Asphalt roof coating composition having improved recycability

Abstract

Roof coating asphalt compositions containing a compatible blend of non-air oxidized paving grade asphalt binder, asphalt softening point modifier comprising a solvent deasphalted pitch or resin that increases the softening point of the paving grade asphalt binder, impact-modifying polymer and asphalt anti-aging additive. The compositions, are substantially free of air-blown asphalt binder, and have advantages including reduced preparation and coating temperatures, reduced equipoise viscosity, increased resistance to aging and increased recyclability in asphalt pavement.

Description

ASPHALT ROOF COATING COMPOSITION HAVING IMPROVED RECVCLABILITVCtw-Reference to Related Application

[0001] The present disclosure claims the benefit of U.S. Provisional Application Serial No. 63 / 625,854, filed January 26, 2024, which is incorporated herein by reference.Technical Field

[0002] This invention relates to asphalt coatings for shingles and other roofing applications. Methods for preparation and use are also provided.Backgronnd

[0003] Asphalt-based roofing products such as shingles and roll roofing typically include a flexible fiberglass mat coated on both sides with an asphalt coating composition containing at least an asphalt binder and a mineral: filler such as limestone. The roofing surface that will be exposed to the weather is typically further covered with inorganic roofing: grannies ami the underlying surface is typically ferfoer covered with fine sand. The asphalt coaling composition is somefimes referred to as ^coating aspWiTor 'Toof coaling asphalt,'' and representx one of the primary ingredients for mainif'actaring asphalt- based roofing materials For asphalt roofing shingles, coating asphalt typically represents about 18 to 30 % of the finished shingle weight.

[0004] Coating asphalt desirably imparts to the finished footing material both durable waterproofing properties and resistance to etivironmenral weathering, Coating asphalts having low penetration at room temperature and high softening points are generally preferred, Penetration values are related to material stiffness, with low er penetration values indicafeg a stiffer asphalt material compared to that of the starring or “base’’ asphalt. Asphalt blowing, also referred io as oxidation or air rectification, is normally used to convert soft base asphalts into oxidized or air-blown coating asphalts liaving a desired Consistency. The blowing proces s increases the soften ing poi nt and reduces the penetration value for the finished air-btown asphalt, Typically, the blowing process includes: heating the base aspbal b generally to a temperature of 232 °C (450 *F) to 260 °C (500eF), and blowing air into the heated asphalt for a duration needed to reach the desired properties. The blowing process is temperahire and time dependent with an inverse relationship of temperature and: time. Thus, at higher temperatures the Mowing time is generally less than flic time required io achieve the same properties ai lower temperatures. The exchangesurface or contact surface between the hot asphalt and the nature and temperature of the air forced into it generally are also factors in tfetermining the blowing process length and the required air quantity ,

[0005] Air blowing is highly energy intensive and may produce greenhouse gases and other undesirable emissions. Air blowing also degrades the base asphalt properties by volatilizing lighter oil fractions that impart flexibility and durability to an asphalt binder.Despite these disadvantages, mostgreater than about 90 %) of all inanufacttired asphalt roofing shingles use air-blown coating asphalt. Air blowing in effect pre-ages the asphalt binder so that its properties have reduced tendency to change during the service life of a roofing material,Summary

[0006] The present invention provides, m one aspect, a roof coating asphalt eomposifion comprising a compatible blend of a ) aon-kif oxidized paving grade asphalt hinder, b) asphalt softening point modifier comprising a solvent deasphalted pitch or resin that increases ths softening point of the paving grade asphalt binder, c) inipacj-niodifMng polymer andd) asphalt ami-aging: additive, the composition being substantially free of' airblown asphalt binder.

[0007] The present invention provides, in another aspect, a method for making a roof coating asphalt composition comprising the steps of blending under low shear conditions a mixture of a) non-air oxidized paving grade asphal t binder, b) asphalt softening point modifier comprising a sol ved deasphalted pitch or resin that increases the softening point of the paving grade asphalt binder, e) impaci-modiiying polymer and d) asphalt anti-aging additi ve, to form a compatible blend that is substantially free of air-blown asphalt binder.

[0008] The present invention provides, in a further aspect, a method for making a rooting material comprising: the steps of applying ttea flexible substrate web a roof coating asphalt composition comprising a molten compatible blend of a) non-air oxidized paving grade asphalt hinder, b) asphalt softening point tnodifc comprising a sol vent deasphalted pitch or resin that increases the softening point of die paving grade asplhdt bifoter, c):iimpaet-modi^mg polymer and d) asphalt ami-aging additive, the composition beingsubstantially free of aii-biawti asphalt binder; followed by applying to the molten, blend a layer of finely-divided inorganic roofing granules.

[0009] The present invention proridest in a yet another aspect, a method for recyd ing:asphalt roofing 'waste comprising the steps of providing roofing waste, crosaitiiiig .anasphalt binder comprising a) non-air oxidized paving grade a sphalt binder, b) asphalt softening point modifier comprising a solvent deasphalted pitch or resin that increased the softening point .of the paving grade asphalt hinder, c) impact-modifymg polymer and. d) asphalt anti-aging additive; grinding or otherwise coiTOtiinuting the roofing waste; mixing the comminuted roofing waste with virgin pavement grade asphalt binder and aggregate; applying the resulting mixture to a pavement substrate; and compacting the resulting applied mixture to form a pavement.

[0010] la. some embtidirhentS die asphalt anti-aging additive comprises a partial ester having a hydroxyl number greater than 25 mg KOH / g. In some embodiments the asphalt anti-aging additive comprises a sterol, e,g., a crude sterol.

[0011] Air In some embodiments the asphalt composition further comprises an asphalt viscosity modifier that increases the viscosity of dis roof coating asphalt composition at: high temperatiites (rig.. temperaiares at or above about 149°C (abmit 300°F), or temperatures at or above about 177°C (about 350°F)). Increased viscosities at such temperatures can fee advantageous in roof shingle mamifacturing operations;

[0012] The disclosed impositions: and methods can reduce roofing materialprocessing time, temperatureand energy requirements via the elim ination of air blowing,and can provide improved roofing materials having one or more -of increased resistance io environmental aging; improved mechanical properties; increased service life; and more recyclable post-consumer shingle waste offering one or both of increased addition levels into recycled pavement and reduced adverse impact upon recycledpavement life,Brief Deseriptfon sf the Drawing

[0013] In the accompanying Drawing, Fig, 1 is a graph showing complex rrtodtilus vs. .ftequcncy curves for unaged and aged- embodiments of the disclosed roof coating Compost lions compared 10 an usaged and aged coit vehtiorsal roof coating composition ebntainuig. air-oxidreed asphalt binder;

