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WO2018148929A1 - Use of aqueous polymer dispersion for interfacial bonding between polymeric porous materials - Google Patents

Use of aqueous polymer dispersion for interfacial bonding between polymeric porous materials Download PDF

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Publication number
WO2018148929A1
WO2018148929A1 PCT/CN2017/073909 CN2017073909W WO2018148929A1 WO 2018148929 A1 WO2018148929 A1 WO 2018148929A1 CN 2017073909 W CN2017073909 W CN 2017073909W WO 2018148929 A1 WO2018148929 A1 WO 2018148929A1
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WO
WIPO (PCT)
Prior art keywords
vinyl
aqueous polymer
polymer dispersion
materials
peeling strength
Prior art date
Application number
PCT/CN2017/073909
Other languages
French (fr)
Inventor
Jin Zheng
Lingyun Huang
Ping Zhang
Haoqing Sun
Yan Wu
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Wacker Chemie Ag
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Filing date
Publication date
Application filed by Wacker Chemie Ag filed Critical Wacker Chemie Ag
Priority to KR1020197024065A priority Critical patent/KR20190103408A/en
Priority to BR112019017015A priority patent/BR112019017015A2/en
Priority to PCT/CN2017/073909 priority patent/WO2018148929A1/en
Priority to CN201780084599.3A priority patent/CN110461888A/en
Publication of WO2018148929A1 publication Critical patent/WO2018148929A1/en
Priority to PH12019501906A priority patent/PH12019501906A1/en

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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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • 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
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • C08F230/085—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 the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes

Definitions

  • the present invention relates to the use of an aqueous polymer dispersion for interfacial bonding between polymeric porous materials.
  • US6624243B2 discloses an aqueous polymer dispersion prepared by the polymerization of polymerizable monomers of silanes, vinyl esters, epoxy compounds and 1, 3 dicarbonyl compounds.
  • the aqueous dispersion can improve the scratch resistance of wall paints.
  • US6863985B2 discloses an aqueous polymer dispersion obtained by the polymerization of polymerizable monomers of silanes, silicone fluids, vinyl esters and epoxy compounds.
  • the dispersion can provide strong water resistance and good water vapor permeability, and can therefore be used especially in exterior paints.
  • WO2014071550A1 describes an aqueous polymer dispersion for textile lamination.
  • the said polymer is obtained by the polymerization of polymerizable monomers of vinyl acetate-ethylene and polyurethanes.
  • the wet peeling strength of said aqueous polymer dispersion-bonded product is from 6 to 8 N, which is obtained from a sample after it is laminated at 160°C for 6 seconds, cures at 180°C for 2 minutes and then is immersed in cold water for 0.5 hour.
  • CN102869828B discloses a carpet coating composition
  • a carpet coating composition comprising an interpolymer prepared by the emulsion polymerization of vinyl acetate monomer, ethylene and an unsaturated silane co-monomer which is effective to alter interpolymer molecular weight, branching and/or flow properties such that a film formed from said interpolymer exhibits an elongation value of less than about 125%at 110 °C.
  • the present invention discloses a use of an aqueous polymer dispersion to improve the water resistance of interfacial bond between polymeric porous materials, wherein said polymer is obtained by the polymerization of a composition comprising components:
  • a –one or more monomers selected from the group consisting of Vinyl esters of unbranched or branched alkylcarboxylic acid having 1 to 15 carbon atoms, vinyl aromatics, olefins, diolefins and vinyl halides;
  • B a polymerizable, hydrolysable silicon-containing compound, selected from among unsaturated hydrolyzable vinyl organosilicon compounds;
  • interfacial bonding between polymeric porous materials is that between the same or different materials selected from among fiber textile materials and polymeric foamed materials, preferably that between the same or different members selected from the group consisting of synthetic fiber textile materials, synthetic fiber non-woven materials, natural fiber textile materials, natural fiber non-woven materials, regenerated cellulose materials, ethylene-vinyl acetate (EVA) copolymer sponges and polyurethane sponges.
  • synthetic fiber textile materials synthetic fiber non-woven materials
  • natural fiber textile materials natural fiber non-woven materials
  • regenerated cellulose materials ethylene-vinyl acetate (EVA) copolymer sponges and polyurethane sponges.
  • EVA ethylene-vinyl acetate
  • the wet peeling strength retention i.e. the ratio of wet peeling strength to dry peeling strength, is equal to or greater than 0.5 as tested according to ST-4 and ST-3.
  • the wet peeling strength according to ST-4 is equal to or greater than 30N/inch.
  • Composite products are obtained in such a way that polymeric porous materials are interfacially bonded. Some of them often come into contact with water during use, or frequently need to be cleaned. Use fields of these composites include, for example, shoe liners, shoe inserts and sportswear. Composite products with poor water resistance are prone to degumming in contact with water, that is, interface debonding, leading to a short service life.
  • the interfacial bonding between polymeric porous materials is preferably the lamination of a fiber textile material onto a polymeric foamed material.
  • the interfacial bonding between polymeric porous materials is preferably that between polyester or acrylic or cotton textile materials and flat EVA ethylene-vinyl acetate copolymer sponges.
  • the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded, the resulting product being exposed to a heat source for a period of time.
  • carpets comprise a primary backing with yarn tufts in the form of cut or uncut loops extending upwardly from the backing to form a pile surface.
  • yarn tufts in the form of cut or uncut loops extending upwardly from the backing to form a pile surface.
