CN114829516A - Composition and preparation method and application thereof - Google Patents

Composition and preparation method and application thereof Download PDF

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Publication number
CN114829516A
CN114829516A CN202080078975.XA CN202080078975A CN114829516A CN 114829516 A CN114829516 A CN 114829516A CN 202080078975 A CN202080078975 A CN 202080078975A CN 114829516 A CN114829516 A CN 114829516A
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China
Prior art keywords
composition
substrate
article
bis
adsorbent
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CN202080078975.XA
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Chinese (zh)
Inventor
朱英丹
金晨
谭淼
赵东波
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Covestro Deutschland AG
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Covestro Intellectual Property GmbH and Co KG
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Priority claimed from CN201911111586.8A external-priority patent/CN112795298A/en
Priority claimed from EP20151335.5A external-priority patent/EP3848423A1/en
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of CN114829516A publication Critical patent/CN114829516A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/324—Alkali metal phosphate
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention relates to a composition, in particular a low VOC, low odor composition, to the preparation and use of the composition, to a two-component system comprising the composition and use thereof, and to articles coated or bonded using the composition or the two-component system. The composition comprises at least one aqueous polyurethane dispersion, at least one adsorbent and at least one chelating agent; the adsorbent is one or more of the following: hydrophilic molecular sieves and amphiphilic molecular sieves; the amount of the aqueous polyurethane dispersion is 50 wt% to 99 wt%, the amount of the adsorbent is 0.1 wt% to 3 wt%, and the amount of the chelating agent is 0.05 wt% to 1 wt%, all based on 100 wt% of the composition.

Description

Composition and preparation method and application thereof
Technical Field
The present invention relates to a composition, the preparation and use of the composition, a two-component system comprising the composition and its use, and articles coated or bonded using the composition or the two-component system.
Background
Along with the improvement of living standard of people and the popularization of automobile domestication, people pay more and more attention to the quality of air in the automobile. The evaluation of the air quality in the vehicle is mainly two aspects, namely the content of volatile organic compounds (VOC for short) in the vehicle and the odor in the vehicle. According to statistics, the problem that the VOC content exceeds the standard exists in nearly 90% of automobiles according to the indoor air quality standard. The excessive content of VOC can cause the immune level disorder of human body, affect the function of nervous system, cause symptoms such as dizziness, headache, somnolence, weakness and the like, affect the digestive system, cause inappetence, nausea and the like, seriously damage liver and hematopoietic system and threaten the health of human. In the PP100 (problem per hundred vehicles) list of new vehicle quality research (IQS), "unpleasant odors/odors" have been high in recent years, and although these odors are not necessarily threatening human health, consumers often do not want odors present in vehicles. Sources of VOC and odor in vehicles are various, such as seat foam, fabric coating, plastic upholstery, adhesives, and the like.
CN 104151540A discloses a method for preparing high-resilience polyurethane foam with low VOC content by using polyether polyol, which is characterized in that a polyol compound is used as an initiator, and an alkali metal hydroxide is used as a catalyst to react under the pressure of 0-0.6 MPa and the temperature of 60-140 ℃, so that the polyurethane foam is polymerized with an epoxy compound step by step and then is obtained by special post-treatment; wherein, the mass of the polyalcohol compounds accounts for 10 to 19.5 percent of the total feeding amount, the mass of the epoxy compounds accounts for 80 to 89.5 percent of the total feeding amount, and the mass of the alkali metal hydroxide accounts for 0.2 to 0.5 percent of the total feeding amount.
CN 104592878B discloses an environment-friendly water-based paint and a preparation method thereof, wherein the preparation method comprises the following steps: the water-based resin coating comprises a water-based resin dispersion, water, composite anion powder, an anion additive, a film forming auxiliary agent, a defoaming agent, a thickening agent, a dispersing agent and a pH regulator. The composite anion powder consists of crystal salt, nano silicon dioxide, nano titanium dioxide phosphate and nano zinc dioxide. The nanometer silicon dioxide, the nanometer titanium dioxide phosphate and the nanometer zinc dioxide are used as photocatalyst materials, and can effectively degrade harmful gases such as formaldehyde and the like in the air under illumination to produce bovine superoxide anion free radicals and associated negative oxygen ions.
The aqueous dispersion system has very low VOC content, and can effectively solve the problem that the VOC content in the vehicle exceeds the standard. And the aqueous dispersion system has low odor, and can solve the problem of unpleasant odor in the vehicle. However, the demand of low odor in the vehicle is becoming more severe for consumers, and the existing aqueous dispersion systems are difficult to satisfy.
CN 103980814A discloses a polyurethane odorless matte wear-resistant finish paint and a preparation method thereof, which is prepared by a main agent, a curing agent and a diluent according to the weight ratio of 1-1.4:0.5-0.7: 0.7-1.2; the specific ratio of the main agent to the curing agent is 1-1.4:0.5-0.7, so that hydroxyl in the main agent and isocyanate in the curing agent are fully and completely reacted, the optimal molar ratio of the hydroxyl to the isocyanate is 2:1, the hydroxyl and the isocyanate are in the optimal ratio in the construction process, and the hydroxyl and the isocyanate are completely reacted to generate stable polyurethane bonds, so that the odor purification effect is achieved, and the pungent odor caused by the raw materials is eliminated.
CN 106009271 a discloses a modified polypropylene composition, which comprises the following blended components: polypropylene, ethylene propylene grafted maleic anhydride copolymer, reinforcing filler, deodorant, antioxidant and processing aid. Wherein the deodorant is an organic salt and/or silicate with micropores, and the silicate with micropores is at least one of sodium silicate salt, aluminum silicate salt, magnesium silicate salt and calcium silicate salt; the specific surface area of the silicate with micropores is 200-600m 2 /g, preferably 300- 2 (ii)/g; the pores of the microporous silicate have an average pore diameter of 0.2 to 2nm, preferably 0.1 to lnm.