[0014] Fig, 2 is a graph showing phase angle vs. ftequency rheology curves for imaged and aged embodiments of the disclosed roof coating compositiniis compared to an imaged arid aged eonvemiona i roof coating compositien containing air-oxidised asphalt binder;

[0015] Fig. 3 shows photos depicting granule adhesion after repeated Scrubbing for asphalt shingles made using embedments of the discl osed roof coating compositions compared to a shingle made using a conventional roof coating composition containing airoxidized asphalt binder;

[0016] Fig. 4 is a graph showing complex modulus vs. fiequency curves for unaged and aged embodiments of the disclosed roof coating compositi ons;

[0017] Fig, 5 is a graph showing phase angle vs. frequepey rheology curves for imaged and aged enibodinients of the disclosed roof coating compositions; and

[0018] Fig. 6 is a graph showing viscosity vs. temperature (®F) for unaged and aged embodiments of the disclosed roof coating compositions compared to a polyiner-modifted aspha lt (PM A) roof coating composition. and an air-blown roof coating compos ition.Deiai I ed D eseri pti on

[0019] The: present specification provides certain definitions and methods to betterdefine the present invention and to guide those of ordinary skill in the art in the practice of the present inveition, Provision, or hekoflhcptoVisibtvof a definition for a particular term or phrase is not meant to bely any particular importance, or lad., thereof. Rather, and unless otherwise noted, terms are to he understood according to conventional usage by those of ordinary skill in: the relevant art.

[0020] The modifier “about” used in connection with a quantity is inclusive oftbe stated value, includes values rounded to the nearest sigm&ant figure, and has the meaning dictated by the context fo.g.. includes the degree of error associated with measurement of theparticular quantity) .

[0021] Where ranges are disclosed, the endpoints of all ranges directed to the -same component or property are inclusi ve and independently Combinable (e.g. , ranges of ‘fop to about 25 wt.ot awtii 5 m. "v to auotit 20 wt A is incluswc of the endpomte mid all isitermedtate values of the ranges of “abou t 5 wt. % io about 25 wt.“about 20 wt, % to about 25 wt. %’*, etc.). Further, ranges are inclusive of all numbers subsumed within that range (reg., 1 to 5 includes I, 1.5, 2, 2:75, 3, 3.SIL 4 and 5).

[0022] The terms “first'’ “second, ' and the like, as used herein do not denote any order, quantity , or importance, but rather arc used to distinguish one dement from another. Also, the terms “a” and “an” do not denote a limitation of quantity , but rather denote the presence of at least one of the referenced items, and the terms “front," “back,” “bottom” and “top "Unless othe wise noted, are merely used fdr fabvenfece of description, arid afe not I fat ted io any one position or spatial orientation.

[0023] Reference ihrougiiout the specification to “one embodiment” or “aft embodiment means that a particular feature, structure, or characteristic described in connection with an Embodiment is included in at least one embodmiEot. Thus. the appearance of the phrases “i n one embodiment” or “in an embodiment” in various places throughput the specification is not necessarily referring to the same embodiment or to only a single embodiment Further, the recited features, structares or characteristics may be combined in any suitable manner iii one or more other embodiments.

[0024] The term “asphalt binder" ’ refers to a highly viscous liquid or setnifalid form of black or dark-colored ( solid,:semisolld. or viscous ) cementitious substances, natural ar tiiimufactiired, composed principally of high molecular weight hydrocarbotis, ofwhich asphalts, tars, pitches, and asphaltenes -are typical The term asphalt binder also includes binders recovered tor extracted (e.g: , via solvent extinction;) fain recycled aged; asphalt pavement, recycled shingle wasted or fain any other a$phalt*eontaining products that can be recycled, Depending on the jurisdiction, the term “binder” may re fer to ‘'asphalt,” “asphalt binder ’ or faitumeiv ' arid these terms may be used Interchangeably within this disclosure.

[0025] The term “aggregate” refers to particulate mineral material such as limes tone, granite, trap rock, gravel, crushed gravel sand, ere sited stone, crushed rock, roofing granules, and minerals added to asphalt binder and useful in certain applications such as creating roofing materials or in pavement applications.

[0026] The term eqniviscous temperamre or “EVT” refers to the temperature at which an asphalt-containing composition has an apparent viscosity of 125 centipoise by ASTM D312 mid ASTM D4492M-23.

[0027] The terms “m-crihcar sr “Creep critical” refer to the low temperature relaxation grade of an asphalt binder. The creep critical temperature is the temperature at which The slope of ihc< flexural creep stiffness versus creep lime has an absolute value of fiJOfe Alteriifavely, the Stifaess and creep critical temperatures: can te determined fem a 4 mm Dynamic Shear Rheometer (DS:R) test, or from a Bending Beam Rheoriietet (BBR) test according ip ASTM D6648-08(2016).

[0028] Unless otherwise specified, the term “molecular weight” refers to number average molecular weight (Mu). Number average and weight average (Mw) molecularweight values nw be deWoined using "Gel Permeation Oitematography (GPC) and a polystyrene standard,

[0029] The terms “neat” and ‘ ‘virgin” when used with respect to an asphalt binder refer to a binder that lias not yet been used in or recycled frotn asphalt tnaternds te.y. , asphalt pavement or asphalt shingles), and can include Performance Grade asphalt binders

[0030] The term “partial ester” refers its a material that contains ester linkages and also contains either or both of unreacted carboxyl groups and unreacted hydroxyl groups,

[0031] The term “partial esterifieatfon” refers to an ester-ferming reaction that produces one or more partial esters,

[0032] The term “P .AV” refers to a Pressurized Aging Vessel , A PAV fest is used to urnntetc acvcLteitet. agit'g oi rtglutt henkr as ocscnbcd m . V' I M D( I - l'k Standard Practice for Accetated Aging of Asphalt Binder bsn <? a Pressurized Aging Vessel (PAV).

[0033] The: terms “polymer modified asphalt'' and ”PMA” refer to an asphalt binder that has Veen combined with one or more polymers to improve desiredfolader physical properties, for example to alter tlte binder's service tempcratute range, improve fatigue and thermal crack; ng resistance, or reduce ruting in pavement made using the asphalt binder,

[0034] The- term “polymer” includes, independently, Iwwolymers, copolymers, ferpalymeny block copolymers, segmented copolymers, graft copolymers:, and any mixture or combination thereof, and iticludcs both virgin (vfe., new) polymers and polymers obtained from recycling sources.