  • the yarn is inserted into a primary backing by tufting needles and a pre-coat or binder is applied thereto.
  • the fibers are embedded and actually held in place by the binder composition.
  • the interfacial bonding between polymeric porous materials does not include the production of polymeric porous materials themselves using a binder, which mainly refers to the bonding together of fibrous polymer materials less than 5 mm in diameter.
  • a binder is used to form non-woven fabrics by bonding together the fibrous materials such as wood pulp fibers, rayon, cottons, wools and acetate fibers; or in the process of paper making, a binder is used to form paper webs, papers or cardboards by bonding pulp fibers together.
  • the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded, the resulting product being exposed to a heat source, at between 150 and 200°C, for a period of time between 25 and 120 seconds to complete the drying step; or the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded, the resulting product being exposed to a heat source, at between 100 and 110°C, for a period of time between 20 and 30 minutes to complete the drying step.
  • the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded using a roll coater with a certain pressure, and simultaneously completing the drying step therein.
  • the coat weight of the aqueous polymer dispersion is between 120 and 210 g/m 2 .
  • the glass transition temperature (Tg) of the dried product of the aqueous polymer dispersion is between -2°C and 4°C as tested according to ST-1.
  • This aqueous polymer dispersion is used for the interfacial bonding between a fiber textile material and a polymeric foamed material, the resultant product being soft to the touch.
  • the aqueous polymer dispersion is an emulsion that is highly stable and has a rate of change in Brookfield viscosity of less than 30 wt%after 14 days of storage at 50°C.
  • Rate of change in Brookfield viscosity refers to the difference between the Brookfield viscosity at day 1 and that at day 14, divided by the Brookfield viscosity at day 1, under the storage condition at 50°C.
  • the Brookfield viscosity of the aqueous polymer dispersion is between 1,500 and 10,000 mPa ⁇ s as tested according to ST-2.
  • the coating roller takes up a small amount of glue during the production, leading to a poor bonding effect of the product; while the viscosity of the aqueous polymer dispersion is too high, the coating roller takes up a large amount of glue, leading to excessive coat weight in the product and high consumption of the aqueous polymer dispersion and thus to diseconomy.
  • component A one or more monomers, is selected from the group consisting of vinyl esters, ethylene, vinyl chloride and acrylates; more preferably component A is vinyl acetate and ethylene.
  • component C is an unsaturated alkylsulfonate, preferably sodium vinylsulfonate, 1-allyloxy-2-hydroylpropyl sulfonate, 2-acrylamido-2-methyipropanesulfonate sodium, more preferably sodium vinylsulfonate.
  • the dry material weight ratio of component B, a polymerizable, hydrolyzable silicon-containing compound, to component C, a polymerizable anionic emulsifier ranges from 1 to 2.
  • the dry material weight ratio of component B, a polymerizable, hydrolyzable silicon-containing compound, to component D, a vinyl-modified epoxy compound ranges from 0.5 to 0.7.
  • the composite prepared according to the use described above has a wet peeling strength retention, i.e. the ratio of wet peeling strength to dry peeling strength, equal to or greater than 0.5 as tested according to ST-4 and ST-3.
  • the composite prepared according to the use described above has a wet peeling strength equal to or greater than 30 N/inch and a wet peeling strength retention equal to or greater than 0.5, both as tested according to ST-4.
  • This aqueous polymer dispersion is used for the interfacial bonding between a fiber textile material and a polymeric foamed material, the resultant product having good water resistance.
  • aqueous polymer dispersion in the invention is used for interfacial bonding between polymeric porous materials, wherein the polymer is obtained by the polymerization of a composition comprising components A-D.
  • Component A one or more monomers, is selected from the group consisting of Vinyl esters of unbranched or branched alkylcarboxylic acid having 1 to 15 carbon atoms, vinyl aromatics, olefins, diolefins and vinyl halides.
  • Vinyl esters of unbranched or branched alkylcarboxylic acid having 1 to 15 carbon atoms are selected from the group of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of ⁇ -branched monocarboxylic acids having up to 10 carbon atoms, for example VeoVa 9 or VeoVa 10, wherein vinyl acetate is particularly preferred.
  • Suitable comonomers are the eaters of unbranched or branched alcohols having 1 to 15 atoms, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate, wherein preference is given to methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
  • the said component A can also be polymerized to form copolymers of vinyl acetate and ethylene, or copolymers of vinyl acetate and ethylene and one or more other vinyl monomers, such as vinyl acetate-ethylene-acrylate copolymers, vinyl acetate-ethylene-vinyl chloride copolymers.
  • Component B a polymerizable, hydrolyzable silicon-containing compound, is preferably selected from among unsaturated hydrolyzable vinyl organosilicon compounds, and is more preferably one or more compounds selected from the group consisting of vinyltrimethoxysilane, vinyldimethoxymethylsilane, vinylmethoxydimethyl-silane, vinyltriethoxysilane, vinyldiethoxymethylsilane, vinylethoxydimethylsilane vinyltris (methylethoxy) silane, vinyltris (methylisopropoxy) silane, 3-methacryloxypropyl-trimethoxysilane and 3-methacryloxypropyltriethoxysilane.
  • the most preferred component B is vinyltrimethoxysilane and/or vinyltriethoxy-silane.