It is desirable to develop a new low VOC, low odor composition that further reduces odor over existing products to meet the demanding odor applications, such as automotive interior coatings or automotive interior binders.
Disclosure of Invention
The object of the present invention is to provide a composition, in particular a low VOC, low odor composition, the preparation and use of the composition, a two-component system comprising the composition and its use, and articles coated or bonded using the composition or the two-component system.
The composition according to the invention comprises at least one aqueous polyurethane dispersion, at least one adsorbent and at least one chelating agent; the adsorbent is one or more of the following: hydrophilic molecular sieves and amphiphilic molecular sieves; the amount of the aqueous polyurethane dispersion is 50 wt% to 99 wt%, the amount of the adsorbent is 0.1 wt% to 3 wt%, and the amount of the chelating agent is 0.05 wt% to 1 wt%, all based on 100 wt% of the composition.
According to one aspect of the present invention, there is provided a method of preparing a composition provided herein, comprising the steps of: the aqueous polyurethane dispersion, the adsorbent and the chelating agent are mixed in any manner.
According to a further aspect of the present invention there is provided the use of a composition provided according to the present invention for the preparation of an article.
According to a further aspect of the present invention, there is provided an article comprising a substrate and a coating formed by applying a composition provided according to the present invention to the substrate.
According to yet another aspect of the present invention, there is provided a method of manufacturing a coated article, comprising the steps of: the compositions provided according to the present invention are applied to a substrate surface and subsequently cured.
According to yet another aspect of the present invention, there is provided a method of manufacturing a bonded article comprising the steps of:
i. applying a composition provided according to the present invention to at least one surface of a substrate; and
contacting the surface of the substrate treated in step i with the surface of the substrate itself or of an additional substrate to obtain the bonded article.
According to a further aspect of the present invention there is provided a two-component system comprising an a-component which is a composition provided according to the present invention and a B-component which is a cross-linking agent.
According to a further aspect of the present invention there is provided the use of a two-component system provided according to the present invention for the preparation of an article.
According to yet another aspect of the present invention, there is provided an article comprising a substrate and a coating formed by applying the two-component system provided according to the present invention to the substrate.
The composition disclosed by the invention is an aqueous composition, has the characteristic of low VOC (volatile organic compounds), has the advantage of low odor, and can meet the application fields with strict requirements on VOC and odor, such as automobile interiors, indoor homes and the like.
Detailed Description
The invention provides a composition comprising at least one aqueous polyurethane dispersion, at least one adsorbent, and at least one chelating agent; the adsorbent is one or more of the following: hydrophilic molecular sieves and amphiphilic molecular sieves; the amount of the aqueous polyurethane dispersion is 50 wt% to 99 wt%, the amount of the adsorbent is 0.1 wt% to 3 wt%, and the amount of the chelating agent is 0.05 wt% to 1 wt%, all based on 100 wt% of the composition. The invention also provides a preparation method and application of the composition, in particular application in the fields of coatings and adhesives, a two-component system of the composition and application thereof, and an article coated or bonded by using the composition or the two-component system.
The term "cure" as used herein refers to the process of a composition or two-component system containing a composition from a liquid to a solid.
As used herein, the term "coating" refers to a chemical substance that can be applied to the surface of an object by various application processes to form a strong, continuous solid coating.
As used herein, the term "adhesive" refers to a chemical substance that can be applied to the surface of an object by different application processes, form a coating on the object itself or the surface of one object to another, and bond the object itself or the surface of one object to another, and is also used as a synonym for adhesive and/or sealant and/or adhesive.
The term "polyurethane polymer" as used herein refers to polyurethaneurea polymers and/or polyurethane polyureas polymers and/or polyurea polymers and/or polythiourethane polymers.
The term "aqueous polyurethane dispersion" as used herein refers to an aqueous polyurethaneurea dispersion and/or an aqueous polyurethane polyurea dispersion and/or an aqueous polythiourethane dispersion.
The term "polyurethane polymer of linear structure" as used herein refers to a polyurethane polymer having a linear structure, which is free of branched structures.
The term "emulsifier" as used herein refers to a compound comprising emulsifying groups or latent emulsifying groups.
The term "isocyanate-reactive group" as used herein means a group containing Zerewitinov-activityThe group of hydrogens, Zerewitinov-active hydrogens, is defined with reference to Rompp's Chemical Dictionary (Rommp Chemie Lexikon), 10th ed., Georg Thieme Verlag Stuttgart, 1996. In general, zerewitinov-active hydrogen-containing radicals are understood in the art to mean hydroxyl (OH), amino (NH) x ) And a thiol group (SH).
The term "chelating agent" as used herein refers to a compound capable of forming a stable complex with metal ions, in particular heavy metal ions or transition metal ions.
The term "amphiphilic" as used herein refers to a hydrophilic oleophilic type.
Composition comprising a metal oxide and a metal oxide
The amount of organic solvent in the composition is preferably not more than 5 wt%, most preferably not more than 0.5 wt%, based on 100 wt% of the composition.
The composition is aqueous, and the composition has the characteristic of low VOC.
The composition is preferably a coating or a binder, most preferably an interior coating or an interior binder.
Aqueous polyurethane dispersions
The amount of the aqueous polyurethane dispersion is preferably 90% to 99% by weight, based on the amount of the composition being 100% by weight;
the solids content of the aqueous polyurethane dispersion is preferably from 30% to 70% by weight, based on 100% by weight of the aqueous polyurethane dispersion.
The amount of residual organic solvent in the aqueous polyurethane dispersion is preferably less than 1.0% by weight, based on 100% by weight of the solids content of the aqueous polyurethane dispersion.
The aqueous polyurethane dispersion may be added to the composition directly as a dispersion or may be added to the composition as a polyurethane polymer and water and mixed to form a dispersion.