[0035] The terms “re-refined engine oil bottoms” teid “REGS” refer to the nan-distillable residuum from a vacuum tower in a used oil re-refinery. In such a re-tefiticry, used motor oil is recycled via atespherte distillation followed by vacuum distillation, leaving a non- distillable residuum ( viz., REOB) fin th? vacuum tower, REOB is also referred to as a ‘ vacuimi tower asphalt extender” or “VTAE”, and the terms REOB and VTAE arc generally intcrchangeahle. REOBfVTAE materials ate further defined and de, scribed hi publication lS-2:35,

[0036] The terms “reclaimed asphalt pavement” and “RAP” refer to asphalt feat has been removed or excavated: &®n a previously used asphalt paventeBtrtqad or other similar structure, and processed for reuse by any of a variety of well-known methods, including milling, ripping, bteakfeg. criishing, or pulverizing,

[0037] The terms “reclaimed asphalt shingles ’ and “R AS" refer to shingles frontWKS including roof tear-off, niatiufitelure's waste asphalt shingles and post-consumer waste.

[0038] The term “RTFO” refers to a Rolling Thin Film Oven. A RFTO test is used for simulating the short-term aging of asphalt b inders as described in ASTM D2872-19, Standard Test Method for E ffect of Heat and Air on a Moving Film of Asphalt (Rolling Thin-Film Oven Test).

[0039] The terms "roof coating asphalt" or“roof coatifig asphalt binder' refer to asphalt binds? that is suitable to make roofing materials as defined by ASTM D 3462-19, and having a minimum sofiening point of 88°C (196° F) to 160°C (320° F) when tested accofoing to ASTM D16 without a mineral filler and having a minimum penetration of 15 dmm at 25°C (77 ° F) when tested according io ASTM D5M-20.

[0040] The terms “roofing fillers” w "fillers" refer to materials such as minerals that are: used in the manufacture of roof coating asphalt binders. The: filler materials typically have a particle size of about 8 Mesh or smaller (for example abort! 30 mesh or smaller, about: 70 mesh or smaller, or about I Off fttesh or smaller) and about 400 titesh larger (for example about 270 mesh or larger, or about 200 mesh or larger), and may range ftora about I to about 80 percent by weight of the total roof coating asphalt composition,

[0041] The terms "roofing granules” or “granules” refer to an inorganic paitieulate material (e.g., a natural or synthetic mineral) that can be applied atop a roofing material a shingle) to provide one or more of improved heat resistance, durability; color or 'infrared reflectivity to the finished roofing material.

[0042] The term “roofing material” refers to an asphalt binder-containing shcetiike product for use on a. roof, including roofing shingles, roll roofing, built-up roofing, postconsumer waste fe.g;, tear-off shingles) or mantifacftire's waste shingles, shingle maiirfetettiring scrap, roofing felt, and the like.

[0004] ] The terms “s-Critical” or “stiffness critical refer to the low temperature stiffness grade of aft asphalt binder The sfifftiess critical temperature is the temperainre at which an asphalt binder tested according to ASTM D6648t-08(2flld) has a fiexural creep Stiffness value of 30(1 MPa or as determined by either the BBR test or 4 him DSR test as described in ATc.The term ”SHRF’ refers to the Strategic Highway Research Program and its performance grade (PG) specifications.

[0045] The term “siibstanrially free of’ when used with respect to a composition thatmay contain a designated material means comainmg less than 5 wt :% and preferably lessthan 2 wt %, less than 1 wt. %, less than 0,5 wt.%, less tfiatj.0,1 wt %, or no detectable amount of such designated material.

[0046] The tern “ ΔTc” is a parameter normally used to evaluate crackfog potential in asphalt paving, but which for purposes of the present disclosure will be adapted to identify cracking potential in asphalt roofing materials ΔTc refers to the value obtained when the low temperature creep ar upvalue critical temperature is subtracted from the low temperature stiffeess critical temperature Tc, To determine the ATc parameter,, a 4 mm DSR test procedure land data analysis methodology according to ASTM D7S43rI6 may be used. Example DSR test procedures and methodology are also disclosed in Published Internatronal Application Nos. WO 2017 / 027096 A2, WO 2017 / 2B692 Al and WO 2017 / 213693 A9, the disclosures of each of which are incorporated herein by -reference in their entirety . Tte 4 -ma DSR test and analysis procedures are also described by SUL C, Farrar, AT , Tuniinello, W., Turner, T„ A New Technique for Measuring fow-temperatijre Properttes of Asphalt Binders with Small Amounts of Material, Transportaiioh Research Record: No 168L, TRB 2010. See also Sui, C., Farrar, M 1. Harnsberger, P. M., Tuminello, W,H., Turner, T. F., New Low Temperature Performance Grading Method Using 4 mm Parallel Plates on a Dynamic Shear Rheometer. TRB Preprint CD, 201 1 , and Farrar, M., et al, (2012), Thin Film Oxidative Aging and Low Te-mpcralure Performance Grading Using Small Plate Dynamic Shear Rhcenietry; An Alternative to Standard RTFO, PAV and BBR. Euraisphalt & Eurobitinne 5th E&E Congress -20.12 Istanbul (Paper O5ee- 467), Istanbul: Foundation Wasphak. The ATc parameter can also be determined using a BBR test procedure based on AASHTO T313 (2ndedition 2019) or ASTM D6648- 08(2016). When the BBR test procedure is Used the test should be conducted at a sufficient number ef temperatures sitch that results for the Stiffeess failure criteria of 300 MPa and Creep or m-value failure criteria of 0.300 arc obtained, with one resul t being: below the feilurc criteria and one result being above the faihire criteria. In some instances, for asphalt binders with ATc values less than -5 W this can .require pcribrnilng the BBR test at three or more test temperatures. ATc values calculated ftom data when the BBR criteria reqiiirements referred to above are no! met may not be accurate,

[0047] The terms “Useful Temperature Interval’ or “UTI” refer to the aumerie interval between the highest temperature and lowest temperature for which pavement made from aspecifi c paving grade asphalt binder is designed . For road paving applications, t he seasonal and geographic extremes of ternperaiare will determine the desired or required UTI, UT1 is determined using a series of AASHTO arid ASTM standard tests developed by the Strategic Highway Research Program (SHRP), also known as the ‘Tgtfonnance Grading” (PG) speeifieation, For example, an asphalt binder designed to accommodate a high temperature of 64sC, and a low temperature of™-22°C. has a UT1 of 86 and may be referred to as a PG 64*22 asphalt binder.

[0048] All weights, parts and percentages are based on weight unless otherwise specified-,

[0049] Qu a weight basis, asphalt payment is die world's most recycled material. At the end of a pavement A service life, the old pavetnenl max ire remo ved using a milling or grinding inaehine, mixed with fresh (also known as ”S ron r ' > asphalt binder and fresh aggregate as needed, and then reapplied and compacted using a paving: machine Used asphalt roofing shingles, waste cut-offs from, shingle manufecturisig: and other post- or ex- ccsisumer asphalt roofing waste can also be recycled by grinding up dr otherwise comrimWing the waste, and adding it to recycled paying material in the above-nteotioned paving process. However, due to exposure to weathering, the coating asphalt in -a -roofing material degrades significantly d uring a roofing product’s service life, Thus, only limited quantities of post- or ex-consumer roofing waste may be added to an asphalt paving material without unduly shortening the service life of the recycled pavement. Instead, most recycled roofing waste winds up in l andfills.

