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WO2018063095A1 - Agent de réticulation pour émulsions polymères - Google Patents

Agent de réticulation pour émulsions polymères Download PDF

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Publication number
WO2018063095A1
WO2018063095A1 PCT/SG2017/050480 SG2017050480W WO2018063095A1 WO 2018063095 A1 WO2018063095 A1 WO 2018063095A1 SG 2017050480 W SG2017050480 W SG 2017050480W WO 2018063095 A1 WO2018063095 A1 WO 2018063095A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating composition
crosslinker
dendritic
hyperbranched
polymeric
Prior art date
Application number
PCT/SG2017/050480
Other languages
English (en)
Inventor
Ting Tai POH
Hairong Li
Shaofeng Wang
Original Assignee
Nipsea Technologies Pte Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nipsea Technologies Pte Ltd filed Critical Nipsea Technologies Pte Ltd
Publication of WO2018063095A1 publication Critical patent/WO2018063095A1/fr

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Classifications

    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/005—Dendritic macromolecules
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/028—Polyamidoamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/02—Polyamines

Definitions

  • the present invention generally relates to a crosslinking agent for use in aqueous polymer compositions or polymer emulsions, methods for curing or crosslinking these compositions and coatings formed therefrom.
  • polymer emulsions are commonly used film formers in the coatings and paints industry.
  • These aqueous-dispersible polymer compositions typically comprise an organic polymer binder phase dispersed in an aqueous solvent phase.
  • These polymer emulsions may be curable / crosslinkable at room temperature conditions (typically around 20 °C - 30 °C).
  • the polymer binder phase of such emulsions is typically comprised of polymers or copolymers having actinic- radiation curable functional groups, such as vinyl groups.
  • a common example of such binders would be polyacrylates or polymethacrylates.
  • a crosslinking agent is usually added to such compositions to increase the hardness of an ultimately formed coating. This is accomplished by increasing the cross-linking density.
  • other benefits of increasing crosslinking density may include, but are not limited to, increased coating resistance to water or chemical solvents (acids, bases).
  • ADH has been observed to be particularly effective in crosslinking polyacrylate binders having functionalized monomers such as, acetone monomers, acetoacetoxyalkylethylacrylate (AAEM) monomers, butyl acetoacetate (BAA) monomers or mixtures thereof.
  • ADH is also commonly used as hardeners for epoxy formulations and has been shown to provide excellent water resistance to coatings.
  • a coating composition comprising: a latex component comprising an acrylic emulsion, said acrylic emulsion having at least one monomer expressing a reactive carbonyl functional group; and a crosslinker component comprising a hyperbranched or dendritic, polymeric or oligomeric crosslinker comprising reactive amine functional groups.
  • the disclosed cross-linker may be non-toxic.
  • the disclosed crosslinker may react with the carbonyl functional group of the monomer unit to thereby crosslink the acrylic emulsion and become integrated into the crosslinked polymerized network.
  • the crosslinker may comprise functional groups that are reactive under ambient temperature and pressure conditions.
  • the disclosed crosslinker is a star-shaped or dendritic polymer.
  • the dendritic polymer may have a substantially globular shape and exhibits a substantially monodisperse structure (uniformly or symmetrically branched structure) with a high density of surface (peripheral functional groups).
  • Dendritic structures are usually formed from a central initiator molecule having two or more reactive sites, wherein further reaction results in the outward growth of the structure with an exponentially increasing number of peripheral functional groups.
  • a dendritic structure may be described by its generation, e.g., a generation 0 dendritic polymer may have 4 functional groups and a generation 1 dendritic polymer may have 8 peripheral functional groups, etc.
