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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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  • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
  • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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  • C08J9/143—Halogen containing compounds
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  • C08J9/22—After-treatment of expandable particles; Forming foamed products
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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  • C08G2110/00—Foam properties
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  • C08J2203/16—Unsaturated hydrocarbons
  • C08J2203/162—Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
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Definitions

• the invention described herein pertains generally to a polyurethane foam composition which is blown using at least one hydrofluoro olefin (“HFO”) propellant.
• HFO hydrofluoro olefin
• Two-component low pressure (less than 250 psi) spray polyurethane foam (SPF) kits require a sufficient amount of blowing agent in order to fully dispense the contents of both the A-side (Isocyanate) and B-side (polyols, surfactants, catalysts, etc.) chemicals. This must be done in such a manner where both A and B components are propelled at a predetermined ratio that is maintained throughout the dispensing of the product.
• one component low pressure polyurethane foam (OCF) systems are already pre-mixed in closed systems where the A/B ratio is predefined. OCF systems are typically blown with hydrocarbons, but flammability concerns restrict their usage in certain cylinders.
• blowing agent(s) used must be at least partially miscible with both A-sides and B-sides and should not react with either contents.
• HFC-134a became the non-flammable blowing agent of choice for the low pressure SPF Industry due to relative ease of transition among other factors. While HFC-134a and other HFC blowing agents have an ODP value of zero, these compounds have a high global warming potential (GWP). Unlike ODP, GWP is measured by atmospheric residence time and infrared radiation absorption relative to the Earth's atmosphere. These factors determine the radiative forcing of the molecule. A positive radiative forcing value indicates a higher potential for warming the planet; that is, more solar radiation is absorbed than reflected out to space. The radiative forcing of a particular molecule is compared against the radiative forcing of carbon dioxide. The resulting number is the GWP of the particular molecule, with carbon dioxide given a GWP of 1.
• GWP global warming potential
• Radiative forcing is not a linear quantity, however, and is dependent on external factors such as climate sensitivity and molecule-specific pulse emissions over a particular time period, denoted as time horizons measured in 20, 100, and 500 years.
• time horizons measured in 20, 100, and 500 years.
• the global warming potential of 134a decreases with an increasing time horizon, but the global warming potential of many perfluorocarbons increases with an Increasing time horizon.
• most GWP values are typically reported at a time horizon of 100 years.
• GWP values have changed over time as improved modeling and empirical data becomes readily available. To this end, the GWP of HFC-134a reported by the Intergovernmental Panel on climate Change has changed from: 1300 in 2001; to 1430 In 2007; to 1550 in 2013.
• HFO blowing agents potential low GWP replacements for HFC blowing agents include hydrofluorooelfin (HFO) blowing agents.
• HFO hydrofluorooelfin
• the Solstice® Gas Blowing agent (GBA, HFO-1234ze, trans 1,3,3,3 tetrafluoropropene) produced by Honeywell has been proposed as a blowing agent for low pressure SPF systems.
• Attractive properties of HFO-1234ze include a low boiling point ( ⁇ 19° C.) and favorable kauri-butanol solubility (25 compared to 9.2 for HFC-134a).
• HFO-1234ze has an ODP of zero, is volatle organic carbon (VOC) exempt, and has a GWP of less than 1 due in part to its low atmospheric lifetime ( ⁇ 18 days) compared with HFC-134a (13.4 years).
• VOC volatle organic carbon
• HFO blowing agents like HFO-1234ze meet requirements for the Kyoto Protocol (GWP ⁇ 150) and are cleared for use under SNAP 21 , the short lifespan of the molecule has led to challenges with the product shelf life of closed SPF systems. Stated earlier, SPF systems contain A-side (isocyanate) and B-side (resin) components stored separately under pressure. Both sides require propellants to fully dispense these mixtures. HFO-1234ze and other HFO blowing agents will break down on the B-side. HFO molecules are believed to react with amine catalysts, for example, via nucleophilic substitution. This reaction produces hydrofluoric acid, which in turn attack surfactants and polyols.
• This invention was developed to overcome some of the limitations of the teachings of the prior art as well as to address long term stability issues when using HFO propellants in blowing polyurethane foams.
• the prior art appears to teach that aromatic polyester polyols are preferred in the “B” side of a two-component polyurethane foam and that there should be no more than approximately 10% aliphatic polyether polyol.
• This composition appeared to be counterintuitive as one having ordinary skill in the art might expect that polyester polyols would be problematic because polyester polyols are greater nucleophiles and therefore, more susceptible to attack.