[0050] The disc losed roof coating asphalt composi tions contain non-air oxi dized.paving grade asphalt binder and an asphalt softening point: modifier comprising, a solvent: deasphalted pitch or resin. If used by themselves or in a neat blend, these ingredients would have inadequate durability foruse in eorameraial roofing materials, which usually are sold with a lengthy service life warranty. For example, potcniially desirable paving grade asphalt binders may have a lower soften mg point and fewer melt viscosity than a typical roof toatihg: asphalt. This can facilitate melt application of the coating when making shingles and Other roofing materials, but the reduced softeiung: point may also make t& finished r, mfing material unsuitable for use in hot ar sunny roofing applications. Also, as discussed in I S Patent No. 10,336,906 B2, a paving grade asphalt that is blown to a suitable softening point may have a penetration value that is too low for a roofing material A conventional raof coating asphalt formnlator would instead supplement orcompletely replace ths disclosed asphalt-based Ingredients wife air-blown asphalt binder. However, as discussed in mere detail below, acceptable melt application properties and acceptable finished product durability can be obtained in a roof coating composition that is substantially free of air-blown asphalt binder by employing the disclosed blend of paving grade asphalt binder and asphalt softesiiag point modifier together wife. the above- mentioned finely-divided impact-modifying solid polymer and asphalt anti-aging additive.

[0051] A variety of non- an osuh / cd pm tr-g giadc asphalt binders indy be used in the discloses! c-onrpositions and methods. The paving grade asphalt binder may for example have a PG 70-22, PG 70-16, PG 70- 10, PG 67-22, PG 67- 10, PG 64-22 / PG 58-2S, PG 58- 22, PG 52-34 or PG 46-34 performance grade rating as evaluated using AASHTQ M320 a 40-50. 60-70, 85- 100 or 12.0-150 penetration grade rating as evaluated using ASTM D046M-20; an All-4000 or AR-8000 viscosity rating as evaluated using ASTM D 338TM- 18; or an AC / 30 grade rating In some embodiments the nornarr oxidized paving grade asphal t binder is a PG 64-22: asphalt hinder. Siritabl e pavi ng grade asphalt 'binders, may be Obtained Win a vari ety of sources including asphalt producing refineries, tins, refinery vacuum tovrc r bottom s, pi tch and other rest dues of processing of vacuum ta wer hot tarns; from bituminous coal; and from other natural bitmninotss materials such as fee products extracted from oil sands in Alberta and elsewhere and the products derived from oil sands by various refinery processes. Exemplary pavement grade asphalt binder suppliers incl ude .(Associated Asphalt, Ergon Asphalt & Emulsions, ExxonMobil, Shell and Valero.

[0052] The noti-aii' oxidized paving grade asphalt binder may be or may include a PMA binder. Exemplary polymers for use in PMA binders include elastomers (e.g,,styfene-butadisne (SBR) or styrene-butifoiene-styretie ( SBS)) rubbers, plastoraers (e.g. , low density polyethylene (LDPE) w ethylene vinyl acetete (EVA)),, and other polymers that will be familiarto persons having ordinary skill in the art of asphalt binder ptadtici on. Exemplary PMA binder suppliers include fee pavement grade asphalt binder suppbeis mentte.ncd above.

[0053] As discussed in ntarc detail below, the disclosed hrof coating compositions also contain an ifopact-wodiiy mg polymer. In some embodiments, fee polymer in a PMA binder may also serve as fee impact-modify Ing polymer or as an add! (Iona! impactmodifying polymer. When PMA binders containing an impact-mo'difyihg'pbiymer arc employ ed, the respective amounts of aon-alr oxidized paving grade asphalt binder and !in:pac(>rnod!fyii!g polymer arc deterrftificd by subtiactlng the polymer weight from fee.PMA binder weight, and by adding the PMA polymer weight to the weight of impact* :mctdifyiRg polymer that may otherwise be: present in the: roof coating composition.

[0054] The non-air oxidized paving grade asphalt binder may also include a variety af chemical modifiers. Exemplary such chemical modifiers include acids (e.g;, pah phe-pi' it tc aci£ <JT'A j ) afitiiAtdaBis or < xhhrb. aiHt-sit ippinjt ac.dmxcs btrfewcd oils, extenders, sulfur), hydrocarbon solvents, rejuvenators and other materials suchas PGXpand™ 502 polymeric additive from Sripath Technologies,

[0055] The non-air oxidized paving grade asphal t binder may for example represent at least about 25 wt. % or at least about 30 wt. % and up to about 40 wt. T« or up to about 35 wt. % of the coating asphali composition ,

[0056] A variety of asphalt softening point modifiers may be used in the disclosed compositions and methods to alter penetration values and viscosities. An increase in viscosity will typically correspond to a decreased penetration value and an increased softening point, and a reduction in viscosity will typically correspond to an increased penetration value and a decreased softening point Exemplary sofenitig point modifiers itic lode solvent deasphalted pitch ( al so referred io as "res id" or “bottoms "' ’) , and a variety of resins discussed in more detail below.

[0057] Exemplary solvent deasphalted pilch mate rials may for example be obtained from a liquid-liquid extraction process that employs a low molecular weight, hydnxaarbon solvent (e g. , a C3 to Ch aliphatic solvent such as propane) io separate an asphalt feedstock imo deasphalted oil and pitch. In some embodiments, the solvent deasphalted pitch is a propane deasphalted asphalt. Exemplary solvent deasphalted pitch suppliers include Ergon Asphalt & Emulsions, ExxonMobil and Valero.

[0058] Exemplary resins for increasing the roof coating asphalt softening point include a wtde variety of chemistries terd are typically classified by their raw material sources, viz., classified as natural, synthetic ora combatariou of both. Exemplary aataralresins include. rosin and rosin-based resins (e.y. , gam rosin from: tree exudates, tall oil rosins from the by-products of paper mamifacruring, and wood rosin extracted from wood chips and splinters). Ota natal resins include terpene resins which are natural hydrocarbon: resins produced from by-products of paper manufacturing and the citrus industry; fossil resins such as asphaltite or Gilsonite; secretion products from insects such as shellac; and natural resins modified by reaction with vegetable oils or fatty acids. Coal Tar Resins, also called Coumarone - Indene resins, are considered by some to be both natural and syntheticresins. Additional classes of synthetic resins include hydrocarbon resins and phenolic resins, Hydrocarbon resin raw materials mostly eoatein co-prortaB from the ethylenecracking process, These resins caiibe fitriher divided into C5, C9, CIO and pure monomer resins. Tire primary ingredient in C5 resins is pipeiylerie, a litrear five carbon diets. C9 resins ate typically produced using a mixed stream containing various aromatic olefins including indene, methyl indene, and styrene. CIG Resins are sometimes called Dicydopentadiene Resins since dicydopeniadiene is the primary reactive component.Pure monomer resins are aromatie resins mosfly produced from high purity vinyl aromatic monomers including styrene, alpha methyl styrene, and vinyl toluene. Phenolic resins, as the name implies, are produced from phenol and phenol derivatives. While there are some phenolic resins produced using raw material sourced from coal, the vast inapt riv at .phenolic resins are produced syntlteticaily from cumene. Common phenol dem jtnes inchide bisphenol A, terhbaiyl phenol, cetyl phenol, npny I phenol, and resorcinol. Phenol and its derivatives are most often reacted with aldehydes to increase their softening point and molecular weight with formaldehyde being (lie most used aldehyde.