  • the disclosed crosslinker may be a generation 0, 1 , 2, 3, or 4 dendritic polymer.
  • the disclosed crosslinker may express reactive peripheral amine groups. These peripheral amine groups may be primary amines capable of reacting with carbonyl compounds to form enamines.
  • the crosslinker is a dendritic polymer such as polyamidoamine (PAMAM).
  • PAMAM polyamidoamine
  • the crosslinker may be a generation 0, 1 , 2, 3, or 4 PAMAM, having a theoretical number of 4, 8, 16, or 32 peripheral amine functional groups respectively.
  • the amine functional groups may be primary amine, secondary amine or tertiary amine groups.
  • the crosslinker is PAMAM having from around 4 to around 16 functional groups.
  • the crosslinker is PAMAM having from around 8 to around 16 functional groups.
  • dendritic or hyperbranched amine functional crosslinker is able to substitute the traditional function of ADH without reducing crosslinking effectiveness.
  • This effect is supported by the comparable coating density and hardness achieved by coatings of the present invention (using the disclosed crosslinkers) when compared to ADH-based coatings.
  • dendritic/hyperbranched polymers are known to act as demulsifiers, it was surprisingly found that the introduction of the amine functional dendritic and hyperbranched crosslinkers into the polymer emulsion systems did not result phase separation between the organic binder phase and the aqueous solvent phase. It has been advantageously observed that, apart from coating hardness, the amine functional dendritic and hyperbranched crosslinkers also achieved improved water resistance and abrasion resistance.
  • coatings according to the present invention also exhibit low or negligible VOC emissions.
  • Yet another aspect of the invention relates to a method of forming a coating, said method comprising: providing a latex component comprising an acrylic emulsion, said acrylic emulsion having at least one monomer expressing at least one reactive carbonyl functional group; adding a hyperbranched or dendritic, polymeric or oligomeric crosslinker comprising reactive amine functional groups to said latex component to form a crosslinkable coating composition; applying said coating composition to a surface; and reacting said crosslinker with said latex component under ambient conditions to form said coating.
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1 % of the stated value, and even more typically +/- 0.5% of the stated value.
  • certain embodiments may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges.
  • a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range.
  • description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1 , 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • Fig. 1 is a photograph depicting the effects after applying a wet abrasive scrub test to an in-house paint formulation X prepared with a crosslinker according to the invention (right image) and a paint formulation prepared without a crosslinker according to the invention (left image).
  • Fig. 2 is a another photograph showing the effects after applying a wet abrasive scrub to an in-house paint formulation Y prepared with a crosslinker according to the invention (right image) and a paint formulation prepared without a crosslinker according to the invention (left image).
  • the disclosed dendritic/hyperbranched cross-linker may be used in combination with a melamine-based crosslinker and/or a dihydrazide crosslinker (e.g., ADH).
  • the coating composition may be substantially absent of a melamine-based crosslinker and/or ADH.
  • the latex or the polymer emulsion used in the disclosed coating composition is not particularly limited. It is preferable that the polymer emulsion is prepared from monomer units comprising at least one a ketone functional group. In one embodiment, the monomer of the emulsion comprises at least one reactive carbonyl group of a ketone moiety capable of undergoing enamine formation with a di-amine functional group.
  • the monomer units may comprise acrylate monomers having at least one vinyl group and a carboxylic acid group.
  • the acrylate monomers may additionally comprise at least one or more of a ketone functional group, an ester functional group or an amide functional group.