The aqueous polyurethane dispersion comprises a polyurethane polymer and water, wherein the polyurethane polymer is preferably obtained by reacting a system comprising a polyisocyanate, a polyester polyol and an emulsifier.
The polyurethane polymer is preferably a polyurethane polymer of linear structure.
Polyisocyanates
The functionality of the polyisocyanate is preferably not less than 2, and further preferably 2 to 4.
The amount of the polyisocyanate is preferably 5% to 70% by weight, further preferably 5% to 40% by weight, still further preferably 5% to 35% by weight, most preferably 10% to 30% by weight, based on 100% by weight of the system for preparing the polyurethane polymer.
The polyisocyanate is preferably one or more of the following: aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and their derivatives with iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea and/or carbodiimide groups.
The aliphatic polyisocyanate is preferably one or more of the following: 1, 6-hexamethylene diisocyanate, 2-dimethylpentanedione diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, butene diisocyanate, 1, 3-butadiene-1, 4-diisocyanate, 2, 4, 4-trimethyl-1, 6-hexamethylene diisocyanate, 1, 6, 11-undecane triisocyanate, 1, 3, 6-hexamethylene triisocyanate, 1, 8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine methyl diisocyanate, lysine triisocyanate, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, butene diisocyanate, 2, 4-dimethylbutene diisocyanate, 2, 4-hexamethylene diisocyanate, 2-dimethylene diisocyanate, 2-diisocyanate, 4-hexamethylene diisocyanate, 1, 6-hexamethylene triisocyanate, 6-hexamethylene diisocyanate, 1, 8-diisocyanate, 4-hexamethylene diisocyanate, 6-hexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 4-hexamethylene diisocyanate, 1, 6-diisocyanate, 6-hexamethylene diisocyanate, 1, 4-diisocyanato, 4-diisocyanat, bis (diisocyanato, bis (isocyanato-bis (isocyanato) carbonate), bis (isocyanato) carbonate), bis (isocyanate), bis (isocyanate), bis (diisocyanate, bis (isocyanato) ether, bis (isocyanate), bis (isocyanato-bis (isocyanate), bis (isocyanato) ether, bis (isocyanate), bis (isocyanate), bis (isocyanato) sulfide, bis (isocyanate, bis (isocyanato) ether, bis (isocyanate), bis (isocyanate), bis (isocyanato) sulfide, bis (isocyanate, Bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1, 5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1, 2, 3-tris (isocyanatomethylthio) propane, 1, 2, 3-tris (isocyanatoethylthio) propane, 3, 5-dithia-1, 2, 6, 7-heptanediisocyanate, 2, 6-diisocyanatomethyl-3, 5-dithia-1, 7-heptanediisocyanate, bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatoethylthio) ethane, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) ethane, 1, 5-dithia-1, 2, 6, 7-heptanediisocyanate, 2, 6-diisocyanatomethyl-3, 5-dithio-1, 7-heptane, 2, 5-diisocyanatomethylthiophene, isocyanatoethylthio-2, 6-dithia-1, 8-octane diisocyanate, thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), dithiobis (2-isothiocyanatoethane), hexamethylene diisocyanate, and isophorone diisocyanate, most preferably one or more of the following: 1, 6-hexamethylene diisocyanate and hexamethylene diisocyanate.
The cycloaliphatic polyisocyanate is preferably one or more of the following: 2, 5-bis (isocyanatomethyl) -bicyclo [2.2.1]Heptane, 2, 6-bis (isocyanatomethyl) -bicyclo [2.2.1]Heptane, bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 2, 5-diisocyanato tetrahydrothiophene, 2, 5-diisocyanatomethyltetrahydrothiophene, 3, 4-diisocyanatomethyltetrahydrothiophene, 2, 5-diisocyanato-1, 4-dithiane, 2, 5-diisocyanatomethyl-1, 4-dithiane, 4, 5-diisocyanato-1, 3-dithiolane, 4, 5-bis (isocyanatomethyl) -1, 3-dithiolane, 4, 5-diisocyanatomethyl-2-methyl-1, 3-dithiolane, norbornane diisocyanate (NBDI), Xylylene Diisocyanate (XDI), hydrogenated xylylene diisocyanate (H). 6 XDI), 1, 4-cyclohexyl diisocyanate (H) 6 PPDI), 1, 5-Pentanediisocyanate (PDI), m-tetramethylxylylene diisocyanate (m-TMXDI), and cyclohexane diisothiocyanate, most preferably one or more of the following: isophorone diisocyanate and dicyclohexyl diisocyanate.
The aromatic polyisocyanate is preferably one or more of the following: 1, 2-diisocyanatobenzene, 1, 3-diisocyanatobenzene, 1, 4-diisocyanatobenzene, 2, 4-diisocyanatotoluene, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, toluene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanateDiisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4 ' -methylenebis (phenyl isocyanate), 4 ' -methylenebis (2-methylphenyl isocyanate), bibenzyl-4, 4 ' -diisocyanate, bis (isocyanatophenyl) ethylene, bis (isocyanatomethyl) benzene, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α ', α ' -tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene, bis (isocyanatomethyl) naphthalene, bis (isocyanatomethyl) ether, bis (isocyanatoethyl) phthalate, 2, 6-bis (isocyanatomethyl) furan, 2-isocyanatophenyl-4-isocyanatophenyl sulfide, tolylene, and tolylene, and tolylene, tolylene, Bis (4-isocyanatophenyl) sulfide, bis (4-isocyanatomethylphenyl) sulfide, bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-6-isocyanatophenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, bis (4-methoxy-3-isocyanatophenyl) disulfide, 1, 2-diisothiocyanatobenzene, 1, 3-diisothiocyanatobenzene, 1, 4-diisothiocyanatobenzene, 2, 4-diisothiocyanatotoluene, 2, 5-diisothiocyanato-m-xylene, 4, 4 '-methylenebis (phenyl isothiocyanate), 4' -methylenebis (2-methylphenyl isothiocyanate), 4 '-methylenebis (3-methylphenyl isothiocyanate), 4' -diisothiocyanatobenzophenone, 4 '-diisothiocyanato3, 3' -dimethylbenzophenone, bis (4-isothiocyanatophenyl) ether, 1-isothiocyanato-4- [ (2-isothiocyanate) sulfonyl group]Benzene, thiobis (4-isothiocyanatobenzene), sulfonyl (4-isothiocyanatobenzene), hydrogenated toluene diisocyanate (H) 6 TDI), diphenylmethane diisocyanate and dithiobis (4-isothiocyanatobenzene), most preferably one or more of the following: 1, 2-diisocyanatobenzene, 1, 3-diisocyanatobenzene, 1, 4-diisocyanatobenzene, diphenylmethane diisocyanate, and 2, 4-diisocyanatotoluene.
