Fusion bonded epoxy rebar powder coatings
11820915 · 2023-11-21
Assignee
Inventors
Cpc classification
C09D163/00
CHEMISTRY; METALLURGY
C09D7/70
CHEMISTRY; METALLURGY
C04B20/1037
CHEMISTRY; METALLURGY
International classification
C09D163/00
CHEMISTRY; METALLURGY
Abstract
This invention relates to fusion bonded epoxy rebar powder coating compositions of enough latency overtime, which cure in seconds upon residual heat up to 239.0° C., exhibiting low temperature flexibility to achieve crack-free rebar bending at −45° C. and a glossy finish without yellowing or discoloration. This invention further relates to rebar powder coatings compounded using suitable dihydrazide amines as the curing agent, in combination with an executive resin blend including a compatible toughening epoxy, and a synergic catalyst package to meet the intended application challenges.
Claims
1. A powder coating composition, comprising: (a) a flexible dihydrazide amine of an averaged particle size less than 10 microns, represented by the following general structure: ##STR00006## where n=4−20; and (b) a dual catalyst package comprising about 1 to 4 phr a principal catalyst and an additive catalyst, wherein the principal catalyst is selected from the group consisting of 2-methyl imidazole (2MI), dimethylaminopyridine, an amine adduct, or an imidazole adduct; and the additive catalyst is an imidazole amine present in an amount of about 1 to 10 wt %, based on the weight of the principal catalyst; and (c) an epoxy binder resin system comprising: a. 10 wt % to 20 wt % of the toughening resin; and b. 80 wt % to 90 wt % of the bulk epoxy resin package comprising a blend of epoxy resins having an EEW of between 800 and 2000; all wt % based on the total weight of the resins, corresponding resin-to-crosslinker stoichiometric molar ratio is 1.2:1 to 3.0:1.
2. The powder coating composition of claim 1, wherein the blend of epoxy resins is a blend of Type 4 resin having an EEW of between 800 and 1225 and Type 7 resin having an EEW of between 1650 and 2000.
3. The powder coating composition of claim 2, wherein the ratio of the amount of the Type 4 resin and the Type 7 resin ranges from 1:8 to 4:1.
4. The powder coating composition of claim 2, wherein the ratio of the amount of the Type 4 resin and the Type 7 resin ranges from 1:6 to 2:1.
5. The powder coating composition of claim 1, wherein the toughening resin is a core-shell-rubber modified (with a MBS copolymer core and a type 4 epoxy shell) or an amphilphilic OP (PEO-PEP) diblock copolymer-modified type 4 epoxy.
6. A coated structural steel rebar, wherein the coated rebar has a coating composition applied thereon, comprising the powder coating composition of claim 1.
7. The coated rebar of claim 6, wherein said powder coating composition cures within 16-28 seconds upon preheat at 239° C.
8. The coated rebar of claim 6, wherein when said coating composition is cured, the coating demonstrates no cracks or tears when rebar bended at −45° C. upon staying at −45° C. for up to 24 hours.
Description
DETAILED DESCRIPTION
(1) This invention solves the crack, micro-tear and peel-off problems of rebar coatings along with improving processability and stability overtime, wherein selected flexible dihydrazides as the crosslinker combined with a novel epoxy resin package consisting of a compatible toughening resin and a balanced bulk epoxy blend, such as a Type 4 and Type 7 blend, provide for flexibility (that prevents cracking) and toughening (that prevents micro-tearing) and adhesion (that prevents peeling off). A dual catalyst package comprising 2PI (that is viscous liquid or semi-solid at room temperature, encapsulated at 60% active with fumed silica as the carrier) affords compatibility and enhanced adhesion. Concurrently, this invention provides sufficient latency as a result of the dihydrazide amines with melting temperatures much higher than phenolics, also allowing for advantageous extrusion temperature up to 125° C. to be used (relatively high temperature extrusion enables fully homogenized compounding.