  • the monomer units are acrylate-based monomers (or acrylic monomers) expressing one or more of the following functional groups:
  • the monomer unit may be an alkylacetoacetate having the following structure: R 1 -0-C(0)-CH 2 -C(0)-CH 3 , wherein R 1 is C1 -6 alkyl selected from methyl, ethyl, propyl, butyl, pentyl and hexyl.
  • the disclosed latex or polymer emulsion may comprise acetoacetoxyethyl methacrylate monomer units, tert-butyl acetoacetate monomer units, diacetone acrylamide and mixtures and blends thereof.
  • the crosslinking between the dendritic / hyperbranched crosslinker and the acrylate monomers may be due to enamine formation between the reactive carbonyl functionality of the ketone group or ester group and the peripheral amine functional groups of the crosslinker. Due to the high density of surface amine groups expressed by the crosslinker, greater crosslinking density can be achieved as opposed to the use of crosslinkers which do not exhibit the globular dendritic/hyperbranched structures.
  • the hyperbranched or dendritic, polymeric or oligomeric crosslinker may have a molecular weight of greater than 250, or greater than 500.
  • the average molecular weight of the cross-linker may be selected from: 250 - 500, 500 - 20,000, 500 - 10,000, 500-7500, 500 - 5,000, 500 - 2500, 500-2000, 500 - 1500, 500 - 1000, 500-900, 500-800, 500-700, or 500-600.
  • the crosslinker may be selected to have a molecular weight that allows it to retain dispersibility or solubility in the emulsion, while exhibiting little or no volatility.
  • the crosslinker according to the invention may experience a weight loss of less than 10 wt. % post-curing, preferably less than 5 wt. %, more preferably less than 2 wt. % and less than 0.5 wt. %. In embodiments, the crosslinker may exhibit a weight loss of less than 0.1 wt. % after curing.
  • the theoretical number of surface amine functional groups may be selected from 4, 8, 16, 32 or 64. Due to imperfect branching, these are theoretical numbers based on the dendritic polymer generation. Actual number of functional groups per dendritic molecule may be from about 1 to 80. In embodiments, the number of functional groups per dendritic molecule may be around 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80 or a range thereof. In one embodiment, a generation 0 polyamine having around 4 amine functional groups per molecule is provided as crosslinker. In another embodiment, a generation 1 polyamine having around 8 amine functional groups per molecule is provided as crosslinker. In yet another embodiment, the crosslinker may comprise mixtures of dendritic polyamine having different generations.
  • the number of functional groups per dendritic molecule may be from about 10 to 80, 10 to 70, 10 to 60, 10 to 50, 10 to 40, 10 to 30, 20 to 80, 20 to 70, 20 to 60, 20 to 50, 20 to 40, 30 to 80, 30 to 70, 30 to 60, 30 to 50, 40 to 80, 40 to 70, 40 to 60 or 40 to 50.
  • a hyperbranched polyamine having around 20 to 50 amine functional groups per molecule is provided as crosslinker.
  • the disclosed crosslinkers were found to provide effective crosslinking, even when provided in a latex:crosslinker weight ratio of 1000:1 .
  • the latex:crosslinker weight ratio may be from 1000: 1 to about 5:1 , e.g., 1000/1 , 900/1 , 800/1 , 700/1 , 600/1 , 500/1 , 400/1 , 300/1 , 200/1 , 100/1 , 90/1 , 80/1 , 70/1 , 60/1 , 50/1 , 40/1 , 30/1 , 20/1 , 10/1 , 9/1 , 8/1 , 7/1 , 6/1 , or 5/1 .
  • the latex may form around 5 to 95 wt. % based on the weight of the coating composition.
  • the latex composition may comprise acrylic monomers comprising at least one or more of a ketone functional group, an ester functional group, or an amide functional group, wherein these acrylic monomers are present in amounts of from about 0.1 to about 20 weight percent based on the total weight of the latex composition.
  • the disclosed functionalized acrylic monomers may be present in an amount of about 0.1 , 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 .0, 1 .2, 1 .4, 1 .6, 1 .8, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, or 20 wt. %, or in a range having an upper and lower limited selected therefrom.