  • Component C a polymerizable anionic emulsifier, is selected from among unsaturated alkylsulfonates, preferably sodium vinylsulfonate, 1-allyloxy-2-hydroylpropyl sulfonate, 2-acrylamido-2-methyipropanesulfonate sodium, more preferably sodium vinylsulfonate.
  • unsaturated alkylsulfonates preferably sodium vinylsulfonate, 1-allyloxy-2-hydroylpropyl sulfonate, 2-acrylamido-2-methyipropanesulfonate sodium, more preferably sodium vinylsulfonate.
  • the optional component D a vinyl-modified epoxy compound, is selected from among glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, vinyl cyclohexene dioxide.
  • the polymers are prepared by the solution polymerization process, emulsion polymerization process or suspension polymerization process, preferably by the emulsion polymerization process, in which the polymerization temperature is generally from 20°C to 100°C, preferably from 45°C to 80°C.
  • the polymerization of gaseous monomers, such as ethylene, 1, 3-butadiene or vinyl chloride, can also be carried out generally in the range of from 5 bar to 100 bar abs.
  • the pH range desired for the polymerization which is in general between 2.5 and 10, preferably 3 and 8, can be established in a known manner by acids, bases or customary buffer salts, such as alkali metal phosphates or alkali metal carbonates.
  • the polymerization is initiated by a water-soluble or monomer-soluble initiator or redox initiator combinations customary for emulsion polymerization or suspension polymerization.
  • water-soluble initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, tert-Butyl peroxypivalate, and azobisisobutyronitrile. These initiators are generally used in an amount of 0.01 to 3%by weight in each case based on the total dry weight of the monomers.
  • Suitable reducing agents are the sulfites or bisulfites of alkali metals/ammonium, derivatives of sulfoxylic acid of alkali metals/ammonium, or sulfinates of alkali metals/ammonium.
  • the amount of said reducing agent is generally from 0.01 to 3 %by weight in each case based on the total dry weight of the monomers of Component A.
  • regulating substances can be used during the polymerization. If regulators are used, they are usually employed in amounts of from 0.01 to 5.0%by weight, based on the total dry weight of the monomers of Component A, and are introduced separately or premixed with reaction components. Examples of such substances are n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptopropionic acid, methyl mercaptopropionate, isopropanol and acetaldehyde.
  • Suitable protective colloids for the polymerization are polyvinyl alcohols; polyvinyl acetals; polyvinylpyrrolidones; polysaccharides in water-soluble form, e.g. starches (amylose and amylopectin) , celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives, dextrins and cyclodextrins.
  • the polymerization can be carried out successively or continuously.
  • an post-polymerization can be carried out to remove residual monomers using known methods, in general by means of an post-polymerization initiated by a redox catalyst. Volatile residual monomers can also be removed by means of distillation, preferably under reduced pressure, and, if appropriate, with inert entrainer gases such as air, nitrogen or steam being passed through or over the polymerization mixture.
  • the aqueous polymer dispersions obtainable in this way have a solids content of from 40 to 70%by weight.
  • Protective colloids used as spray additives
  • defoamers and anti-caking agents can be added to the aqueous polymer dispersions herein for subsequent preparation of water-redispersible polymer powders by means of a traditional process: fluidized-bed drying, freeze drying or spray drying.
  • Tg glass transition temperature
  • the viscosity of the sample is determined with a Brookfield RV/DV rotational viscometer according to GB/T 11175-2002 using spindle No. 4 at 20 rpm at 25°C.
  • a dry fabric sample mentioned above is tested for 180° peeling strength in reference to the method shown in Figure 1 of ISO11339-2010 on Shandong Labthink XLW (G) -PC smart electronic tensile tester.
  • the dry sample with its width remaining 25.4 mm (1 inch) , is vertically stretched at a speed of 100 mm/min for a distance of 40 mm. The stretches up to 2 mm at both the beginning and end of the test are not taken into account.
  • the wet fabric sample is tested for 180° peeling strength in reference to the method shown in Figure 1 of ISO11339-2010 on Shandong Labthink XLW (G) -PC smart electronic tensile tester.
  • Heating time 15 ⁇ 30 s
  • EP706K a commercially available product from Wacker Chemie AG, which is not the aqueous polymer dispersion as described in the claims of the present invention, is used as the binder to select a lab-scale sample preparation method for peeling strength closest to the industrial-scale one. From the test data in Table 1, it can be seen that the lab-scale preparation method for peeling strength test that involves heat treatment at 105°C for 30 minutes is virtually equivalent to its industrial-scale counterpart.
  • the aqueous polymer dispersions in Examples 1 to 9 and Comparative Examples C1 to C3 were prepared according to the basic formulation in Table 2.
  • the basic formulation in Table 2 contains the type of monomers, amount of monomers, type of protective colloid, initiator system, initial charge and subsequent feed of each raw material, and the like.
  • the concentration of a solution is the weight of solute divided by the weight of solution, in the form of percent by weight.
  • GMA glycidyl methacrylate
  • Genapol 3214 tridecyl alcohol ethoxylate, having an alkyl chain length of about C13 and an HLB value of about 17, is supplied by Clariant;
  • RHODASURF 6530 aliphatic alcohol ethoxylate with an HLB of about 17, is supplied by Rhodia Solvay Group;
  • Polyvinyl Alcohol 25/88 having an alcoholysis degree of 88 wt%, 4 wt%aqueous solution of which has a viscosity of 25 mPa ⁇ s at 20°C according to DIN 53015, is prepared into a 10.3 wt%aqueous solution before use.