The polyisocyanate may also have isocyanate groups and isothiocyanate groups such as 1-isocyanato-6-isothiocyanatohexane, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3-isocyanato-1-isothiocyanatobenzene, 2-isocyanato-4, 6-diisothiocyanato-1, 3, 5-triazine, 4-isocyanato-4-isothiocyanatophenylthioether and 2-isocyanato-2-isothiocyanatoethyldisulfide.
The polyisocyanate may also be a halogen substituent of the above polyisocyanates, for example a chlorine substituent, a bromine substituent, an alkyl substituent, an alkoxy substituent, a nitro substituent or a silane substituent such as isocyanatopropyltriethoxysilane or isocyanatopropyltrimethoxysilane.
Polyester polyols
The amount of the polyester polyol is preferably 5 to 95% by weight, preferably 10 to 90% by weight, based on 100% by weight of the amount of the system for preparing the polyurethane polymer.
The hydroxyl value of the polyester polyol is preferably 20 to 80.
The polyester polyol is preferably a linear polyester polyol.
The linear polyester polyol or the lightly branched polyester polyol is prepared by comprising the following components: aliphatic, alicyclic or aromatic di-or polycarboxylic acids, such as succinic acid, methylsuccinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, azelaic acid, decanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, malonic acid or trimellitic acid; anhydrides, such as phthalic anhydride, trimellitic anhydride or succinic anhydride or mixtures thereof; and low molecular weight polyols, and optionally higher functional polyols, such as trimethylolpropane, glycerol or pentaerythritol, cycloaliphatic and/or aromatic di-and poly-hydroxy compounds.
Emulsifier
The amount of emulsifier is preferably from 0.1% to 20% by weight, based on 100% by weight of the system for preparing the polyurethane polymer.
The emulsifier preferably comprises at least one isocyanate-reactive group and at least one emulsifying group or latent emulsifying group.
The isocyanate-reactive groups are preferably one or more of the following: hydroxyl, thiol and amino groups.
The emulsifying groups or potential emulsifying groups are preferably one or more of the following: sulfonic acid groups, carboxylic acid groups, tertiary amino groups, and hydrophilic polyethers.
The emulsifier comprising sulfonic acid groups and/or carboxylic acid groups is preferably one or more of the following: diamino compounds comprising sulfonic acid groups and/or carboxylic acid groups and dihydroxy compounds comprising sulfonic acid groups and/or carboxylic acid groups, further preferably one or more of the following: sodium, potassium, lithium, tertiary amine salts of N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -3-aminopropanesulfonic acid, N- (2-aminoethyl) -3-aminopropanesulfonic acid, like carboxylic acids, dimethylolpropionic acid or dimethylolbutyric acid, most preferably one or more of the following: n- (2-aminoethyl) -2-aminoethanesulfonate and dimethylolpropionic acid.
The sulfonic acid or carboxylic acid groups can be used directly in their salt form, such as sulfonates or carboxylates.
The sulfonic acid or carboxylic acid groups can also be obtained by partial or complete addition of neutralizing agents during or after the preparation of the polyurethane polymer.
The neutralizing agent for salt formation is preferably one or more of the following: triethylamine, dimethylcyclohexylamine, ethyldiisopropylamine, ammonia, diethanolamine, triethanolamine, dimethylethanolamine, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, methyldiethanolamine, and aminomethylpropanol, most preferably one or more of the following: triethylamine, dimethylcyclohexylamine and ethyldiisopropylamine.
Organic solvent
The system for preparing the polyurethane polymer may further comprise an organic solvent that is miscible with water but inert to isocyanate groups.
The amount of the organic solvent is preferably 0.001 wt% to 20 wt%, based on 100 wt% of the amount of the system for preparing the polyurethane polymer.
The organic solvent is preferably one or more of the following: acetone, 2-butanone, tetrahydrofuran, xylene, toluene, cyclohexane, butyl acetate, dioxane acetate, methoxypropyl acetate, N-methylpyrrolidone, N-ethylpyrrolidone, acetonitrile, dipropylene glycol dimethyl ether, and solvents containing ether or ester units, most preferably one or more of the following: acetone and 2-butanone.
The organic solvent may be added only at the beginning of the preparation, or may be added in part during the preparation as needed.
Reactive diluent
The system for preparing the polyurethane polymer may further comprise a reactive diluent.
The amount of the reaction diluent is preferably 0.001 wt% to 90 wt%, based on 100 wt% of the amount of the system for preparing the polyurethane polymer.
The reaction diluent is preferably one or more of the following: acrylic acid and acrylic esters.
The aqueous polyurethane dispersion is preferably an anionic aqueous polyurethane dispersion, most preferably one or more of the following: dispercoll U56 and Dispercoll U54.
Adsorbent and process for producing the same
The amount of the adsorbent is preferably 0.5 wt% to 3 wt%, based on 100 wt% of the composition.