  • the latex composition comprises the functionalized acrylic monomers in an amount of from 0.1 to 10 weight percent.
  • the functionalized acrylic monomers may be AAEM monomers as disclosed herein, the acetoacetate monomers as disclosed herein or a blend thereof.
  • the disclosed coating composition may be formulated in such a way so that the molar ratios between the crosslinkable functional groups of the dendritic crosslinker (e.g., NH 2 ) and the reactive functional groups of the acrylic monomers are between 1 :4 to 4:1 , e.g., 1 :4, 1 :3.5, 1 :3, 1 :2.5, 1 :2, 1 :1 .5, 1 :1 . 1 .5:1 , 2:1 , 2.5:1 , 3:1 , 3.5:1 or 4:1 .
  • the crosslinkable functional groups of the dendritic crosslinker e.g., NH 2
  • the reactive functional groups of the acrylic monomers are between 1 :4 to 4:1 , e.g., 1 :4, 1 :3.5, 1 :3, 1 :2.5, 1 :2, 1 :1 .5, 1 :1 . 1 .5:1 , 2:1 , 2.5:1 , 3:1 , 3.5:1 or 4:1 .
  • the molar ratio of the groups to the crosslinkable functional group is around 1 :4 to 4:1 . In one o
  • crosslinkable functional group is around 1 :4 to 4:1 .
  • the coating composition may be a clear coat, which comprises around 77 to 98% by weight of the latex component, and about 0.1 to about 25 wt. % crosslinker, preferably from 4 wt.% to 20 wt.%, 0 to 30 wt. % one or more additives, wherein the total weight percentage does not exceed 100% or is 100%.
  • the coating composition may be a pigmented coat, which comprises around 15 to 50% by weight of the latex component, and about 0.01 to about 25 wt. % crosslinker preferably from 4 wt.% to 20 wt.%, 10-30% pigment or organic filler, 0 to 30 wt. % one or more additives, wherein the total weight percentage does not exceed 100% or is 100%.
  • another embodiment of the invention relates to a two-pack coating composition
  • a two-pack coating composition comprising: in a first pack, a latex component as defined herein; and in a second pack, a polyamine crosslinker as described hereinabove.
  • the present disclosure further relates to a method of forming a coating on a surface, said method comprising: providing a latex component comprising an acrylic emulsion, said acrylic emulsion having at least one monomer expressing at least one reactive carbonyl functional group; adding a hyperbranched or dendritic, polymeric or oligomeric crosslinker comprising reactive amine functional groups to said latex component to form a crosslinkable coating composition; applying said coating composition to the surface; and reacting said crosslinker with said latex component under ambient conditions to form said coating.
  • the hyperbranched or dendritic, polymeric or oligomeric crosslinker may be a dendritic or hyperbranched polyamine as disclosed herein.
  • the latex component and its associated acrylate monomers may be as disclosed hereinabove.
  • the disclosed method may expressly exclude a step of adding a melamine based crosslinker or a dihydrazide crosslinker (e.g. ADH) to the latex component.
  • a melamine based crosslinker or a dihydrazide crosslinker e.g. ADH
  • melamine crosslinkers or ADH may be added in combination with the dendritic or hyperbranched polyamine.
  • a method for crosslinking a polymer emulsion having the acrylate monomers as defined herein comprises the step of reacting said polymer emulsion with a dendritic or hyperbranched polyamine as disclosed herewith under ambient condition to cause said crosslinking.
  • the present invention further provides the use of a dendritic polyamine as a crosslinker for crosslinking an aqueous polymer composition, wherein the aqueous polymer composition may be an acrylic emulsion as disclosed herein.
  • the reactive carbonyl group is of the ketone group.
  • Amine functional groups including primary amines and second amines with at least one active hydrogen
  • ketones can react with ketones to form enamines with H 2 0 as a side product.
  • alkali conditions e.g. at pH of 8- 10
  • the reaction may be suppressed.
  • mildly acidic conditions e.g., pH is ⁇ 5 or ⁇ 7 may result in the dehydration of the water and shift the reaction equilibrium to the product side.
  • Evonik Tego 815 defoamer that is an emulsion of a polyether siloxane copolymer and contains fumed silica
  • Gel content is analyzed using an in-house method relying on acetone solvent as dissolving medium for the analysis.