  • EP 706K is an ethylene-vinyl acetate aqueous polymer dispersion available from Wacker Chemie AG.
  • the amount of ethylene used in Table 2 refers to the amount of ethylene gas fed in each example.
  • a premix of 584.43 g of deionized water, 443 g of 10.3 wt%polyvinyl alcohol 25/88, 13 g of Mersolate H95, 110.77 g of 65 wt%Genopol 3214, 20.1 g of 25 wt%sodium vinylsulfonate, 2.78 g of 2 wt%EDTA-Na and 20.3 g of sodium acetate were added into a 5-liter reactor.
  • the premix was mixed well and its pH was adjusted to 5 with acetic acid.
  • the reactor was heated to 70°C, into which 252 g of vinyl acetate and 400 g of ethylene were added, and the pressure in the reactor was maintained below 45 bar.
  • the temperature was raised to 70°C while the aqueous solutions of 1.25 wt%ammonium persulfate and 5 wt%aqueous 2-hydroxy-2-sulfinic acid disodium acetate were added dropwise with a pump to initiate reaction and the dropwise addition continued until the reaction was completed.
  • 2, 265.6 g of vinyl acetate was added at a rate of 12.6 g/min, and a mixed solution of 318.76 g of deionized water, 115 g of 10.3 wt%Polyvinyl Alcohol 25/88, 7.12 g of XL 10 and 12.2 g of glycidyl methacrylate were added at a rate of 2.5 g/min.
  • the mixture was transferred to a degassing tank, where 1 g of defoamer Foamaster 223 was added, and after degassing for 30 minutes, the aqueous polymer dispersion was obtained.
  • the pH of resulting aqueous polymer dispersion was between 4.5 and 5, after 14 days storage at room temperature.
  • Table 4 shows the performance test results of Examples 1-9 and Comparative Examples C1-C3
  • the product prepared in accordance with Comparative Example C3 was demulsified after stored at room temperature for one day and could not be used in actual production.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Adhesives Or Adhesive Processes (AREA)
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Abstract

The present invention relates to the use of an aqueous polymer dispersion for interfacial bonding between polymeric porous materials.

Description

Use of Aqueous Polymer Dispersion for Interfacial Bonding between Polymeric Porous Materials Field of the Invention
The present invention relates to the use of an aqueous polymer dispersion for interfacial bonding between polymeric porous materials.
Background of the Invention
US6624243B2 discloses an aqueous polymer dispersion prepared by the polymerization of polymerizable monomers of silanes, vinyl esters, epoxy compounds and 1, 3 dicarbonyl compounds. The aqueous dispersion can improve the scratch resistance of wall paints.
US6863985B2 discloses an aqueous polymer dispersion obtained by the polymerization of polymerizable monomers of silanes, silicone fluids, vinyl esters and epoxy compounds. The dispersion can provide strong water resistance and good water vapor permeability, and can therefore be used especially in exterior paints.
WO2014071550A1 describes an aqueous polymer dispersion for textile lamination. The said polymer is obtained by the polymerization of polymerizable monomers of vinyl acetate-ethylene and polyurethanes. According to the testing method for wet peeling strength disclosed therein, the wet peeling strength of said aqueous polymer dispersion-bonded product is from 6 to 8 N, which is obtained from a sample after it is laminated at 160℃ for 6 seconds, cures at 180℃ for 2 minutes and then is immersed in cold water for 0.5 hour.
CN102869828B discloses a carpet coating composition comprising an interpolymer prepared by the emulsion polymerization of vinyl acetate monomer, ethylene and an unsaturated silane co-monomer which is effective to alter interpolymer molecular weight, branching and/or flow properties such that a film formed from said interpolymer exhibits an elongation value of less than about 125％at 110 ℃.
Summary of the Invention
The present invention discloses a use of an aqueous polymer dispersion to improve the water resistance of interfacial bond between polymeric porous materials, wherein said polymer is obtained by the polymerization of a composition comprising components:
A –one or more monomers, selected from the group consisting of Vinyl esters of unbranched or branched alkylcarboxylic acid having 1 to 15 carbon atoms, vinyl aromatics, olefins, diolefins and vinyl halides；
B –a polymerizable, hydrolysable silicon-containing compound, selected from among unsaturated hydrolyzable vinyl organosilicon compounds；
C –a polymerizable anionic emulsifier； and
optionally D –a vinyl-modified epoxy compound；
wherein the interfacial bonding between polymeric porous materials is that between the same or different materials selected from among fiber textile materials and polymeric foamed materials, preferably that between the same or different members selected from the group consisting of synthetic fiber textile materials, synthetic fiber non-woven materials, natural fiber textile materials, natural fiber non-woven materials, regenerated cellulose materials, ethylene-vinyl acetate (EVA) copolymer sponges and polyurethane sponges.
According to the use as described above, wherein the improvement of water resistance is such that the following conditions are satisfied: the wet peeling strength retention, i.e. the ratio of wet peeling strength to dry peeling strength, is equal to or greater than 0.5 as tested according to ST-4 and ST-3.
According to the use as described above, wherein the improvement of water resistance is that the wet peeling strength according to ST-4 is equal to or greater than 30N/inch.