[0059] Combinations of naiurai and synthetic resins are often referred to as hybridresins. Exemplary hybrid resins are exfremely varied but include 1 ) dicyelopentadicnc coreacted with various materials including vegetable oils, fetty acids, rosins, phenolic monontet's, styrene, dibasic acids, diaciris, or polyols; 2) terpene feedstocks reacted with .styrene or phenolic monomers; and 3) rosin reacted with various materials including phenolic monomers, styrene, dibasic acids, diacids, or dicyclopen tadiene.

[0060] The asphalt softening poin l modifier may for ex ample represent at least about25 wi. %, at least about 30 wt %, at least about 35 wt. %, at least about 40 wt. %, at least about 45 wt. %, at least about 50 wt %, or at least about 55 wt. %, and up to about 75 wt. to about 70 wt.%, up to about 65 wt% or up to about 60 wt %, of the coating asphalt eompcsiritoi

[0061] c uwd n tlxcompositions and methods. The polymer inhibits crack propagation; to the rotfr coating composition arid improves impact resistance in the finished roofing material. The polymer desirably is a roiid at room temperature. In some embodiments the polymer has a melting point or glass transition temperature above tire normal highest intended service tanperawre of the roofing material and below the asphalt bi nder melting point; As mentioned, above, the polymer may be introduced via a PMA binder, and may also beseparately introduced. For separate mtoduetfon, the polymer is:mixed with the molted asphalt binder to provide a homogeneous cotnpositton that desirably does not undergo separation after mixing. Exemplary polymers include homopolymers, copolymers (including terpolymers and tetrapolymera), block copolymers, graft eopolyfficrs, waxes, rubbers, and mixtures or blends thereof, including thwoplastic piyolefins such as low- density polyethylene (LDPE), linear low-density polyethylene (LWPE), very-low-density polyethylene (VT.DPE), ultra-low’deasily polyethylene (IJLDRE), medium-density poIyetfeyletK- (M.D.PE), polypropylene (PE), polym^hylpentene (PM'P), polybatene- 1 (PB- 1), polybutadienes, ethylene-octene copolymers, ethylene-vinyl acetate copolymers, reactive ethylene terpolymers (e.g., .ELVALOY,’Mpolymers}, stereo-block polypropylene, olefin block c^olymer^propylene-butane co|wlymm and polystyrene (PS); polyolefin elastomers such as polyisobiitylcne (PIB j. poly (ft-oiefms), ethylene propylene rubber ( EPR) and ethylene propylene diene monomer (M-class) rubber (EPDM rubber), chloroprene polymers (e.g., ; rteopren.es), and the like In some: embodiments the polymer is ah elastomeric block copolymer with polystyrene end blocks and rmsaturated elastomeric mid blocks, such as a tri-block (A-B-A) terpolyrnet; and having: a linear or radial structure,: Exemplary such elastomers include thermoplastic rubbers of styrene-butadie®-stytene- (5BS), and styTene'-lsopretie-styrene (SIS) block copolymers, such as -those available from Kraton Corporation as KtatoufMSBS or SIS copolymers.

[0062] Exemplary waxes include fimctionalized or synthetic waxes and naturally occurring waxes. Suitable synthetic waxes include ethylene bts-stearannde wax (EBS), Fiseher-Tropsch wax (FT), oxidized Flacher-Tropsch wax (FTO), polyolefin waxes such as polyethylene wax (PE), oxidized ^polyethylene wax (PEO), polypropylene wax, polypr^iylene / polyethylcno wax, alcohol wax. silicone wax and petroleum waxes such as naic-rocrystallmc wax and paraffin waxes. Suitable fonctionalixed waxes include amine waxes, amide waxes, ester waxes and carboxylic acid waxes. Suitable naturally oecurrmg waxes may be derived fium plants, animals or minerals, and include plant waxes such as candelillawax, cai'&aiiba wax, rice wax, Japan wax aiid jpjaba oil; animal waxes such ax beeswax, lauolw and whale wax; aud minerarwaxeksueh as Montan Wax, ozokerite and ceresin, fa some embodiments:, the wax is a high density oxidized polyethy lene homopedymer such as Honeywell Titan™ 7686 wax. Ollier exemplary wax suppliers include Sasol Performance Chemicals and Romonta.

[0063] Exemplary rubbers include natural rubber and syttfhe& rubbers such as polyisoprene and isohiiylcnsriseptene copolymers (vfe. . butyl rubbers) . In some embodiments the rubber is a devuleanized rubber made ftnm ground tire rubber, such as the modified devtilcaniaed rubber materials described in ILS, Patent Nos, 6,313d 83 Bl , OOi ,212 82 and 10, 0011,082, and hi IIS, Published Application No, US 2016 / 019449SA1 the dmifeasized rubbers sold under the ECORPHALT trademark. In some embodintenB the polymer is a blend, such as a blend of io w*deus ity PE such as aa LDPE wax and a ground tire robber material such as the above-iaeationed ECORP.HALT polymer.

[0064] The polymer may for example represent at least about 0.1 wt. %, at least about (15 wt %, ar least about I wt %, at least about 2%, or at least about 5 wt. %. and up to about 20 wt. %, up to about 15 wt,%. up to about 10 wt,%, or up to about 8 wt. % of the coating asphalt composition. Waxes may be used in a somewhat broader range of amounts, and may for example represent at least about 0.01 wt. %, at teast about 0.55 wt. least about 50 wt. % or at least about 55 wt. % and up to about 75 wt, %, up to about 70 wL%, up to about 65 wl% Or up to about 60 wt. % of the coating asphalt composition,

[0065] A variety of partial esters having a hydroxyl number greater than 25 mg KOH / gmay be used in the disclosed compositions and methods. The disclosed partial esters help reduce weathering-rslated deterioration of the roofing asphalt composition and roofing materials containing such compositions. Exemplary such partial esters are described in U.S. Patau Application Publication No. US 2022 / 026760 A1 and in Published International Application No. WO 2022 / 1596 WAI, the disclosures of which are ineorporated herein by roferesice, Exemplary suppliers of suitable partial esters include Resina! I Crop.