(2) The combinations of flexibility (via dihydrazides and resin blends) and adhesion (via flow and wetting as partially conferred by 2PI) and cohesion (via toughening) as well as fully dispersed dihydrazide resin particles among coating ingredients address the challenges of rebar coatings.
(3) The coatings of this invention primarily take advantage of the dihydrazide chemistry, (1) achieving crack free bending performance down at −45° C.; 2) improving product latency (DSC onset temperatures >130° C. vs. existing phenolic formulations ≤120° C. run at 20° C/min) that lead to adequate shelf life for storage and transportation with few concerns about premature curing or impaired end performance over time. In addition, they allow regular and friendly extrusion temperature settings up to 125° C. (no more limited to ≤90° C. as sometimes applied onto phenolic cured rebar products).
(4) The coatings of this invention utilize flexible dihydrazides together with an epoxy resin package of maximized flexibility and flow potentials that allow the coating upon cure to withstand cracking when bent at varying degrees per pipe diameter (°/PD) at extremely low temperatures (down to −45° C.) while maintaining strong adhesion to steel rebar substrates. Epoxy thermosetting cure is a complicated process involving a series of competing reactions consisting of etherification (epoxy homo-polymerization) and cross-linking polyaddition initiated or catalyzed by tertiary (3°) amines. Homo-polymerization represents linear chain propagation that eventually provides flexibility to support crack-free bending while cross-linking leads to a polymeric network with adequate toughness, mechanical strength and integrity.
(5) Dihydrazides
(6) The curing agents or crosslinkers employed in this invention include one or more flexible dihydrazides of four (4) active primary (1°) amine functionalities having the following general structure:
(7) ##STR00002##
where n=4−20;
The ratio of epoxy equivalent weight (EEW) to amine hydrogen equivalent weight (EW-NH) in this invention should be selected within 1.0:1 to 6.0:1, preferably between 1.2:1 and 3.0:1. For example, for an epoxy resin that has reactive glycidyl groups, a more preferred molar ratio of glycidyl groups in the epoxy resin to amino groups in the curing agent is in a range of 1.5:1 to 2.8:1.
(8) In one embodiment, dihydrazides such as ADH, SDH, DDH, LDH, and UDH are identified as suitable curing agents in this invention with SDH (melting temperature T.sub.m=187° C. vs. T.sub.m of phenolics<115° C.) preferred. SDH has a linear CH.sub.2 chain of eight (8) in between functional end groups imparting flexibility. SDH has a high melting point that provides desired latency. Preferred dihydrazides include the following:
(9) ##STR00003##
(10) In one embodiment, between carbonyl parts of the hydrazide can contain saturation, such as in the following:
(11) ##STR00004##
SDH as the core crosslinker composition used in this invention preferably has a fine particle size of averaged 3 to 6 microns. Fine particle size and narrow particle size distribution permit unmelt SDH resin particles to be fully and uniformly dispersed into the resin system by extruder, eventually in favor of acceptable and best possible performance in terms of bending cracks. By comparison, coarse particle size of SDH at averaged 30 to 60 microns are determined to consistently fail rebar crack performance.
Catalysts
(12) The catalyst used in this invention is a dual catalyst system. The principal catalyst useful in this invention is an amine catalyst, preferably 2-methyl imidazole (2MI) or DMAP or an amine adduct or an imidazole adduct, as structurally shown below, 2MI and DMAP and the imidazole adduct (shown) are equivalent in terms of reactivity at a given phr (per one hundred resin) loading level according to DSC cure kinetic data. Amine adducts (such as, e.g., Epikure P100, Aradur 3088, or Epikure P101) are slightly less reactive but their reactivity can be elevated by increasing the loading level. DMAP and an imidazole adduct (containing 3° amines only) tend to promote more epoxy homo-polymerization over crosslinking than 2MI does; homo-polymerization imparts flexibility as taught by this invention. Preferably, the amount of 2MI or DMAP or an amine adduct or an imidazole adduct in these inventive compositions ranges generally from 1 to 4 phr in one embodiment; more preferably from 1 to 2 phr, closely related to the stoichiometric ratio to be chosen and depending on the gel and cure time to be achieved in another embodiment.