Composite products are obtained in such a way that polymeric porous materials are interfacially bonded. Some of them often come into contact with water during use, or frequently need to be cleaned. Use fields of these composites include, for example,  shoe liners, shoe inserts and sportswear. Composite products with poor water resistance are prone to degumming in contact with water, that is, interface debonding, leading to a short service life.
According to the use as described above, the interfacial bonding between polymeric porous materials is preferably the lamination of a fiber textile material onto a polymeric foamed material.
According to the use as described above, the interfacial bonding between polymeric porous materials is preferably that between polyester or acrylic or cotton textile materials and flat EVA ethylene-vinyl acetate copolymer sponges.
According to the use as described above, the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded, the resulting product being exposed to a heat source for a period of time.
According to the use as described above, uses in carpet area are excluded. Most conventional carpets comprise a primary backing with yarn tufts in the form of cut or uncut loops extending upwardly from the backing to form a pile surface. In the case of tufted carpets, the yarn is inserted into a primary backing by tufting needles and a pre-coat or binder is applied thereto. In the case of non-tufted or bonded pile carpets, the fibers are embedded and actually held in place by the binder composition.
According to the use as described above, the interfacial bonding between polymeric porous materials does not include the production of polymeric porous materials themselves using a binder, which mainly refers to the bonding together of fibrous polymer materials less than 5 mm in diameter. For example, in the process of manufacturing non-woven, a binder is used to form non-woven fabrics by bonding together the fibrous materials such as wood pulp fibers, rayon, cottons, wools and acetate fibers； or in the process of paper making, a binder is used to form paper webs, papers or cardboards by bonding pulp fibers together.
According to the use as described above, the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded, the resulting product being exposed to a heat source, at between 150 and 200℃, for a period of time between 25 and 120 seconds to complete the drying step； or the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded, the resulting product being exposed to a heat source, at between 100 and 110℃, for a period of time between 20 and 30 minutes to complete the drying step.
According to the use as described above, the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded using a roll coater with a certain pressure, and simultaneously completing the drying step therein.
According to the use as described above, after the drying step is completed using the roll coater, no further hot press treatment is required.
According to the use as described above, the coat weight of the aqueous polymer dispersion is between 120 and 210 g/m2.
According to the use as described above, the glass transition temperature (Tg) of the dried product of the aqueous polymer dispersion is between -2℃ and 4℃ as tested according to ST-1. This aqueous polymer dispersion is used for the interfacial bonding between a fiber textile material and a polymeric foamed material, the resultant product being soft to the touch.
According to the use as described above, the aqueous polymer dispersion is an emulsion that is highly stable and has a rate of change in Brookfield viscosity of less than 30 wt％after 14 days of storage at 50℃. Rate of change in Brookfield viscosity refers to the difference between the Brookfield viscosity at day 1 and that at day 14, divided by the Brookfield viscosity at day 1, under the storage condition at 50℃.
According to the use as described above, the Brookfield viscosity of the aqueous polymer dispersion is between 1,500 and 10,000 mPa·s as tested according to ST-2.
When the viscosity of the aqueous polymer dispersion is too low, the coating roller takes up a small amount of glue during the production, leading to a poor bonding effect of the product； while the viscosity of the aqueous polymer dispersion is too high, the coating roller takes up a large amount of glue, leading to excessive coat weight in the product and high consumption of the aqueous polymer dispersion and thus to diseconomy.
According to the use as described above, component A, one or more monomers, is selected from the group consisting of vinyl esters, ethylene, vinyl chloride and acrylates； more preferably component A is vinyl acetate and ethylene.
According to the use as described above, component C, a polymerisable anionic emulsifier, is an unsaturated alkylsulfonate, preferably sodium vinylsulfonate, 1-allyloxy-2-hydroylpropyl sulfonate, 2-acrylamido-2-methyipropanesulfonate sodium, more preferably sodium vinylsulfonate.
According to the use as described above, the dry material weight ratio of component B, a polymerizable, hydrolyzable silicon-containing compound, to component C, a polymerizable anionic emulsifier, ranges from 1 to 2.
According to the use as described above, the dry material weight ratio of component B, a polymerizable, hydrolyzable silicon-containing compound, to component D, a vinyl-modified epoxy compound, ranges from 0.5 to 0.7.
The composite prepared according to the use described above has a wet peeling strength retention, i.e. the ratio of wet peeling strength to dry peeling strength, equal to or greater than 0.5 as tested according to ST-4 and ST-3.
The composite prepared according to the use described above has a wet peeling strength equal to or greater than 30 N/inch and a wet peeling strength retention equal to or greater than 0.5, both as tested according to ST-4. This aqueous polymer dispersion is used for the interfacial bonding between a fiber textile material and a polymeric foamed material, the resultant product having good water resistance.
The aqueous polymer dispersion in the invention is used for interfacial bonding between polymeric porous materials, wherein the polymer is obtained by the polymerization of a composition comprising components A-D.
Component A, one or more monomers, is selected from the group consisting of Vinyl esters of unbranched or branched alkylcarboxylic acid having 1 to 15 carbon atoms, vinyl aromatics, olefins, diolefins and vinyl halides.
Preferred Vinyl esters of unbranched or branched alkylcarboxylic acid having 1 to 15 carbon atoms are selected from the group of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of α-branched monocarboxylic acids having up to 10 carbon atoms, for example VeoVa 9 or VeoVa 10, wherein vinyl acetate is particularly preferred.