The adsorbent is preferably one or more of the following: hydrophilic molecular sieves and amphiphilic molecular sieves.
The average particle size of the hydrophilic molecular sieve and the average particle size of the amphiphilic molecular sieve are respectively and independently 0.1 mu m-10 mu m.
The chemical solvent content of the hydrophilic molecular sieve and the amphiphilic molecular sieve are each independently preferably not more than 0.5 wt%, most preferably without any chemical solvent.
The hydrophilic molecular sieve is preferably MCM 41.
The amphiphilic molecular sieve is preferably Zeoflair 200.
Chelating agents
The amount of the chelating agent is preferably 0.08 wt% to 0.8 wt%, based on 100 wt% of the composition.
The chelating agent is preferably present in the form of a water-soluble salt, satisfying the following conditions: in the water solution of water-soluble salt, when the content of the water-soluble salt is 4.3 x 10 -7 The pH of the aqueous solution at mol/g is greater than 4, preferably greater than 6, most preferably greater than 9.
The solubility of the water-soluble salt in water is preferably not less than 0.15g/100g of water, more preferably not less than 1g/100g of water, most preferably 1g/100g of water to 100g/100g of water, as measured at room temperature of 20 ℃.
The chelating agent is preferably one or more of the following: ethylenediaminetetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate and gluconate, further preferably one or more of the following: ethylenediaminetetraacetate, alkali metal tartrate, alkali metal citrate, alkali metal pyrophosphate, alkali metal tripolyphosphate, alkali metal hexametaphosphate, and alkali metal gluconate; further preferred is one or more of the following: ethylenediaminetetraacetic acid monovalent cation salt, tartaric acid monovalent cation salt, citric acid monovalent cation salt, pyrophosphoric acid monovalent cation salt, tripolyphosphoric acid monovalent cation salt, hexametaphosphoric acid monovalent cation salt, aminotrimethylenephosphonic acid monovalent cation salt, ethylenediaminetetramethylenephosphonic acid monovalent cation salt, diethylenetriaminepentamethylenephosphonic acid monovalent cation salt, and gluconic acid monovalent cation salt, and further preferably one or more of the following: ethylenediaminetetraacetic acid monovalent cation salts, tartaric acid monovalent cation salts, citric acid monovalent cation salts, pyrophosphoric acid monovalent cation salts, tripolyphosphoric acid monovalent cation salts, hexametaphosphoric acid monovalent cation salts, and gluconic acid monovalent cation salts, most preferably one or more of the following: tetrasodium ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, and tetrasodium pyrophosphate.
Stabilizer
The composition may further comprise a stabilizer which is beneficial to reduce hydrolysis of the composition and prolong the pot life of the composition.
The stabilizer is preferably one or more of the following: carbodiimide compounds, epoxy compounds, oxazoline compounds and aziridine compounds.
The content of the stabilizer is preferably 0 to 10% by weight, more preferably 0.5% by weight to 10% by weight, most preferably 0.5 to 2% by weight, based on 100% by weight of the solid component of the composition.
Additive agent
The composition may further comprise an additive.
The additive is preferably one or more of the following: co-binders, thickeners, adhesion promoters, lubricants, wetting additives, dyes, light stabilizers, aging inhibitors, pigments, flow control agents, antistatic agents, UV absorbers, film-forming aids, defoamers and plasticizers.
The amount of the additive may be an amount well known to those skilled in the art.
Aqueous dispersion
The composition may further comprise an aqueous dispersion different from the aqueous polyurethane dispersion, preferably one or more of the following: aqueous polyester dispersions, aqueous polyurethane-polyacrylate dispersions, aqueous polyester-polyacrylate dispersions, alkyd resins, aqueous polyamide/imide dispersions and aqueous polyepoxide dispersions.
The weight ratio of the aqueous dispersion different from the aqueous polyurethane dispersion to the aqueous polyurethane dispersion is preferably between 0.01 and 0.9.
Process for preparing a composition
When the adsorbents are a combination of two or more kinds, each of the adsorbents may be premixed and then mixed with the aqueous polyurethane dispersion and the chelating agent, or each of the adsorbents may be directly mixed with the aqueous polyurethane dispersion and the chelating agent.
The aqueous polyurethane dispersion is preferably obtained from a reaction comprising the following steps:
a. reacting some or all of the polyisocyanate and the polyester polyol to obtain a prepolymer, the reaction being carried out in the presence of or after the optional water-miscible organic solvent which is inert to isocyanate groups to dissolve the prepolymer;
b. reacting the prepolymer, an emulsifier, an optional reaction diluent, a polyisocyanate that is not added in step a, and a polyester polyol that is not added in step a to obtain the polyurethane polymer; and
c. introducing water and optionally an emulsifier before, during or after step b to obtain the aqueous polyurethane dispersion.
The aqueous polyurethane polymer is preferably prepared using a prepolymer mixing process, an acetone process or a melt dispersion process, most preferably using the acetone process.
The order of mixing of the components of the system for preparing the aqueous polyurethane dispersion can be carried out in a conventional manner.
The polyisocyanate and polyester polyol may be added in one portion or in multiple portions, either of the same or different composition as previously added.
The organic solvent present in the aqueous polyurethane dispersion can be removed by distillation. The organic solvent may be removed during or after the polyurethane polymer is formed.
The chelating agent may be added as a solid or as an aqueous solution. Preferably in the form of an aqueous solution of the chelating agent, which will facilitate the dispersion of the chelating agent.
The chelating agent can be added directly or can be formed in the composition in an acid-base neutralized form. The acid-base neutralization may be complete or incomplete neutralization, preferably complete neutralization.