(13) ##STR00005##
A second and additive catalyst in accordance with this invention is also from the imidazole amine group, more specifically, 2P1, which is the only viscous liquid or semi-solid imidazole at ambient temperatures. Because of its liquid form, 2PI is of better compatibility or dispersibility with epoxies than 2MI or DMAP or amine/imidazole adducts, facilitating homogenized mixing of coating ingredients in this invention, and promoting flow and leveling thus to improve adhesion in support of crack or peel free bending performance even at a low phi loading level in combination with the principal catalyst. Meanwhile, 2PI is of much higher latency (due to steric effects) than 2MI or DMAP or amine/imidazole adducts while it becomes highly reactive (as reactive as amine adducts but not so reactive as 2MI or DMAP or imidazole adducts) upon thermal activation, hence improving coating stability while maintaining reactivity required for snap cure. The amount of 2PI can be selected by cure kinetic results as well. For instance, the amount of 2PI of 100% active may range from 1 to 10% by weight of the amount of the principal catalyst such as 2MI or DMAP or amine/imidazole adducts used in one embodiment of this invention.
Toughening Resins
(14) The use of a toughening epoxy in the resin composition of the present invention typically leads to enhanced cohesion (supporting bending tear free) while not impairing flexibility (supporting bending crack free), provided that the toughening resin is highly compatible with the bulk resins.
(15) The toughening agent is typically an organic polymer additive that phase separates in a cured epoxy resin network. The toughening resin useful in the present invention may include for example MBS or methyl methacrylate-butadiene-styrene copolymer modified type 4 epoxy of core-shell rubber (CSR) structures, block copolymer modified, polyol modified, DCPD (dicyclopentadiene) modified, rubber (CTBN, acrylic, and others) modified, or mixtures thereof.
(16) One embodiment of the toughening epoxy useful in the present invention may include for example, a CSR modified such as Fortegra 304 used in this invention, and alternatively an amphiphilic diblock copolymer-modified epoxy. Polyol- and DCPD-modified (such as XU-19741 and Epiclon HP-7200H or XD-1000, respectively) are tested to be slightly inferior in terms of micro-tearing. Preferably, the amphiphilic diblock copolymer-modified epoxy useful in the present invention may include PEO-PEP (polyethylene-polyethylene-propylene) modified epoxy derived from bisphenol A; more preferably, the toughening agent used in this invention is FORTEGRA™ 664-12. Both Fortegra 304 and 664-12 turn out to be highly compatible with compositions of this invention, and they can self-assemble to form the second phase of toughening rubber core during cure.
(17) The concentration of the toughening agent used in the curable compositions described herein may depend on a variety of factors including the equivalent weight of the polymers, and the desired flexibility and toughening properties of the product made from the curable composition. In general, the toughening agent may be used in an amount sufficient to provide the resulting composite enough toughness to prevent micro-cracking (i.e., tearing) of the coating. For example, the amount of the toughening resin may range generally from about 7.5 wt % to about 22.5 wt % in one embodiment, from about 10 wt % to about 20 wt % in another embodiment, and from about 12 wt % to about 15 wt % in even still another embodiment, based on the total weight of the resin composition.
(18) Bulk Epoxy Resins
(19) A bulk epoxy resin package as one of viable options preferably consists of 70% Type 7 (e.g., Epon 1007F), 17.5% Type 4 (e.g., Epon 2004), and 12.5% toughening resin (e.g., Fortegra 664-12 or Fortegra 304), creating a system of superior flexibility and adhesion and toughness desired once preferably cured by dihydrazides with ADH and SDH used at an equivalent ratio of 1:1.5 to 1:2.8 (crosslinkers to resins) and preferably catalyzed by the above described dual catalyst package of 2MI at 1.25 to 1.80 phr along with 2PI at ˜3.0% of the 2MI total by weight. It should be noted that the amounts of catalysts are selected from cure kinetic results; 2PI is confirmed to improve or compliment performance within.