Suitable comonomers, i.e. methacrylates or acrylates, are the eaters of unbranched or branched alcohols having 1 to 15 atoms, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate and norbornyl acrylate, wherein preference is given to methyl acrylate, methyl methacrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
The said component A can also be polymerized to form copolymers of vinyl acetate and ethylene, or copolymers of vinyl acetate and ethylene and one or more other vinyl monomers, such as vinyl acetate-ethylene-acrylate copolymers, vinyl acetate-ethylene-vinyl chloride copolymers.
Component B, a polymerizable, hydrolyzable silicon-containing compound, is preferably selected from among unsaturated hydrolyzable vinyl organosilicon compounds, and is more preferably one or more compounds selected from the group consisting of vinyltrimethoxysilane, vinyldimethoxymethylsilane, vinylmethoxydimethyl-silane, vinyltriethoxysilane, vinyldiethoxymethylsilane, vinylethoxydimethylsilane  vinyltris (methylethoxy) silane, vinyltris (methylisopropoxy) silane, 3-methacryloxypropyl-trimethoxysilane and 3-methacryloxypropyltriethoxysilane.
The most preferred component B is vinyltrimethoxysilane and/or vinyltriethoxy-silane.
Component C, a polymerizable anionic emulsifier, is selected from among unsaturated alkylsulfonates, preferably sodium vinylsulfonate, 1-allyloxy-2-hydroylpropyl sulfonate, 2-acrylamido-2-methyipropanesulfonate sodium, more preferably sodium vinylsulfonate.
The optional component D, a vinyl-modified epoxy compound, is selected from among glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, vinyl glycidyl ether, vinyl cyclohexene dioxide.
The polymers are prepared by the solution polymerization process, emulsion polymerization process or suspension polymerization process, preferably by the emulsion polymerization process, in which the polymerization temperature is generally from 20℃ to 100℃, preferably from 45℃ to 80℃. The polymerization of gaseous monomers, such as ethylene, 1, 3-butadiene or vinyl chloride, can also be carried out generally in the range of from 5 bar to 100 bar abs. The pH range desired for the polymerization, which is in general between 2.5 and 10, preferably 3 and 8, can be established in a known manner by acids, bases or customary buffer salts, such as alkali metal phosphates or alkali metal carbonates.
The polymerization is initiated by a water-soluble or monomer-soluble initiator or redox initiator combinations customary for emulsion polymerization or suspension polymerization. Examples of water-soluble initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, tert-Butyl peroxypivalate, and azobisisobutyronitrile. These initiators are generally used in an amount of 0.01 to 3％by weight in each case based on the total dry weight of the monomers.
As redox initiators, use is made of combinations of the initiators above-mentioned in combination with reducing agents. Suitable reducing agents are the sulfites or bisulfites of alkali metals/ammonium, derivatives of sulfoxylic acid of alkali metals/ammonium, or sulfinates of alkali metals/ammonium. The amount of said reducing agent is generally from 0.01 to 3 ％by weight in each case based on the total dry weight of the monomers of Component A.
To control the molecular weight, regulating substances can be used during the polymerization. If regulators are used, they are usually employed in amounts of from 0.01 to 5.0％by weight, based on the total dry weight of the monomers of Component A, and are introduced separately or premixed with reaction components. Examples of such substances are n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptopropionic acid, methyl mercaptopropionate, isopropanol and acetaldehyde.
Suitable protective colloids for the polymerization are polyvinyl alcohols； polyvinyl acetals； polyvinylpyrrolidones； polysaccharides in water-soluble form, e.g. starches (amylose and amylopectin) , celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives, dextrins and cyclodextrins.
The polymerization can be carried out successively or continuously.
After conclusion of the polymerization, an post-polymerization can be carried out to remove residual monomers using known methods, in general by means of an post-polymerization initiated by a redox catalyst. Volatile residual monomers can also be removed by means of distillation, preferably under reduced pressure, and, if appropriate, with inert entrainer gases such as air, nitrogen or steam being passed through or over the polymerization mixture. The aqueous polymer dispersions obtainable in this way have a solids content of from 40 to 70％by weight.
Protective colloids (used as spray additives) , defoamers and anti-caking agents can be added to the aqueous polymer dispersions herein for subsequent preparation of water-redispersible polymer powders by means of a traditional process: fluidized-bed drying, freeze drying or spray drying.
Sample Preparation and Test Method
Sample preparation and method ST-1 for glass transition temperature measurement:
sample a certain amount of the aqueous polymer dispersion and dry at 25℃overnight and then let stand in a vacuum oven at 40℃ for 24 hours to obtain an dried product of the aqueous polymer dispersion.
Take 8-15 mg of the dried product and heat from -80℃ to 100℃ at a heating rate of 10 K/min using NETZSCH F203 analyzer in a closed sample cell in protective nitrogen atmosphere, according to ISO11357-1 2014, to determine the glass transition temperature (Tg) of the dried product of the aqueous polymer dispersion.
Method ST-2 for viscosity inspection:
The viscosity of the sample is determined with a Brookfield RV/DV rotational viscometer according to GB/T 11175-2002 using spindle No. 4 at 20 rpm at 25℃.