[0066] The disclosed partial esters preferably have a hydroxyl value that provides a less negative ATc in aged roof coating asphalt captaining the partial ester ata 20 hours of PAV aging at 100 degrees Celsius compared to a similarly-aged roof coating asphalt that does not contain the partial ester. A 20 tair comparison RAV aging test is used in this instance because after longer (e;g., 40 hours) PAY aging, an air oxidized roof coating asphalt may no longer be sufficiently pliable to perfonn ATc festmg.|0067| Exemplary hydroxyl number values may for example be greater than aboui 35 mg / KOH / g, greater than about 50 mgf KOH-'g, greater than about 75 mg / KOH / g or greatertftan about" 100 mg / KFWg, and up to about 250 mg KDlFg, up to about 200 mg KQHfa, up to abo u t 175 mg KOH / g, up to about 150 mg KOH / g, or up to about 120 mg KQH- g.

[0068] The disclosed partial esters, may conveniently be farmed by partially reacting a starting materia! containing carboxyl groups (e.g.. a fatty acid) with one or more polyols or amine aleohds In. some embodiments, the final hydroxyl value of the partial ester maydepend in part on the starting material acid value. For example, reacting fatty acid materials with one or more polyols ©r amine alcohols may cause at least sonic of tire carboxyl groups of the fatty acids to react with the polyols (e.g., through esierification) or amine alcohols fa.g., through amide formation) and lower the resultant acid ftumber of the final partial ester. In some etobodiments, the partial ester may have an acid value of less than about 100, less than about 70, less than about 30, or even lower values. In some embodiments, the acid value o f the starting material may be initially increased to provide mote reactive acid groups within the starting material for bonding with the disclosed polyols or amme nkolirils . The acid values of the starting materials may be increased using a variety of techniques. For example, the starting materials include or may be reacted with an acid or anhydride, acrylic :gcid, adipic acid, fumaric acid, maleic acid, maleic anhydride, succinic acid, neodecanoic acid, other diacids, and the like) to increase the number of carboxylic acid groups in the starting molecule through, for example. Diels- Alder addition or ester addition. The increase in available carboxylic acid groups may allow for additional bonding with polyols w amine alcohols. Additionally, or alternatively, at least some of the available carboxylic acid groups of the starting material may remain within the resultant modified partial ester to, for example, serve other functions in the roof coating asphalt composition. For example, the remaining carboxylic acid groups may help the asphalt binder mix with and bond to rninerai materials.

[0069] In some embodiments., the disclosed modification process may include an alcolwlysis-tansesteritfoation, process to increase the partial ester hydroxyl value. For example, a starting material that already includes erne or more ester linkages (e.g., soybean oi I or other planrtbased ail) may he reacted with a polyol using a transesterification catalyst. A polyol having more than two hydroxyl groups can replace an organic group at such ester linkage. One of the hydroxyl groups of the polyol will be donated to the removed organic group to form a new alcohol which may be left in the reaction product or removed, The polyol (absent that hydroxyl group) will form a new ester linkage with thede-eslerifed -carbonyl group (absent the rertwed organic gfoup) in the thwmbdiM starting material and will provide o® or more additional flee hydroxyl groups.:

[0070] In some enfoodimcms, the starting material for making die partial e ster may be a crude or refined tnatcrial, For example, the starting material may be a low cost, pure or impure, side product or waste stream from the mamtfacmre of a higher value product.

[0071] In some embodiments, the partial esters may include modified tall oil. Conventional tall oil is a byproduct of paper milling and includes a complex mixture of ditBrent compounds including various rosin and fatty acid materials including rosin acids such as abietic acid and its isomers; various fatty acids Including palmitic acid, oleic acid, and linoleic acids, fatty alcohols; sterols; and other alkyl hydrocarbon derivatives, The composition of tall oil varies a great deal depending on supply source, level of refinement, and the like. A typical technique for quantifying the quality or refinement pf tail oil is io refer to the acid number, level of fatty add content, or both. Conventional tall od can be purchased with acid values ranging from about 100-200. or from about 125-165. Tail oil is available in several other forms including for example cmde tall oil and distilled or refined crude tail oil, Distillation of crude tall oil provides various isolated forms of fatty acids including .highly saturated and volatile long-chain fatty acids known as tall oil heads, tall oil fatty acids including CfoCaii felly acids having varying degrees of iinsatu radon, and tall oil rosins or pitch which include largely Css-Csv tricyclic monocarboxylic acids.Commercially distilled tall oil includes a mixture of mostly tall oil faty acid and a varying proportion of tali oil rosin. In some embodiments, the partial esters may be derived from crude tall oil, distilled tall oil, tall oil head, tall oil pitch, ora mixture thereof.

[0072] The hydroxyl value of tall oil, in particular the hydroxyl value of such fatty acids, rosin acids, and similar compounds present in tall oil, may be increased by reacting tali oil under relatively low;temperatures with polyo Is or amine alcohols. The hydroxyl groups or artiiac groups can react with one or more carbonyl groups fog, carboxy lie acid groups) of the fatty acid and rosin acifo 'f ull oil to form an: ester or amide linkage. While reaetion conditions, limes, and sioicbiometsy may be unique to the individual carbonyls and polyols used in. the reaction, the reaction kinetics can be: controlled to fever the addition of such polyols or amine alcohols while promoting tlte retention of a large quantity of residual hydroxyl groups through control of the reaction temperatures and stoichiometric ratios. The disclosed reactions may be carried out at relatively tow temperatures and with the exclusion of ester catalysts to help ensure that availablehydroxyl groups are not consumed though subsequent: crosslinking side reactions thereby prortdittg a high hydroxyl value in the resultant eainpowid,

[0073] .For reactions using polyols and Ihity acids, the reactioft temperatures may be less than 200eC, Temperatures ra excess of 200s>€ may promote the fonnatipn of ester groups and will significantly decrease the hydroxyl value of the resulting eonipounds.

[0074] For reactions using amine alcohols and fatty addy the reaction temperatures may be high enough to favorthe amide reactionabout 150 °C I but generally less than reaction temperatures that favor esterification (e.g. , more than about IhO -Q Temperatures in excess of 2® ®C may promote the formation of ester groups and wfl I xiginifieantly decrease the hydroxyl value of the resulting compounds.

[0075] Larger molecular weight starting materialsrosin acids and high molecular weight acids) and ester-based starting materialspolyesters, vegetable oils, triglycerides, and the like) may require higher reaction temperatures, longer reaction times, or a reaction catalyst to react with the disclosed polyols or atrutte alcohols ax compared to the lower molecular weight fitly acids discussed above.