(20) TABLE-US-00001 Type 4 Type 5 Type 7 EEW, g/eq 800-1225 1300-1350 1650-2000 T.sub.m, ° C. 90-120 105-125 115-140 Viscosity, cST at 3,000-10,000 30,000-55,000 over 50000 125□ C.
(21) Various combinations for epoxy resins can be used if desired, although the disclosed combination in this invention appears to perform best. The solid epoxy resin may have an equivalent epoxy weight (EEW) of 800 to 2000. These resins are often described by their “type” to indicate molecular weight (MW). Type 4 and 7 are suitable here; again, it does not mean the resin package in the compositions of this invention is limited only to this specific option.
(22) Type 4 resins may have an EEW of 800-1225, Type 5 resins have an EEW of 1300-1350 and Type 7 resins may have an EEW of 1650-2000. Commercial examples of Type 4 resins include Epon-2004, KD-214C, YD-904. Commercial examples of Type 5 resins include EPON 2005, YD-905, and commercial examples of Type 7 resins include Epon-1007F, YD-017.
(23) In a preferred embodiment, the powder coating composition includes an epoxy resin system comprising: (a) 7.5% to 22.5 wt % toughener resin, wherein the toughener resin is Fortegra 304 or 664-12; (b) 7.5% to 62.5 wt % of an epoxy Type 4 having an EEW of between 800 and 1225; and (c) 15.0% to 85.0 wt % of an epoxy Type 7 having an EEW of between 1650 and 2000, all wt % based on the total weight of the resin.
(24) In accordance with this invention, where Type 4 and Type 7 resins arc employed, the ratio of the Ty
(25) pe 4 resin and the Type 7 resin ranges from 1:8 to 4:1.
(26) Accordingly, in a preferred embodiment, the powder composition described herein is a fusion-bonded epoxy (FBE) composition. Preferred compositions include an epoxy resin prepared from a homogenous mixture of a toughening resin, and Type 4 epoxy resin, and Type 7 epoxy resin, along with a flexible dihydrazide curing agent and dual imidazole catalysts. In an aspect, the fusion-bonded epoxy composition is present in an amount of about 65 to 95 wt %, preferably about 70 to 95 wt %, more preferably about 77.5 to 92.5 wt %, and most preferably about 80 to 92.5 wt % based on the total weight of the powder composition.
(27) In one embodiment, the polymeric binder is dry mixed together with any additives, functionalized pigments and fillers, and the like, and then is typically melt blended by passing through an extruder. The resulting extrudate is solidified by cooling, and then ground or pulverized to form a powder. Alternatively, the additives described herein may be combined with other compositions to be added to the powder composition after extrusions as post adds.
(28) As discussed above, additives may be added prior to extrusion and be part of the extruded powder composition, or may be added after extrusion. Suitable additives for addition after extrusion include materials that would not perform well if they were added prior to extrusion.
(29) Optional additives can include materials that provide a desired effect on the powder finish or the powder composition, or additives that can improve the application of the powder, the melting and/or curing, or the final performance or appearance. Examples of optional additives which may be useful include: pigments and fillers, else cure catalysts, antioxidants, color stabilizers, anti-corrosion additives, degassing additives, flow control agents, and the like.
(30) Examples
(31) These examples are merely for illustrative purposes only and are not meant to be limiting on the scope of the appended claims. All parts, percentages, ratios, etc. in the examples and the specification are by weight, unless noted otherwise.
(32) An exemplary coating composition of the current invention may include additional materials in varying concentrations as individual needs may require. For example, the composition may further include one or more fillers to control cobwebbing, pigments, fillers, adhesion promoters, and combinations thereof.
(33) If desired, a coating composition of the present invention can include at least 0.1 wt % of a pigment, based on the total weight of the dry epoxy resin. Typically, if used, a coating composition of this invention includes no greater than 5.0 wt % of a pigment, based on the total weight of the solid resin.
(34) When ready for application, the various parts of the coating composition are mixed together immediately prior to spray application. The coating composition can be applied directly over preheated steel with immediate residual heat curing. The flexibility properties of the cured coating composition can be measured pursuant to a bend test provided.