Lab-scale sample preparation method for peeling strength test:
Cut a piece of white cotton fabric to size 20cm × 35 cm in reference to the test method improved as per ISO11339-2010. Lay the fabric on the glass, the upper and lower ends being fixed with 1.8cm wide 3M electrical tape. Spread the aqueous polymer dispersion over the white fabric using a doctor blade, scraped tight with a 40-μm scraper bar, and after 1 minute, spread another layer of aqueous polymer dispersion on the coated fabric, scraped tight with a 50-μm scraper bar. After 1 minute, fold the fabric in half lengthwise and press it twice with a 2-kg pressure roller. Place the fabric sample in an oven for heat treatment at 105℃ for 30 minutes before removing and cutting it into pieces of 2.54cm × 35cm dry fabrics.
Method ST-3 for dry peeling strength test:
A dry fabric sample mentioned above is tested for 180° peeling strength in reference to the method shown in Figure 1 of ISO11339-2010 on Shandong Labthink XLW (G) -PC smart electronic tensile tester. The dry sample, with its width remaining 25.4 mm (1 inch) , is vertically stretched at a speed of 100 mm/min for a distance of 40 mm. The stretches up to 2 mm at both the beginning and end of the test are not taken into account.
Method ST-4 for wet peeling strength test:
Preparation of wet fabric samples: A dry fabric sample mentioned above is soaked in water at 25℃ for 1 hour and then taken out.
The wet fabric sample is tested for 180° peeling strength in reference to the method shown in Figure 1 of ISO11339-2010 on Shandong Labthink XLW (G) -PC smart electronic tensile tester.
Industrial-scale sample preparation method: by an industrial roll coater
Roller length: L ＝ 6.28 m
Heating temperature: T ＝ 160℃
Heating time: 15 ～ 30 s
Coat weight: 120 g/m2
Figure PCTCN2017073909-appb-000001
 EP706K, a commercially available product from Wacker Chemie AG, which is not the aqueous polymer dispersion as described in the claims of the present invention, is used as the binder to select a lab-scale sample preparation method for peeling strength closest to the industrial-scale one. From the test data in Table 1, it can be seen that the lab-scale preparation method for peeling strength test that involves heat treatment at 105℃ for 30 minutes is virtually equivalent to its industrial-scale counterpart.
Figure PCTCN2017073909-appb-000002
Examples
The aqueous polymer dispersions in Examples 1 to 9 and Comparative Examples C1 to C3 were prepared according to the basic formulation in Table 2. The basic formulation in Table 2 contains the type of monomers, amount of monomers, type of protective colloid, initiator system, initial charge and subsequent feed of each raw material, and the like.
The amounts in the present invention are, unless otherwise specified, in parts by weight.
In Tables 2 and 3, unless otherwise specified, the part by weight of each raw material are calculated on the basis of 100 parts by weight of the vinyl acetate monomer as a reference.
In Tables 2 and 3, the concentration of a solution is the weight of solute divided by the weight of solution, in the form of percent by weight.
Mersolat H95, a mixture of primarily secondary sodium alkyl sulfonate comprising saturated alkyl groups with an average chain length of C15, is supplied by Rhein Chemie；
Figure PCTCN2017073909-appb-000003
 XL 10, vinyltrimethoxysilane, is supplied by Wacker Chemie AG；
GMA, glycidyl methacrylate, is supplied by Sinopharm Chemical Reagent；
Genapol 3214, tridecyl alcohol ethoxylate, having an alkyl chain length of about C13 and an HLB value of about 17, is supplied by Clariant；
RHODASURF 6530, aliphatic alcohol ethoxylate with an HLB of about 17, is supplied by Rhodia Solvay Group；
Polyvinyl Alcohol 25/88, having an alcoholysis degree of 88 wt％, 4 wt％aqueous solution of which has a viscosity of 25 mPa·s at 20℃ according to DIN 53015, is prepared into a 10.3 wt％aqueous solution before use.
Foamaster 223, a mineral oil-based defoamer, supplied by BASF.
Figure PCTCN2017073909-appb-000004
 EP 706K is an ethylene-vinyl acetate aqueous polymer dispersion available from Wacker Chemie AG.
Table 2 Basic Formulation
Figure PCTCN2017073909-appb-000005
* The amount of ethylene used in Table 2 refers to the amount of ethylene gas fed in each example.
The raw materials primarily adjusted in Examples 1-9 and Comparative Examples C1-C3 were referred to Table 3. The procedure was similar to that of Example 1.
Table 3
Figure PCTCN2017073909-appb-000006
Figure PCTCN2017073909-appb-000007
Example 1
A premix of 584.43 g of deionized water, 443 g of 10.3 wt％polyvinyl alcohol 25/88, 13 g of Mersolate H95, 110.77 g of 65 wt％Genopol 3214, 20.1 g of 25 wt％sodium vinylsulfonate, 2.78 g of 2 wt％EDTA-Na and 20.3 g of sodium acetate were added into a 5-liter reactor. The premix was mixed well and its pH was adjusted to 5 with acetic acid.
The reactor was heated to 70℃, into which 252 g of vinyl acetate and 400 g of ethylene were added, and the pressure in the reactor was maintained below 45 bar.
The temperature was raised to 70℃ while the aqueous solutions of 1.25 wt％ammonium persulfate and 5 wt％aqueous 2-hydroxy-2-sulfinic acid disodium acetate were added dropwise with a pump to initiate reaction and the dropwise addition continued until the reaction was completed. After the initiation reaction, 2, 265.6 g of vinyl acetate was added at a rate of 12.6 g/min, and a mixed solution of 318.76 g of deionized water, 115 g of 10.3 wt％Polyvinyl Alcohol 25/88, 7.12 g of 
Figure PCTCN2017073909-appb-000008
 XL 10 and 12.2 g of glycidyl methacrylate were added at a rate of 2.5 g/min.