• the present invention overcomes some of the limitations taught in the prior art by teaching that higher loading of polyether polyols is possible in HFO blown two-component polyurethane foams, this improvement being achieved by the use of a milder catalyst package in combination with the inclusion of glycerol, a low molecular weight triol.
• a two component low pressure polyurethane foam comprising: an A-side comprising: at least one dilsocyanate, and an HFO propellant, and a B-side comprising: approximately 30-50% by weight of at least one polyester polyol; approximately 10-40% by weight of at least one polyether polyol; approximately 1-15% by weight of a triol or a polyol (including diols) having a functionality a ⁇ 2 and having a molecular weight between approximately 90-1,500 inclusive; approximately 0.3-1% by weight of an amine catalyst; approximately 0.3-1% by weight of a potassium-based catalyst; and an HFO propellant.
• the triol is glycerin.
• It is another aspect of the present invention to provide a process to extend the shelf-life of a low-pressure two-component polyurethane spray foam comprising the step of: adding approximately 1-15% by Weight of a triol or a polyol (including diols) having a functionality ⁇ 2 and having a molecular weight between approximately 90-1,500 inclusive to a B-side, the B-side further comprising: approximately 30-50% by weight of at least one polyester polyol; approximately 10-40% by weight of at least one polyether polyol; approximately 0.3-1% by weight of an amine catalyst; approximately 0.3-1% by weight of a potassium-based catalyst; and an HFO propellant; the A-side further comprising: at least one dilsocyanate; and an HFO propellant.
• the triol is glycerin.
• the word “and” Indicates the conjunctive; the word “or” indicates the disjunctive; when the article is phrased in the disjunctive, followed by the words “or both” or “combinations thereof” both the conjunctive and disjunctive are intended.
• the literature would appear to teach that to achieve shelf life stability for an HFO propellant-based two-component polyurethane composition, there should preferably be at least one aromatic polyester polyol (in a major amount) and no more than approximately 10% aliphatic polyether polyol.
• the literature appears to highlight the benefits of polyester polyols, and more specifically aromatic polyester polyols, over those of aliphatic polyether polyols. This composition was believed to be counterintuitive, as one skilled in the art might expect the polyester polyols to be problematic due to the polyester polyols being greater nucleophiles and, therefore, more susceptible to attack.
• the prior art would appear to be teaching that polyether polyols seem to be significantly detrimental to the shelf life of the foam product.
• a shelf-life stable formula blown with a gaseous hydrofluoroolefin (HFO) was selected in the following study to show differences between polyether and polyester polyol loadings.
• the polyester-containing formula observes minimal drift in physical properties while the polyether-containing formula failed over a 6-month accelerated aging process (kit stored at 50° C. for 24 days per the Arrhenius relationship correlates to 6 months real-time aging). Hydroxyl numbers were kept constant for both formulations. Catalysts, surfactants, plasticizers, and relative concentrations thereof were also kept constant.
• Pairs of 12-oz. aluminum cans, 7.5-inch, or 12-inch steel cylinders were filled with appropriate amounts of isocyanate or resin. HFO-1234ze. and nitrogen in order to have a consistent A/B ratio as the kit emptied.
• the A-side and B-side components were sprayed onto a cardboard substrate from pressurized cylinders or cans using a gun or wand dispensing unit, respectively, with a replaceable static mixing nozzle head. Kits were sprayed out at room temperature conditions (23° C. ⁇ 2° C.) and were conditioned (stored) at room temperature conditions prior to spray-out unless stated otherwise. The resultant foam was used for the testing of physical properties.
• Gel and tack-free times were recorded along with the measured A/B ratio, determined by the weights of each cylinder or can before and after the spray-out.
• Gel time is defined as the time in which the strength of the foamed product is greater than that of the adhesive strength of the curing foam to a particular probe, such as a toothpick, spatula, etc.
• a gel time is reached when a probe can be inserted into the product and removed cleanly without any material adhered to the probe. This is facilitated by an increase of the crosslink density through the formation of urethane and urea linkages. At a particular conversion fraction, the majority of reacted components behave as a structure of seemingly infinite molecular weight.
• Tack-free time is defined as the time at which the foam surface is no longer sticky to the touch.
• A/B ratio is simply the ratio of the weight of the contents sprayed out from the A-side divided by that of the B-side. The target A/B ratio is 1.10 for this product.