[0076] la some embodiments: the partial ester is denved from one or more M soybean oil, tall. oil. rosin acid, gum rosin, wood rosin, or tatty acids, with partial esters derived from rosin acid being especially preferred.

[0077] A variety of polyols and amine alcohols may be employed to make the disclosed: partial esters, Suitable polyols and amine alcohols may include, but are not limited to, polyols containing two or more free hydroxyl groups or amines comaimag one or more hydroxyl groups including, for example, ethylene glycol, diethylene glycol., trie-thylene glycol, propylene glycol, dimethylolpropfonie acid, glycerin, trinicfoylo'lpropane. neopentyl, glycol, pentaeiythrifol, di-pcnteen'thritol, sorbitol, sucrose, polyethylene glycol s, polypropylene glycols, mctlianolanline, dimethylethttnolamiiie, ethanolaiiiiuc, aimn&mcthyl propanol, pol><su.llitte polyols, propanolamines, mixtures thereof and the like. Tn some entombments, the source for hydroxyl groups may include polyalliylene ether polyols such as a polyethylene: glycol (PE6), pdyteiramethylene ether glycol, polypropylene glycol, or similar ether polyols having a plurality of aval Sable hydroxyl groups. Additionally, or alternatively, the source for hydroxyl groups may include a polyalkylciie polyol such as poly butadiene diol. In some embodiments the source for hydroxyl groups may include a etude or refined material. For example, the source for hydroxy! groups may be a low cost, pure or impure, side product or waste stream from themanufeteure of a higher value product (lor exanfele glycerin obtained during the maiiitfaeture of ethanol from grains).

[0078] Exemplary polyalkylene glycols preferably are miscible, soluble or dispersible in the starting material and include repeating units of ethyl oxide, propyl oxide, or butyl oxides of low to high molecular weight e.g., having a number average molecular weight of from about 190 to about 8000 g / mol, and preferably greater than about 190 gfinol. Such polyali- ylcne glycols can include liquids as supplied, for example PEG 300 and PEG 400, respcctu <-ly atfable from Dow Chemical Co. as CARBOWAX1*1PEG 300 and CARBOWAX PEG 400; waxes: solids; or combinations thereof Polyethylene polyols represent a preferred class of polyo ls that when reacted with starting materials such as tall oil provided modified agents exhibiting’ comparable rejuvenating properties at lower hydroxyl values compared to other polyols tested. Without being bound by theory, it is believed that the long chain polyefher linkages of such materials may also help increase thepolarity of fee resultant partial esters,: thereby making the modified partial ester mere compatible with aging asphalt binders and perhaps slowing the agglomeration of the oxidized molecules in the aged binder,

[0079] In some embodiments tint partial esters may be prepared by reacting one or both of the reaction ingredients (e.g., a first material containing the carbonyl groups, a second material that contributes the hydroxyl groups, or both) with a third material (e.g., a t'o-reaciaiit) to produce the partial ester reaction product. The third material may contain one or rnc-rc unsaturated groups configured to react aud join wife at least one of the other starting materials in producing the resultant reaction product. The third material nmy be used to modify the physical properties of the resultant reaction product by, far example, increasing the reaction product's molecular weight modifying the product’s flash point nr helping to reduce manufacturing costs for the reaction predact. The third material may or may not include either ctrbonyl or hydroxyl groups. Wtuut x that may be used for the third material include, but are not. limited to, dicyclppentadicne (DCP'D), pipmleiic, isoprene, or au Vnsatiitated akohol such as a fatty alcohol, f or example, starting materials fetch as soybeaii oil or tall oil. mateic anhydride, And .DCPD may be initially reacted together followed by reaction with one or more polyols or amine alcohols to provide a restilfatt reaction product having a hydroxyl value of greater than about : 25 trig KOH / g. Other usable reactions may include Diels Alder reactions between DCPD, styrene, an unsaturated acid or anhydride; DCPD and vegetable or plant-based oils; vegetable orplahi-based oils reacted with maleic anhydride, fumaric add, adipic add, neodecanmc add, or acrylic add rosin add reacted with rogleie anhydride; and the like. The reactions may be performed stepwise in rhe production of the reaciion product or as a single reaction scheme,

[0080] A variety of sterols may be used as asphalt ami-aging additives. Exemplary1 1,667,570 B2, the disclosures of which are meorporated herein by reference, Exemplary suppliers of suitable sterols include Arborts and Itigeviiy.

[0081] Other asphalt anti-aging additives include conventional paving asphalt binder modifiers (sometimes cal k'd ’“rejuvenate” or "iofieners”), even though in some instances such paving asphalt modifiers merely soften a,ti asphalt binder to which they am added without necessarily materially delaying aging or restoring the properties of a virgin hinder Exemplary such modifiers include vegetable oil asphalt modifiers such as ANOVA™ 1845 commercially available from Cargill, Inc , soybean oil asphalt nwliftirts such as the refined, bleached and deodorized soybean oils commercially available ton AMD Oil Sales, tall oil asphalt modifiers -such as TufffrekI Mrecycling agent commercially available from Bakelite Synthetics arid Arrmulsf5s!220 emulsifier commercially available from Road Science, asnithe petroleunr-based asphalt modifiei' ReelaniitefMcronuneroiaiiy available from Trims Refining LLC,

[0082] In some embodiments, the asphalt ant i-agiag additive can maintain a ATc value greater than or equal to -5S'C as the roofing material is aged. In some embodmtents, the asphalt anti-aging additive can provide a roofing asphalt composition with a, ATc of greater than or eaual to -5 %' after 40 hours of PAV aging at 100or more preferably a ATc of greater tai or equal to -3CC after such aging. In some embodiments:, the asphalt anti-aging additive provides a roofing asphalt composition with a more positive ATc value and a decreased R-Valnc following aging, when compared to a similarly-aged roofing asphalt composition without the asphalt airti-agirsg additive;

[0083] The disclosed asphalt anti-aging additi ves desirably are a solid at room temperature. In sante embodiments the asplialt anti-aging additive has alineltitig point oi glass transition temperatiire above the normal highest iniended serviee temperatBre of the roofing material and below the asphalt binder melting point. The asphalt anti-agingaddilive is mixed with the molted roofing asphalt binder to provide a homogeneous composition that desirably does not tmdergo separation after mixing,

[0084] The asphalt anti-aging additive may tor example represent ar least atom 0.1 wt. %, at least about 0.5 wt. %, at least about 1 wt. %, ai least about 2%, or at least about 4 wt, %, and up to about 15 wt %, up to about 13 wt %, up to about 10 wt %, up to about h wl.%, or up to about 6 wt.% of the roof coating asphalt composition.