(35) Examples
(36) Premix batches of about 1500 grams each was mixed by a high shear propeller mixer for 35 sec (adequate mixing should be guaranteed in production as well). Mixture was extruded using protective twin screws at 85° C. (Z3) and 123° C. (Zone 4) running at 500 rpm with a 18-20 feeding rate. Chips were ground by a Bantam mill and subsequently sieved by a 94T sized screen.
(37) TABLE-US-00002 Example A (parts by wt) Example B (parts by wt) Type 7: 1005.8 Type 7: 1000.0 Type 4: 251.45 Type 4: 250.0 Toughener: 179.6 Toughener: 178.57 ADH: 27.16 SDH: 35.44 Primary Catalyst: 17.8 Primary Catalyst: 17.4 2nd Catalyst: 0.89 2nd Catalyst: 0.87 Wet flow agent: 13.9 Wet flow agent: 13.9 Pigments: 14.94 Pigments: 14.94 Dry flow agent: 0.4% Dry flow agent: 0.4% TOTAL: 1511.1 TOTAL: 1511.1 T.sub.g: 102.0° C. T.sub.g: 101.4° C.
(38) Powder was sprayed onto rebars and dowel bars preheated at 232° C. or 239° C. for designed cure times of 30, 25 and 20 sec (35 and 30 secs if 232° C. preheat) or else as specified. Rebar and dowel bar were coated at 8-12mil, bend at −45° C. free of cracks or peels, with minimal tears and normal amounts of cobwebbing for Example B that performed consistently up to 12 months, in addition to a glossy finish without yellowing or discoloring. It should be noted that the existing was a commercial product with a coating composition based on conventional phenolic cure chemistry and its T.sub.g was of 106.7° C. vs. lower T.sub.g's for amine formulations of this invention at 101-103.0° C., Lower Tg's are typically advantageous in terms of flexibility because the latter is inversely proportional to the former to some extent.
(39) Test Method: Flexibility testing was carried out with a Tecmor Model SEIM mechanical bender, at −45 ° C. for 2 hours post cure, and for 24 hours post cure. It was 239° C. for 45 min preheat for all.
(40) TABLE-US-00003 Example B Example New New New New ACR A SDH SDH SDH SDH (−45° C. Existing New (fresh & in (in 3 (in 6 (in 12 bending) Phenolic ADH 2 weeks) mos) mos) mos) Residual 45, 35, 32, 27, 45, 35, 30, 30, 25, 30, 25, 30, 25, heat cure 30 22 25, 20 20 20 20 time, sec 2 hours ≥0.19 ≥0.19 0 0 0 0 (avg.) (avg.) 24 hours ≥0.19 ≥0.19 0 0 0 0 (avg.) (avg.) NOTE: ACR (actual crack rate) ≤0.19 is considered a pass
Example C of formulation (corresponding to Fig. 5 in the appendix), manufacturing and testing:
(41) TABLE-US-00004 Comments Ingredient wt % Formulation: High MW Type 7 65.90 Medium MW Type 4 16.48 Toughening resin, Toughener 11.77 EEW981.3 SDH (3-6 microns) Sebacic dihydrazide 2.02 Polyacrylate Wet flow agent 0.57 Principal catalyst Imidazole, 2-methyl 1.663 Additive catalyst 2PI (60%) 0.076 Misc. Pigments and fillers 1.06 Post add Dry flow agent 0.45 Processing: Premix: REOS at high speed for 35 sec; Extruder settings: Zone 3 & 4 85° C. & 118° C.; Grinding: Bantam mill, 94T sieve. Coating DSC Enthalpy −49.3 J/g, T.sub.peak 131.1° C., T.sub.onset 107.2° C., T.sub.g 103.1° C. at 7.0° C./min:
(42) Cure kinetics determined for Example C (i.e., the upgraded SDH formulation) by DSC is listed in the table above, which predicts cure times of 17.3 and 14.9 seconds at 232 and 239° C., respectively, consistent with and confirmed by rebar bending results.