The acid may be a free acid capable of undergoing a neutralization reaction with a base to form a chelating agent in the form of a water-soluble salt. The free acid is preferably one or more of the following: aminocarboxylic acids, hydroxycarboxylic acids, inorganic polyphosphoric acids, hydroxyaminocarboxylic acids, organic polyphosphonic acids, and polycarboxylic acids. The aminocarboxylic acid is preferably ethylenediaminetetraacetic acid and/or nitrilotriacetic acid. The hydroxycarboxylic acid is preferably one or more of the following: tartaric acid, citric acid and gluconic acid. The inorganic polyphosphoric acid is preferably one or more of the following: tripolyphosphoric acid, hexametaphosphoric acid and pyrophosphoric acid. The hydroxyamino-carboxylic acid is preferably hydroxyethylethylenediaminetriacetic acid and/or dihydroxyethylglycine.
When the composition further comprises a stabilizer, additive or aqueous dispersion, the process for preparing the composition of the invention preferably comprises the steps of: mixing the aqueous polyurethane dispersion, the adsorbent, the chelating agent, the optional stabilizer, the optional additive, and the optional aqueous dispersion in any manner.
The article is preferably selected from automotive interiors and interior furnishings.
The substrate is preferably one or more of the following: wood, plastic, metal, glass, textile, alloy, fabric, artificial leather, paper, cardboard, EVA, rubber, leather, glass fiber, ethylene vinyl acetate copolymer, polyolefin, thermoplastic polyurethane, polyurethane foam, polymer fiber, and graphite fiber, most preferably one or more of the following: EVA, rubber, genuine leather, artificial leather, ethylene vinyl acetate copolymer, polyolefin, thermoplastic polyurethane, and polyurethane foam.
The application may be the application of the composition to the entire surface of the substrate or only to one or more portions of the surface of the substrate.
The application may be brushing, dipping, spraying, rolling, knife coating, flow coating, pouring, printing or transferring, preferably brushing, dipping or spraying.
In the method of manufacturing a bonded article, a step iii between the step i and the step ii may be further included. When the method of making a bonded article further comprises a step iii, step ii is contacting the substrate surface treated in step iii with the substrate itself or a surface of an additional substrate to obtain the bonded article.
The step iii of heating and drying the surface of the substrate to which the adhesive is applied may refer to heating and drying only the surface of the substrate, or may refer to heating and drying a part of the substrate including the surface of the substrate to which the adhesive is applied or the entire substrate.
The heating and drying may remove volatile components. The volatile component may be water.
The heating and drying is preferably one or more of: infrared thermal radiation, near infrared thermal radiation, microwaves and the use of convection ovens or spray dryers at elevated temperatures.
The higher the temperature of the heating, the better, but should not be above the temperature limit at which the substrate deforms in an uncontrolled manner or suffers other damage.
The contacting is preferably performed before the temperature of the substrate surface is reduced below the temperature at which the adhesive can bond.
The additional substrate may be any substrate that requires adhesion.
The additional substrate and the base material may be the same or different.
The further substrate is preferably coated and heat treated as the substrate.
Two-component system
The amount of organic solvent of the two-component system is preferably not more than 5 wt.%, most preferably not more than 0.5 wt.%, based on 100 wt.% of the two-component system.
The two-component system is aqueous, and the VOC content of the two-component system is low.
The a and B components are preferably stored separately and mixed prior to use.
The weight ratio of the component A to the component B is preferably 1: 1-100: 1, most preferably 15: 1-25: 1.
the crosslinking agent is preferably an isocyanate group-containing compound.
The two-component system is preferably a coating or a binder, most preferably an interior coating or an interior binder.
The article is preferably selected from automotive interiors and interior furnishings.
The substrate is preferably one or more of the following: wood, plastic, metal, glass, textile, alloy, fabric, artificial leather, paper, cardboard, EVA, rubber, leather, glass fiber, ethylene vinyl acetate copolymer, polyolefin, thermoplastic polyurethane, polyurethane foam, polymer fiber, and graphite fiber, most preferably one or more of the following: EVA, rubber, genuine leather, artificial leather, ethylene vinyl acetate copolymer, polyolefin, thermoplastic polyurethane, and polyurethane foam.
The application may be the application of the composition to the entire surface of the substrate or only to one or more portions of the surface of the substrate.
The application may be brushing, dipping, spraying, rolling, knife coating, flow coating, pouring, printing or transferring, preferably brushing, dipping or spraying.
Examples
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term in this specification conflicts with a meaning commonly understood by those skilled in the art to which the invention pertains, the definition set forth herein shall govern.
Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained.
As used herein, "and/or" means one or all of the referenced elements.
As used herein, "comprising" and "comprises" encompass the presence of only the recited elements as well as the presence of other, non-recited elements in addition to the recited elements.
All percentages in the present invention are by weight unless otherwise indicated.
The analytical measurements according to the invention were carried out at 23 ℃ unless otherwise stated.
As used in this specification, the terms "a", "an" and "the" are intended to include "at least one" or "one or more" unless otherwise indicated. For example, "a component" refers to one or more components, and thus more than one component may be considered and may be employed or used in the practice of the described embodiments.
The solids content of the aqueous polyurethane dispersions was determined using a HS153 moisture meter from Mettler Toledo according to DIN-EN ISO 3251-2019.
The isocyanate group (NCO) content was determined volumetrically according to DIN-EN ISO 11909-and 2007, the data determined including the free and potentially free NCO content.
The pH was measured at 23 ℃ using a PB-10pH meter from Sartorius, Germany.
The specific surface area is obtained by testing according to the DIN ISO 9277-2014 standard test method.
Raw materials and reagents
Dispercoll U56: anionic aqueous polyurethane dispersions having a solids content of 50. + -. 1% are available from Kostew Innovation, Germany.
Desmodur DN: an aliphatic polyisocyanate crosslinker based on HDI having an isocyanate (NCO) content of 21.8% and a viscosity of 1250mPa.s is available from Kostew, Germany.