After reaction for 4 hours, the mixture was transferred to a degassing tank, where 1 g of defoamer Foamaster 223 was added, and after degassing for 30 minutes, the aqueous polymer dispersion was obtained.
The pH of resulting aqueous polymer dispersion was between 4.5 and 5, after 14 days storage at room temperature.
Table 4 shows the performance test results of Examples 1-9 and Comparative Examples C1-C3
Table 4
Figure PCTCN2017073909-appb-000009
The product prepared in accordance with Comparative Example C3 was demulsified after stored at room temperature for one day and could not be used in actual production.

Claims (12)

  1. A use of an aqueous polymer dispersion to improve the water resistance of interfacial bond between polymeric porous materials, wherein said polymer is obtained by the polymerization of a composition comprising components:
    A – one or more monomers, selected from the group consisting of Vinyl esters of unbranched or branched alkylcarboxylic acid having 1 to 15 carbon atoms, vinyl aromatics, olefins, diolefins and vinyl halides；
    B – a polymerizable, hydrolysable silicon-containing compound, selected from among unsaturated hydrolyzable vinyl organosilicon compounds；
    C – a polymerizable anionic emulsifier； and
    optionally D – a vinyl-modified epoxy compound；
    wherein the interfacial bonding between polymeric porous materials is that between the same or different materials selected from among fiber textile materials and polymeric foamed materials, preferably that between the same or different members selected from the group consisting of synthetic fiber textile materials, synthetic fiber non-woven materials, natural fiber textile materials, natural fiber non-woven materials, regenerated cellulose materials, ethylene-vinyl acetate (EVA) copolymer sponges and polyurethane sponges.
  2. The use according to Claim 1, wherein the improvement of water resistance is such that the following conditions are satisfied: the wet peeling strength retention, i.e.the ratio of wet peeling strength to dry peeling strength, is equal to or greater than 0.5 as tested according to ST-4 and ST-3.
  3. The use according to Claim 1 or 2, wherein the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded, the resulting product being exposed to a heat source, at between 150 and 200℃, for a period of time between 25 and 120 seconds to complete the drying step； or the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded, the resulting product being exposed to a heat source, at between 100 and 110℃, for a period of time between 20 and 30 minutes to complete the drying step.
  4. The use according to Claim 1 or 2, wherein the aqueous polymer dispersion is applied onto the surfaces of the polymeric porous materials to be bonded using a roll coater with a certain pressure, and simultaneously completing the drying step therein.
  5. The use according to Claim 1 or 2 or 4, wherein the glass transition temperature (Tg) of the dried product of the aqueous polymer dispersion is between -2℃ and 4℃ as tested according to ST-1.
  6. The use according to Claim 1 or 2 or 4, wherein the Brookfield viscosity of the aqueous polymer dispersion is between 1,500 and 10,000 mPa·s as tested according to ST-2, a rate of change in Brookfield viscosity of less than 30 wt％after 14 days of storage at 50℃.
  7. The use according to Claim 1 or 2 or 4, wherein component A, one or more monomers, is selected from the group consisting of vinyl esters, ethylene, vinyl chloride and acrylates； more preferably component A is vinyl acetate and ethylene.
  8. The use according to Claim 1 or 2 or 4, wherein component C, a polymerisable anionic emulsifier, is an unsaturated alkylsulfonate, preferably preferably sodium vinylsulfonate, 1-allyloxy-2-hydroylpropyl sulfonate, 2-acrylamido-2-methyipropanesulfonate sodium, more preferably sodium vinylsulfonate.
  9. The use according to Claim 1 or 2 or 4, wherein the dry material weight ratio of component B, a polymerizable, hydrolyzable silicon-containing compound, to component C, a polymerizable anionic emulsifier, ranges from 1 to 2.
  10. The use according to Claim 9, wherein the dry material weight ratio of component B, a polymerizable, hydrolyzable silicon-containing compound, to component D, a vinyl-modified epoxy compound, ranges from 0.5 to 0.7.
  11. The composite prepared according to the use described in claim 1-10, having a wet peeling strength retention, i.e.the ratio of wet peeling strength to dry peeling strength, equal to or greater than 0.5 as tested according to ST-4 and ST-3.
  12. The composite prepared according to claim 11, having a wet peeling strength equal to or greater than 30 N/inch and a wet peeling strength retention equal to or greater than 0.5, both as tested according to ST-4.
PCT/CN2017/073909 2017-02-17 2017-02-17 Use of aqueous polymer dispersion for interfacial bonding between polymeric porous materials WO2018148929A1 (en)

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BR112019017015A BR112019017015A2 (en) 2017-02-17 2017-02-17 use of aqueous polymer dispersion for interfacial bonding between porous polymeric materials
PCT/CN2017/073909 WO2018148929A1 (en) 2017-02-17 2017-02-17 Use of aqueous polymer dispersion for interfacial bonding between polymeric porous materials
CN201780084599.3A CN110461888A (en) 2017-02-17 2017-02-17 The purposes that aqueous polymer dispersion is bonded in high-molecular porous material interface
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WO2023016627A1 (en) 2021-08-10 2023-02-16 Wacker Chemie Ag Construction material dry mixes containing solid vinyl ester resins

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