  • a latex film was prepared on a glass panel using an initial weight of the coating composition (0.5 grams to 1 gram). The film is cured for more than 7 days at room temperature and removed from the glass panel by peeling off.
  • the filter paper and its contents are removed from the solvent after 24 hours.
  • the film and the filter paper are then air dried.
  • the film is then dried again in oven at 1 10 °C for 30 minutes. Thereafter, the film is cooled to room temperature before its final weight measurement is taken.
  • % gel content (Weight of latex film after solvent, 24 hours) X100
  • Latex film was casted on glass panel and cured at room temperature for more than 7 days.
  • a glass tube (diameter measuring 2cm and 4cm in height) was used to contain the latex film surface.
  • Cotton wool with equal weight was placed into the glass tube to cover the film surface. 2 ml of de-ionized water is dropped into the glass tube to wet the cotton wool. The cotton wool is then pressed down to ensure fully contact with the film surface. Water contact for 30 minutes is allowed before removing the glass tube and cotton wool to observe latex film appearance for severity of whiteness or formation of spots.
  • a latex film was casted on a BYK byko-charts black scrub panel (#PB-5015). The filme is cured at room temperature for more than 7 days before proceeding with the test.
  • FTIR-ATR analysis A mixture comprising a predetermined weight ratio of AAEM with PAMAM material (or the comparative ADH crosslinker) is prepared under methanol medium and allowed to react. The ambient crosslinking reaction is then monitored using Fourier Transform Infrared spectroscopy - Attenuated Total Reflection (FTIR-ATR). The mixture liquid was spotted on a sample compartment and blown dry using hair drier before the IR spectrum is collected.
  • FTIR-ATR Fourier Transform Infrared spectroscopy - Attenuated Total Reflection
  • EXAMPLES 1 to 29 (Latex Film Samples) 29 latex film samples are prepared in accordance with the compositions provided in Tables 2-5 as follows: The latex composition is gradually dosed with the crosslinker component under constant stirring to achieve homogeneity. A latex film of 100 microns in thickness is then casted on a glass panel and left to cure under ambient conditions for more than 7 days to ensure complete curing. The latex film is peeled and collected for analysis under General Analysis procedures 1 and 2 (Gel Content and water resistance)
  • Latex SF 240 96.95 95.95 94.95 92.95 88.95 96.95 95.65 94.45 91 .95
  • Latex SF 240 86.95 95.55 94.15 91 .35 85.75 95.35 93.85 90.65 84.35
  • Emulsion paint (named as Paint-X) containing latex SF240
  • Emulsion paint (named as Paint-Y) containing latex MV100
  • Paint-Y was produced in-house according to the formulation in Table 8. Firstly deionized water was added to the dispersion tank, controlling speed at 800-1000 rev/min, and then adding (sequentially) raw materials 2-7, i.e., HEC thickeners, AMP-95, sodium polycarboxylate-based dispersants, silicone defoamers, titanium dioxide, kaolin were added to the dispersion tank.
  • raw materials 2-7 i.e., HEC thickeners, AMP-95, sodium polycarboxylate-based dispersants, silicone defoamers, titanium dioxide, kaolin were added to the dispersion tank.
  • Emulsion paint prepared according to Example 31 is used.
  • CYD-120A polyamidoamine crosslinker
  • the preparation of the paint film is according to General Analysis Procedure #3.
  • Applying the wet abrasion scrub test demonstrated improvement in the paint comprising a crosslinker according to the presentinvention as seen in Figure 1 .
  • the incorporation of CYD-120A appears to have significantly increased the crosslinking density of the paint film resulting in the mechanical wear improvement.
  • Example 31 An emulsion paint is prepared according to Example 31 .
  • CYD-120A is post added into the paint formulation and the preparation of the paint film is according to General Analysis Procedure #3. Applying the wet abrasion scrub test showed improvement as can be observed by comparing Figures 2. The incorporation of CYD-120A appears to have increased the crosslinking density of the paint film resulting in the mechanical wear improvement.
  • Example 34