Dispercoll S4020: hydrophilic, fumed nanosilica dispersions having a solids content of 40% by weight, an average particle size of 15nm, BET 200m 2 Per g, available from Kossi Innovation, Germany.
Aerosil 200: hydrophilic fumed nano silicon dioxide with average particle size of 12nm and BET of 200 +/-25 m 2 Per g, available from Germany winning.
Aerosil 380: hydrophilic gasPhase nano-silica, average particle size 7nm, BET 380 + -30 m 2 Per g, available from Germany winning.
Aerosil R812S: hydrophobic fumed nano-silica with average particle size of 7nm and BET 220 +/-25 m 2 Per g, available from Germany winning.
Aerosil R972: hydrophobic fumed nano-silica with average particle size of 16nm and BET of 110 +/-20 m 2 Per g, available from Germany winning.
Zeoflair 200: the amphiphilic molecular sieve has the average particle size of less than 7 mu m and can be purchased from Zeochem company.
Zeoflair 100: the hydrophobic molecular sieve has an average particle size of less than 7 mu m and can be purchased from Zeochem company.
MCM 41: the hydrophilic molecular sieve has an average particle size of 0.2-1 mu m and can be purchased from Nanjing Xiancheng nanometer material science and technology company Limited.
Sodium pyrophosphate: chelating agent, sodium pyrophosphate content in sodium pyrophosphate aqueous solution being 4.3 x 10 -7 The pH value of the sodium pyrophosphate aqueous solution is 9.89 at mol/g, the solubility of the sodium pyrophosphate in water measured at room temperature of 20 ℃ is 6.2g/100g, and the sodium pyrophosphate aqueous solution can be purchased from Jiangyin Chengxing Xingxi industries group Ltd.
Method for preparing compositions of examples 1-2 and comparative examples 1-12
Table 1 shows the compositions of the compositions and two-component systems of the examples and comparative examples, and the results of odor testing of the compositions and two-component systems.
Comparative example 1
The aqueous polyurethane dispersions are referred to according to the content of the components shown in table 1.
Comparative example 7
According to the content of the components shown in table 1, the aqueous polyurethane dispersion is added into a container, the molecular sieve adsorbent is added while stirring at a stirring speed of 700rpm, and finally the stirring speed is increased to 900 rpm-1000 rpm, and stirring is continued for about 30min until all the components are uniformly dispersed.
Example 1 and comparative example 9
According to the content of the components shown in table 1, the aqueous polyurethane dispersion was added into a vessel, the sodium pyrophosphate solution (dissolved with water, concentration of 5%) and the molecular sieve were added in order at a stirring speed of 700rpm, the stirring speed was increased to 900 rpm to 1000 rpm, and stirring was continued for about 30min until all the components were uniformly dispersed.
Comparative examples 2 to 6 and comparative example 8
Adding the aqueous polyurethane dispersion into a container according to the content of the components shown in the table 1, adding a small amount of silicon dioxide adsorbent, stirring at the speed of 200rpm until the silicon dioxide is uniformly dispersed, suspending stirring and adding a small amount of silicon dioxide adsorbent, stirring at the speed of 200rpm until the silicon dioxide is uniformly dispersed, repeating the steps until the addition of the silicon dioxide with the amount shown in the table 1 is finished, finally increasing the stirring speed to 900 rpm-1000 rpm, and continuously stirring for about 30min until all the components are uniformly dispersed. Among them, the adsorbents of comparative examples 5 and 6 were not uniformly dispersed in other components and always floated on the surface.
Comparative example 10
According to the content of the components shown in the table 1, the aqueous polyurethane dispersion is added into a container, then sodium pyrophosphate solution (dissolved by water, the concentration is 5%) is added in turn at the stirring speed of 800rpm, stirring is suspended and a small amount of silica adsorbent is added, then stirring is suspended and a small amount of silica adsorbent is added at the stirring speed of 200rpm until the silica is uniformly dispersed, the steps are repeated until the addition of the amount of the silica shown in the table 1 is finished, finally the stirring speed is increased to 900 rpm-1000 rpm, and stirring is continued for about 30min until all the components are uniformly dispersed. Of these, the composition of comparative example 10 gelled during stirring.
Process for the preparation of two-component systems
Example 2
According to the content of the components shown in Table 1, the aqueous polyurethane dispersion is added into a container, stirred at the speed of 700rpm, then sodium pyrophosphate solution (dissolved by water and with the concentration of 5%) and a molecular sieve are added in turn under stirring, the stirring speed is increased to 900 rpm-1000 rpm, the stirring is continued for about 30min until all the components are uniformly dispersed, and then the crosslinking agent is added under stirring at the speed of 400 rpm to obtain a two-component system.
Odor test method
The evaluation of the odor of the composition or of the two-component system is carried out by means of an electronic nose, with the following specific steps:
1. cutting the aluminum foil into a rectangle with the size of 10cm by 20 cm;
2. taking 1.5ml of the composition to be tested or the bi-component system by a dropper, uniformly coating the composition or the bi-component system on an aluminum foil matt surface, and standing the composition or the bi-component system at room temperature until the composition or the bi-component system is completely dried;
3. putting the completely dried sample together with aluminum foil paper into a transparent glass bottle with the capacity of about 1L and no peculiar smell per se, and sealing;
4. putting the glass bottle into an oven, heating for 2h at 80 ℃, then cooling to 60 ℃ and preserving heat for more than half an hour;
5. the vial was removed from the oven, and a Cosmos odor sensor (Cosmos XP-329IIIR, new comamosse electronic (shanghai) ltd) probe was inserted into the vial immediately after the lid was opened, and measurements were taken and recorded in Batch mode. A larger reading value indicates a greater odor of the composition or the two-component system.