• the cured foam sample was cut approximately 18-24 hours after initial spray-out. Density measurements were made in accordance with ASTM 01622 and involved a simple weight to volume ratio calculation. R-value is a measure of foam insulation potential and was recorded via 8 ⁇ 8 ⁇ 1 in 3 foam samples utilizing a LaserComp Fox 250 (TA Instruments, New Castle, Del.) in accordance with ASTM C518. While not important to adhesive properties of the foam, it was utilized as a means to measure cell structure degradation over time. Compression stress was measured as an average of six 2 ⁇ 2 ⁇ 1 in 3 samples in accordance with ASTM 01621. Compressive stress was taken at 10% deformation from the original height of the foam specimen and were parallel to the rise of the foam.
• Foam dimensional stability was measured in accordance with ASTM D2126.
• 4 ⁇ 4 ⁇ 1 In 3 foam samples were subjected to 23° C. and 50% relative humidity, 70° C. and ambient relative humidity, 70° C. and 100% relative humidity, and ⁇ 20° C. and ambient relative humidity for 3, 7, and 30 days each. Changes in volume were measured as a percentage growth or shrink to the initial volume of the foam sample.
• Kits stored for a period of 12 days at 50° C. will simulate 3 months room temperature shelf life. Kits were sprayed out after different accelerated aging intervals and underwent the physical property testing listed above in the preceding paragraphs.
• the catalytic decay rate (CDR) or the ratio of accelerated aging gel time to that of initial gel time, was also recorded in order to determine gel time shift over the age of the kit.
• Adhesive Failure was defined as the final loading before board-to-board separation of the test “sandwich.” This number was then subtracted from the steel plate of the top of the testing jig (17.5 lbs) and divided by 4 to produce the Resistance value. Mode of failure (adhesive, cohesive) average bead width, and amount of chemical were all recorded.
• FTIR Fourier Transform Infrared Spectroscopy
• polyester polyols and more specifically aromatic polyester polyols, over that of the especially aliphatic (and typically lower viscosity) polyether polyols.
• polyester polyols, with their longer, stiffer backbones do not reptate as much as the polyether polyols, thereby limiting the probability of fluoride attack.
• Aromatic groups on the polyester polyols could also induce a pi-pi shielding effect, therefore reducing (but not preventing) fluoride interaction.
• a shelf life stability study was performed under accelerated aging conditions for a polyester polyol based polyurethane foam control; and a polyether polyol based polyurethane foam comparative.
• the polyester polyol control formula included mostly polyester polyols, while the polyether formula contained mainly aliphatic ether polyols. Catalysts, surfactants, plasticizers, and relative concentrations thereof were kept constant. B-side OH-values were kept constant.
• Hydroxyl numbers were kept constant for both formulations to remove any isocyanate index concerns. Catalysts, surfactants, plasticizers, and relative concentrations thereof were also kept constant.
• An HFO-blown formula should preferably meet or exceed the adhesive properties of similar, current HFC-blown adhesive products and must be shelf life stable up to 12 months or more.
• Good adhesives tend to have a mix of both polyester and polyether polyols because their adhesion mechanisms are different but beneficial in their own right.
• Polyether polyols tend to offer greater flexibility, hydrolytic stability, and are low in viscosity while polyester polyols offer greater cohesive strength yet are higher in viscosity. It is therefore desirable to determine a means of introducing polyether polyol or polyols into an adhesive formula in addition to polyester polyols. Yet as it was shown earlier in this application that polyether polyols are more difficult to formulate into a stable HFO-blown formula.
• HFO-blown product with significant polyether polyol and polyester polyol loading on the B-side blend was developed.
• the HFO molecule selected was HFO-1234ze, commercially-known as Solstince® Gas Blowing Agent (GBA), producted by Honeywell.
• GBA Solstince® Gas Blowing Agent
• HFO LPSPF Adhesive a formulation technique was developed so that the polyether poylols would be stable enough over the shelf life of this particular adhesive, henceforth referred to as HFO LPSPF Adhesive.
• the formulated HFO LPSPF adhesive product of the present invention was able to reach a 12-month accelerated aged shelf life stability first in pairs of 12-oz aluminum cans. Physical comparisons of core foam samples of taken at initial, 3, 8, and 12 months accelerated aging were taken. Qualitatively, the core foam samples appear almost indistinguishable to one another, as the product undergoes minimal change in cell structure appearance or color body shift (a B-side color body shift toward a yellower color could be a qualitative sign of formula degredation).
