group in DIN standard EN204 are:
the bars were boiled in boiling water for 6 hours and then immersed in water at 20 ℃ for 2 hours. The shear strength of the bars was tested immediately in the wet state.
And testing the tensile shear strength of the sample bar in a universal material testing machine, wherein the tensile speed is 50mm/min until the joint breaks, reading the pressure value at the moment, namely the shear strength of a final sample, and repeating each sample for 4-5 times to obtain an average value.
TABLE 1
As can be seen from Table 1, in the case where MFFT is equal to or higher than 4deg.C, or Tg is equal to or higher than 10deg.C, the shear strength is higher at D4 (5.34 MPa vs. 4.15 MPa) for the VAE redispersible powders containing ethylene of example Ex.1 than for the comparative example C.Ex.3 (VA-Veova redispersible powders (without ethylene)). The adhesive composition of the invention has higher water-and heat-resistant adhesive properties, i.e. a shear strength of 4.3MPa or more, than the requirements of the D4 performance group in DIN standard EN 204.
In the rubber powder A of the comparative example C.Ex.3, the redispersible rubber powder only containing VA-Veova (without ethylene) has the defect of too high MFFT and difficult construction in a low-temperature environment.
TABLE 2
As can be seen from Table 2, higher water and heat resistant adhesion is achieved when the weight ratio of the redispersible powders of component (a+b1+b2) to the crosslinker MDI of component (D) is between 1.4 and 2.0 and the weight ratio of the water contained in component C to component D is between 1.2 and 2.9.
Claims (18)
1. A three-component composition comprising
Component A comprises
100 parts by weight of a redispersible powder of component (a+b1+b2), and
55 parts by weight or more of the filler of the component (c),
wherein the component (a+b1+b2) is redispersible rubber powder containing ethylene comonomer,
component D, comprising (D) a crosslinker comprising MDI,
component C, comprising (e) water and/or (b 3) an aqueous solution of a homo-or copolymer of vinyl alcohol,
wherein the weight ratio of the redispersible powders of component (a+b1+b2) to the crosslinking agent of component (d) is between 1.4 and 2.0;
wherein the weight ratio of water contained in component C to component D is between 1.2 and 2.9.
2. The three-part composition according to claim 1, wherein the amount of the component (c) is between 80 parts by weight and 200 parts by weight.
3. The three-part composition according to claim 1, wherein the amount of the component (c) is between 100 and 160 parts by weight.
4. A three-part composition according to any one of claims 1 to 3, wherein part (a+b1+b2) comprises:
100 parts by weight of component (a) an ethylene-vinyl ester copolymer,
0.1 to 5 parts by weight of one or more partially hydrolyzed homopolymers or copolymers of vinyl alcohol of component (b1+b2).
5. A three-part composition according to any one of claims 1 to 3, wherein part (a+b1+b2) comprises:
100 parts by weight of component (a) an ethylene-vinyl ester copolymer,
0.5 to 3 parts by weight of one or more partially hydrolyzed homopolymers or copolymers of vinyl alcohol of component (b1+b2).
6. A three-part composition according to any one of claims 1 to 3, wherein part (a+b1+b2) comprises:
100 parts by weight of component (a) an ethylene-vinyl ester copolymer,
1 to 3 parts by weight of one or more partially hydrolyzed vinyl alcohol homopolymers or copolymers of component (b1+b2).
7. A three-part composition according to any one of claims 1 to 3, wherein component (a) is an ethylene-vinyl acetate copolymer, or component (a) is an ethylene-vinyl ester-vinyl chloride copolymer, wherein vinyl chloride is used in an amount of between 20 and 30wt% or between 65 and 75wt%, calculated as 100wt% of the total amount of all comonomers.
8. The three-part composition of claim 4 wherein component (a) is an ethylene-vinyl acetate copolymer or component (a) is an ethylene-vinyl ester-vinyl chloride copolymer wherein vinyl chloride is present in an amount of between 20 and 30wt% or between 65 and 75wt%, calculated as 100wt% of the total amount of all comonomers.
9. A three-part composition according to any one of claims 1 to 3, wherein
The glass transition temperature Tg of the component A is between-5 and 20 ℃, the Tg test method is carried out according to the standard ISO11357-5 by using a differential scanning calorimeter, the temperature test range is between-20 ℃ and 120 ℃, and the temperature rising rate is 10 ℃/min.
10. The three-part composition of claim 4, wherein
The glass transition temperature Tg of the component A is between-5 and 18 ℃, the Tg test method is carried out according to the standard ISO11357-5 by using a differential scanning calorimeter, the temperature test range is between-20 ℃ and 120 ℃, and the temperature rising rate is 10 ℃/min.
11. The three-part composition of claim 7, wherein
The glass transition temperature Tg of the component A is between 10 ℃ and 18 ℃, the Tg test method is carried out according to the standard ISO11357-5 by using a differential scanning calorimeter, the temperature test range is-20 ℃ to 120 ℃, and the temperature rising rate is 10 ℃/min.
12. A composition according to any one of claims 1 to 3, 8, 10, 11 wherein the minimum film forming temperature MFFT of the redispersible powders of component (a+b1+b2) is greater than or equal to 0 ℃;
the test method of the minimum film forming temperature MFFT is carried out according to the standard ISO 2115-1996, and the temperature test range is-10 ℃ to 50 ℃.
13. The composition of any one of claims 1-3, 8, 10, 11, component a being a solid composition.
14. The composition according to claim 6, wherein component A is a solid powder composition having a particle size of not more than 400 μm and not more than 4% by weight.
15. Use of a composition according to any one of claims 1-3, 8, 10, 11, 14 for the preparation of a woodworking glue.
16. Use of the composition of claim 7 for the preparation of a two-component EPI panel glue.
17. Use of the composition of claim 12 for the preparation of a two-component EPI panel glue.
18. Use of the composition of claim 13 for the preparation of a two-component EPI panel glue.
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| PCT/CN2019/074830 WO2020163989A1 (en) | 2019-02-12 | 2019-02-12 | Adhesive composition |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183796A (en) * | 1994-12-08 | 1998-06-03 | 瓦克化学有限公司 | Wood glue powder |
| CN1358778A (en) * | 2000-12-14 | 2002-07-17 | 瓦克聚合系统两合公司 | Process for preparing volatility content reduced polymer |
| CN102066513A (en) * | 2008-06-23 | 2011-05-18 | 瓦克化学股份公司 | Heat resistant emulsion polymer dispersion |
| CN104837939A (en) * | 2012-12-14 | 2015-08-12 | 汉高股份有限及两合公司 | Method for producing aa polyvinyl acetate dispersion |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1801154B1 (en) * | 2004-09-28 | 2011-08-31 | The Nippon Synthetic Chemical Industry Co., Ltd. | Ethylene/vinyl alcohol copolymer composition and multilayer structure comprising the same |
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2019
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183796A (en) * | 1994-12-08 | 1998-06-03 | 瓦克化学有限公司 | Wood glue powder |
| CN1358778A (en) * | 2000-12-14 | 2002-07-17 | 瓦克聚合系统两合公司 | Process for preparing volatility content reduced polymer |
| CN102066513A (en) * | 2008-06-23 | 2011-05-18 | 瓦克化学股份公司 | Heat resistant emulsion polymer dispersion |
| CN104837939A (en) * | 2012-12-14 | 2015-08-12 | 汉高股份有限及两合公司 | Method for producing aa polyvinyl acetate dispersion |
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