Table 1: composition and odor test results for compositions and two-component systems of inventive examples (Ex) and Comparative Examples (CE)
Composition/g Ex 1 Ex 2 CE 1 CE 2 CE 3 CE 4 CE 5 CE 6 CE 7 CE 8 CE 9 CE 10 CE11 CE12
Dispercoll U 56 100 100 100 100 100 100 100 100 100 100 100 100 100 100
Aerosil 200 1 2.5 3 3 2.5
Aerosil 380 2
Dispercoll S 4020 5
Aerosil R812S 1
Aerosil R972 1
Zeoflair 200 1 1
Zeoflair 100 1
MCM 41 5
Pyrophosphoric acid sodium salt 0.1 0.1 0.1 1.5 0.1 0.8
Desmodur DN 5
Odor test reading value 159 141 575 394 322 333 * * 462 337 450 ** 291 295
Remarking: the adsorbent cannot be uniformly dispersed in other components and always floats on the surface;
components gelled during stirring and therefore no odor test could be performed.
Comparing comparative examples 1-8 with example 1, the compositions of the present invention comprising an aqueous polyurethane dispersion, an adsorbent and a chelating agent, the compositions of the comparative examples comprising only an aqueous polyurethane dispersion and optionally an adsorbent, the odor test readings of the compositions of the present invention are significantly lower than those of the comparative examples. The adsorbents of comparative examples 5 and 6 are both of a hydrophobic type, and the adsorbents cannot be uniformly dispersed in other components, i.e., cannot form a composition suitable for practical use.
The composition of comparative example 9 comprised an aqueous polyurethane dispersion, an adsorbent and a chelating agent, but the adsorbent content of the composition exceeded 3% by weight, and the odor test reading of the composition was high.
The composition of comparative example 10 comprised an aqueous polyurethane dispersion, an adsorbent and a chelating agent, but the chelating agent content of the composition exceeded 1% by weight, and the components of the composition gelled during stirring and were not subjected to the odor test.
The compositions of comparative examples 11-12 comprise an aqueous polyurethane dispersion, an adsorbent, and a chelating agent, but the adsorbent is a hydrophilic fumed silica. The composition has high odor test readings.
Example 2 is a two-component system comprising an a-component and a B-component. The component A is the composition of the invention, the component B is Desmodur DN, and the odor test reading value of the two-component system is low. Comparing example 2 and example 1, it can be seen that the odor test reading value of the two-component system is lower than that of the composition.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing description, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description; and therefore any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.

Claims (18)

1. A composition comprising at least one aqueous polyurethane dispersion, at least one adsorbent, and at least one chelating agent; wherein the adsorbent is one or more of: hydrophilic molecular sieves and amphiphilic molecular sieves; the amount of the aqueous polyurethane dispersion is 50 wt% to 99 wt%, the amount of the adsorbent is 0.1 wt% to 3 wt%, and the amount of the chelating agent is 0.05 wt% to 1 wt%, all based on 100 wt% of the composition.
2. The composition of claim 1, wherein the aqueous polyurethane dispersion comprises water and a linear structure polyurethane polymer.
3. The composition of any one of claims 1-2, wherein the average particle size of the hydrophilic molecular sieve and the amphiphilic molecular sieve is each independently 0.1 μm to 10 μm.
4. A composition according to any one of claims 1 to 3, wherein the chelating agent is present as a water-soluble salt, provided that: in the water solution of water-soluble salt, when the content of the water-soluble salt is 4.3 x 10 -7 The pH of the aqueous solution at mol/g is greater than 4, preferably greater than 6, most preferably greater than 9.
5. The composition of any one of claims 1 to 4, wherein the chelating agent is one or more of: ethylenediaminetetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate, and gluconate; further preferred is one or more of the following: ethylenediaminetetraacetate, alkali metal tartrate, alkali metal citrate, alkali metal pyrophosphate, alkali metal tripolyphosphate, alkali metal hexametaphosphate, and alkali metal gluconate; most preferably one or more of the following: tetrasodium ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, and tetrasodium pyrophosphate.
6. The composition of any one of claims 1 to 5, wherein the composition is a coating or an adhesive.
7. A process for preparing a composition as claimed in any one of claims 1 to 6, comprising the steps of: the aqueous polyurethane dispersion, the adsorbent and the chelating agent are mixed in any manner.
8. Use of a composition according to any one of claims 1 to 6 for the preparation of an article.
9. Use according to claim 8, wherein the article is selected from automotive interiors and interior furnishings.
10. An article comprising a substrate and a coating formed by applying the composition of any one of claims 1-6 to the substrate.
11. A method of making a coated article comprising the steps of: applying a composition according to any one of claims 1 to 6 to a substrate surface followed by curing.
12. A method of making a bonded article comprising the steps of:
i. applying a composition according to any one of claims 1 to 6 to at least one surface of a substrate; and
contacting the surface of the substrate treated in step i with the surface of the substrate itself or of an additional substrate to obtain the bonded article.
13. A two-component system comprising an a-component which is a composition according to any one of claims 1 to 6 and a B-component which is a cross-linking agent.
14. The two-component system according to claim 13, wherein the crosslinking agent is an isocyanate group-containing compound.
15. Two-component system according to claim 13 or 14, wherein the two-component system is a coating or a binder.
16. Use of the two-component system according to any of claims 13-15 for the preparation of an article.
17. Use according to claim 16, wherein the article is selected from automotive interiors and interior furnishings.
18. An article comprising a substrate and a coating formed by applying the two-component system of any of claims 13-15 to the substrate.
CN202080078975.XA 2019-11-13 2020-11-09 Composition and preparation method and application thereof Pending CN114829516A (en)

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EP20151335.5A EP3848423A1 (en) 2020-01-13 2020-01-13 Composition, preparation method and application thereof
PCT/EP2020/081409 WO2021094228A1 (en) 2019-11-13 2020-11-09 Composition, preparation method and application thereof

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