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de revêtement comprenant : un constituant de type latex comprenant une émulsion acrylique, ladite émulsion acrylique présentant au moins un monomère exprimant un groupe fonctionnel carbonyle réactif ; et un constituant de réticulation comprenant un agent de réticulation polymère ou oligomère, hyperramifié ou dendritique comprenant des groupes fonctionnels amine réactifs ; et des procédés de formation de revêtements à l'aide de ceux-ci. La composition de revêtement présente des émissions de composés organiques volatils (COV) faibles ou négligeables.
PCT/SG2017/050480 2016-09-29 2017-09-26 Agent de réticulation pour émulsions polymères WO2018063095A1 (fr)

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SG10201608158W 2016-09-29
SG10201608158W 2016-09-29

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022053357A1 (fr) 2020-09-10 2022-03-17 Evonik Operations Gmbh Procédé de préparation de (méth)acrylates de vanilline
CN117567912A (zh) * 2023-11-22 2024-02-20 江西科技师范大学 一种可回收聚丙烯酸酯乳液涂层及其制备方法和应用
CN117946349A (zh) * 2024-03-26 2024-04-30 潍坊弘润新材料有限公司 一种树枝状聚合物改性羟基丙烯酸乳液、制备方法及应用

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US5939482A (en) * 1994-11-29 1999-08-17 Vianova Resins Aktiengesellschaft Method for the two-stage preparation of aqueous autocrosslinking copolymer dispersions and their use for coating materials
US20080289539A1 (en) * 2007-05-25 2008-11-27 Basf Corporation Coating compositions having hyperbranched polymers and methods of producing same
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US20130333840A1 (en) * 2011-03-04 2013-12-19 3M Innovative Properties Company Polyether hybrid epoxy curatives
US20150004420A1 (en) * 2012-03-14 2015-01-01 Valspar Sourcing, Inc. Modified Crush Resistant Latex Topcoat Composition for Fiber Cement Substrates
ES2538180A1 (es) * 2015-04-17 2015-06-17 Universitat Politècnica De Catalunya Composición para el entrecruzamiento de una amina con un compuesto vinílico alfa,beta-conjugado a un grupo carbonilo de éster y posterior polimerización del compuesto vinílico y procedimientos correspondientes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5939482A (en) * 1994-11-29 1999-08-17 Vianova Resins Aktiengesellschaft Method for the two-stage preparation of aqueous autocrosslinking copolymer dispersions and their use for coating materials
US20080289539A1 (en) * 2007-05-25 2008-11-27 Basf Corporation Coating compositions having hyperbranched polymers and methods of producing same
CN101967343A (zh) * 2010-10-22 2011-02-09 广州市博兴化工科技有限公司 一种光固化色漆
US20130333840A1 (en) * 2011-03-04 2013-12-19 3M Innovative Properties Company Polyether hybrid epoxy curatives
US20150004420A1 (en) * 2012-03-14 2015-01-01 Valspar Sourcing, Inc. Modified Crush Resistant Latex Topcoat Composition for Fiber Cement Substrates
ES2538180A1 (es) * 2015-04-17 2015-06-17 Universitat Politècnica De Catalunya Composición para el entrecruzamiento de una amina con un compuesto vinílico alfa,beta-conjugado a un grupo carbonilo de éster y posterior polimerización del compuesto vinílico y procedimientos correspondientes

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022053357A1 (fr) 2020-09-10 2022-03-17 Evonik Operations Gmbh Procédé de préparation de (méth)acrylates de vanilline
CN117567912A (zh) * 2023-11-22 2024-02-20 江西科技师范大学 一种可回收聚丙烯酸酯乳液涂层及其制备方法和应用
CN117567912B (zh) * 2023-11-22 2024-05-28 江西科技师范大学 一种可回收聚丙烯酸酯乳液涂层及其制备方法和应用
CN117946349A (zh) * 2024-03-26 2024-04-30 潍坊弘润新材料有限公司 一种树枝状聚合物改性羟基丙烯酸乳液、制备方法及应用

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