• the formula is stable with respect to gelation and tack-free times, as tack-free drift advances 1:10 minutes and gelation drift advances 0:49 minutes, resulting in a catalytic decay rate (COR) of 1.30—well within the prescribed stability range of less than 2. Furthermore, the desired AB ratio of 1.00 remains tight and in-specification ( ⁇ 0.1 or less varation) throughout the shelf life study.
• the density of the product does increase with respect to age (3.60 lbs/ft 3 at initial conditions versus 4.09 lbs/ft 3 at 12 months acceratated aging) but should not work to the detriment of the formula. Kit temperatures were kept constant in order to rule out any possible density shift due to errant heating. Intuitively, a higher density merited higher compressive stress at 10% strain loading (52.8 psi vs. 61.6 psi). Furthermore, blend monitoring with the FTIR did not show appreciable blend degradation in comparison with previous studies.
• the first few data points collected in Table 1 were conducted at similar kit age and similar kit temperature but with A/B ratio varied. For most sampled A/B ratios, the density holds at about 2.60 lbs/ft 3 . To obtain the extreme A/B ratios, the kit was choked on the A or 8-side as it was difficult and undesirable to spray A/B ratios that far from the target A/B ratio of 1.00.
• HFO LPSPF Adhesive product decreases in density once it reaches higher A/B ratios, from 2.70 lbs/ft 3 at an extremely low A/B ratio of 0.69 to 2.20 lbs/ft 3 at an extremely high A/B ratio of 1.31.
• a linear R 2 dependence of 0.71 demonstrates moderate correlation between increasing A/B ratio and decreasing density. This was unexpected, but is plausible given the fact that reduced catalytic behavior will allow for greater foam expansion and, consequently, lower density.
• Kit age and A/B ratios should impact foam properties as little as possible, but of course that only accounts for standard operating temperature spray-outs. It is imperative to know how the kit will behave at temperatures outside of these prescribed ranges. Therefore, two kits were conditioned at 5° C. and 50° C. for a period of 1 week in a controllable refrigerator and an oven, respectively.
• the kit sprayed out at 5° C. had a gel time that mimicked the spray-out at 6 months (267 seconds vs. 260 seconds) but had a longer tack-free time (597 seconds vs. 480 seconds—a difference of roughly two minutes). This longer cure time resulted in a lower density (2.38 lbs/ft 3 ) than at room temperature for most sampled A/B ratios.
• the kit was able to maintain both a bead and spatter pattern spray-out.
• the kit also had percent empties greater than 90% on both the A- and B-side cylinders and stayed between +0.2 of the target 1.00 A/B ratio for over 80% of the kit, resulting in a total through-kit A/B ratio of 0.96.
• the 50° C. spray out also produced a bead and spatter spray patterns as well as the majority of the kit operating between ⁇ 0.2 of the target 1.00 A/B ratio for over 80% of the kit. Note the change in gel and tack-free free times, which increased by just over one minute at similar A/B ratios for gel (142 seconds vs.
• the foam samples at all NB ratio ranges, kit ages, and temperature spray-outs were dimensionally stable, falling between ⁇ 1% volume change after 30 days of subjecting the foam specimens to the respective environments of room temperature, ⁇ 20° C., 70° C., and 70° C. with 100% relative humidity. The importance of this cannot be overlooked, as an adhesive which shrinks or expands over time in multiple environments will reduce the look and performance of the foam and is therefore undesirable. This product appears to be dimensionally stable.
• Table II organizes the pull test data. A total of two trials were conducted for each product. Kit age was kept constant, and A/B ratios were kept within ⁇ 0.1 of the target A/B ratio of the product. Amount of product sprayed onto the boards was also kept relatively consistent.
• the HFC-blown adhesive product demonstrated consistent adhesive failure which correlated to similar Resistance values of 176 lbf and 178 lbf. Both samples failed via cohesive failure; that is, the foam itself failed and not the adherence to the substrates.
• the HFO LPSPF Adhesive pull test was inconclusive. On both cases, the adhesive did not fail. Instead, an external event prevented proper measurement of the adhesive strength. In the first trial, anchoring screws holding the plywood to the base popped.
• HFO LPSPF Adhesive is a product with significant polyether and polyester loading on the B-side that has demonstrated stability over a 12-month accelerated aging study. Excellent wetting characteristics as well as system robustness and tensile properties are highlights of this product. In addition, a bead and spatter spray pattern are obtainable with this product.
• Pairs of 12-oz aluminum cans were aged at 50° C. for 12 days to simulate three months of accelerated aging.
• the density increased (3.60 lbs/ft 3 initial vs. 4.09 lbs/ft 3 at 12 months), which resulted in enhanced compression strength at 10% loading (52.7 psi vs. 61.6 psi).
• gel and tack-free times remained fairly consistent, undergoing a 49 second increase in gel and a roughly 1.5 minute increase in tack-free time across twelve months. This resulted in a maximum catalytic decay rate (CDR) value of 1.30.
• CDR catalytic decay rate
• the HFO LPSPF Adhesive system had values of 1640 lbf and 2200 lbf, which correlated to Resistance values of 406 and 546.
• this product did not fail under both tests. Instead, the first test was stopped when the anchoring screws securing the plywood sandwich to the base failed, and the second test was stopped when the load cell maxed out. Therefore, the actual Resistance of this product is unknown, but is understood to be high. A potential issue of some foam expansion while curing resulted in small (3 ⁇ 8-inch max.) gaps between the two plywood substrates. Such an issue may be remedied with small formula adjustments.
• HFC-blown polyurethane foams and HFO-blown polyurethane foams are not drop-in replacements.
• polyether polyols have better adhesive properties than polyester polyols. This is believed to be due to the lower polarity of polyether polyols, which reduces surface tension and therefore increases wetting with the substrate.
• polyester polyols allow for increased tensile properties and higher modulus. It is therefore beneficial to determine a means of introducing polyether polyol or polyols into an adhesive formula along with polyester polyols.
• a formula with a reduced catalyst package was utilized in order to meet the reactivity profile of the adhesive polyurethane product. By reducing the amount of catalyst present in the system, and through general formulation adjustments, a product with 35% polyether polyol loading on the B-side blend was developed.
• glycerin as a fluoride ion scavenger may beneficially increase the shelf life stability of this product.
• Comparisons of HFO formulations are illustrated in Table III. Note that it is now possible to have significant amounts of polyester polyols and polyether polyols In the composition, provided that at least some glycerin (synonymously “glycerol”) is also present, a simple triol. It is recognized that the fluoride ion scavenger will preferably have a functionality of ⁇ 2.0, preferably ⁇ 2.2.
• glycerin is one specific example of a triol with scavenging capabilities
• the invention is not limited to such.
• lower molecular weight polyols e.g., a triol or specifically a polyol (including diols) having a functionality a ⁇ 2, preferably ⁇ 2.2 are believed to be useful in this invention.
• Molecular weight ranges of the polyol(s) are anticipated to range between ⁇ 90 to ⁇ 1500 g/mol are believed to be applicable to this invention.
• composition “A” which is a no glycerin, pure polyester polyol formulation
• This composition was a borderline fall on CDR (gel), and a fall on CDR (tack-free).
• the conclusion that may be drawn is that by simply taking an HFO generation I formula (High Density) and reducing catalyst content did not produce an acceptable formula.
• This composition was a borderline fail on CDR (gel), and a fail on CDR (tack-free). The conclusion that may be drawn is that adding water to system exacerbates Tack-Free CDR, even in small amounts. The foam is still very rigid. A softer foam product is desired for an adhesive product, which is the targeted end-use for this composition.
• the product was a solid pass for both CDR (gel) and CDR (tack-free). The conclusion that may be drawn is that even as polyether and polyester polyols are added with glycerin added to the low catalyst concentration, the composition shows improved reaction stability over the course of its shelf life.
• BDO another small molecule like glycerin, appears to help with reactive stability.
• the collapsing foam product may be attributable to the fact that BDO is di-functional and fluoride ion scavenging creates chain terminus. Glycerin is tri-functional, which significantly reduces the likelihood of chain terminus forming (two fluoride ions on glycerin molecule is highly unlikely due to probability and polarity).
• the composition was a solid pass for both CDR (gel) and CDR (tack-free).
• the conclusion that may be drawn is that wwapping out TMR-20 with T-120 merits a solid pass for the foam product.
• composition “C” it is possible to add in polyether polyols to the blend.
• the composition was again a solid pass for both CDR (gel) and CDR (tack-free). The conclusion that may be drawn is that even as polyether polyols are added, glycerin added to the low catalyst concentration improves reaction stability over the course of its shelf life.
• the composition was again a solid pass for both CDR (gel) and CDR (tack-free). The conclusion that may be drawn is that polyester/polyether systems are stable under this formulation.

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• 2018
  • 2018-09-07 US US16/125,052 patent/US20190077934A1/en not_active Abandoned
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