[0085] A variety of asphalt viscosity iiiodificrs may be employed in the disclosed compositions and methods. Exemplary asphalt viscosity modifiers include modified clays (e.x.. rnodifiee bentonite clays , omainckns and pre-sv.ellcd eiays} reactive isocyanates (e.g., B2LasfrMasphalt pavement modifier from BASF), and naturally bccurrihg polymers lignin, biopolymers and other naiurally-oceumhg polymeric materials). In some embodiments, the viscosity modifier is a viscosity improver feat increases viscosity at elevated temperatures (such as the coating temperatures at which the disclosed roof asphalt coating composiiions are applied). Ah increased viscosity at such temperamres can be helpful in shingle maftufactitring, In some embodiments the viscosity modifier reduces viscosity .al the lower service temperatures at which the disclosed roofing materials are used. A reduced viscosity at such temperatures may correspond to either or both of increased stiffness and increased impact resistance. Preferred viscosity improvers fer use in the disclosed roof coating asphalt compositions include otherwise low value KEOB / VTAE materials, which appear to provide Mb increased viscosity at higher coaling tempcramies and reduced viscosity at lower service temperatures, as well as softening point modification,

[0086] The disclosed roof coaling asphalt compositions may include s variety of optional adjuvants. Exemplary such adjuvants include fillers (e,g , finely ground inorganic particulate reader such as ground limestone, dolomite, magnesium carbonate, rock dust,adhesion promoters, cploratifs (ttg., pigments or dyes), oils, solvents, sEabifers and other ingredients that will be familiar to persons having ordinary skill its the art

[0087] The ingredients in fee disclosed roof coaling asphalt compoaftions preferably arc mixed using a suitable low shear mixer. Exemplary mixing devices are avaihble from a wide variety of suppliers. The disclosed method may for example employ include a heated tank and an immersed or immersible impeller having a variable speed control. AB extruder (e.g., , a single screw extruder) may also be Used. The iiigrcdierns may be added to-the mixing de vice in unhcatecl (e.g:, rctoto iemperataP solid) or in molten form, and preferably are mixed at or not for above the higher of a) the pavement grade asphalt melting point and b) the solvent deasphalted pitch or resin melting point, as used. Mixing: desirably takes place for as long as may he needed to also melt the polymer and asphalt anti-aging additive and form a compatible blend, in some embodiments, a mixing temperature of about 166°C (33O:F> w about 193°C (380°C F) and a mixing time of about .one or two hours may suffice. In some embodiments, lower mixing temperatures (e„g.,temperatures below about 14B°C (300sF) or below about 138°C (280sF) may be desired to avoid aging the asphalt and to provide further energy savings compared to air blowing.

[0088] In. some embPdimems. the molten roof coating composition has, before the additi on of any mineral fillet., a viscosity of less than about 4110 cP, less than about 300 cP, les® than about 200 cP or less than about 100 cP tit 204°C (400 °F), In some embodirments, thsnaulten roof coating composition has, before the addi tion of any mi-neral filler, a viscosity of .less than about 300 cP or less than about 200 cP at 176°C (350 °F). In some embodiments, the molten roof coating composition Iras, before the addition of any mineral filler, an equi viscous temperature less than about 204°C (400 °F).

[0089] The molten roof coming composition may be allowed to cool and harden and be stored for later use. The composition may also or instead be kept in a molten state until needed.

[0090] The disclosed roof coaling asphalt compositions may be used to make a varie ty of roofing materials. For example, the disclosed molten roof asphalt coating composition may be applied to a flexible substrate (ris,, a: roofing mat) using coating devices that will be familiar to persons having ordinary skill in the art. Ifor example, the roofing mat may be fed through a heated bath containing the molten roof costing The mat can be any type known for use in reinforcing asphalt-based roofing materials, such as a web, scrim or felt of fibrous materials such as mineral fibers, synthetic fibers such as polymer fibers, cellulose fibers, rag fibers, or a mixture thereof. In some embodiments, the mat is a nonwoven mat of glass fibers. The roofing mat can also include any suitable binder, such as urea formaldehyde, acrylic resin, or sty rene -butadiene latex.

[0091] Typically, a thin layer of fineh-d.'. sded inorganic roofing granules is applied to the molies ronf coating atop the mat, and allowed to become partially embedded into the molten r oof coating asphalt . .Exemplary roof coating granules wi ll be famil iar to persons having ordinary skill in the art, Tile granules typically will have .a particle size of about 8-40 mesh and may Wcolorairinfi^’ed-Teflective- or both colored and mfiared-retl^iive; The -disclosedroofing materials may also include aninorgantcw organic agent (g,f.ssilica sand) On the underside layer of roof asphalt coating: to aid. in packaging and help prevent individual shingles or layers in a roll from sticking together during shipping, After the coating has hardened, the coated mat is cut or slit as needed, to form individual roofing shingles, roll roofing or other desired roofing materials.Test Methods

[0092] The disclosed roof coating asphalt compositions, roofing materials made therefrom, and asphalt pa vement made using post-consimier waste containing foe disclosed roofing materials may be evaluated using a variety of test methods. General specifications for roofing materials are set out m ASTM D225-07 (“ Asphalt binder Shingles (Organic Feit) Smfoxed fore Mineral Granules.55American Society for Testing and Materials, Armual Book of ASTM Standards, Volume 04.04, West Cpn&hohocken, PA. 1936); and ASTM D3462M-I9 (‘'Aspfedt binder Shingles Made From Glass Felt: and Surfirecd wifo Mineral Clfomtfos.” American Society for Testing and Materials, Annual Book of A STM Standards. Volume 04.04, West Conshohocken, PA, 1996).

[0093] Tests and specifications for the disclosed roofing asphalt binder compositions include: performance grading by AASHTO M320 using dynamic shear rheology and bending beam rheology; penetration or “pen" by ASTM D5M-20 run at 25 C (77 °F) or at 46 X (.1 15 T); ductility by ASTM DI 13-17 run at 25°Ct 77 °F J; softening point or W' b y, A S TMD3M- 14( 2020) meltKArf 'f (40u' I ; prat 177 °C (350°F) with a Mode! IV Brookfield Viscotneter, using a no, 1 $ spindle. 6 RPM or a Model RV Brookfield Visoomete' using a no. 21 spindle, 50 .RPM; eguiviseous teniperaiure by ASTM D31'2 and ASTM D44t1"’M- ? y durability by ASTM D4798M- 1 1(2019); flashpoint by ASTM D92- 18; und stabfoiy by ASTM D3?91M41 (20U) modified to ran at oven temperature of 260 °C (500 T) for up to 5 days or similar test procedure.

[0094] Separatfoij tendency (W , foe compaiibil ily of a composition based on the iendcticy of ingredients in the composition & separate wider static heated storage umdiiremdbe esaludieJ xnre a ffompaffofolx Test .ukt rivd (fore ,‘51 M B7173-20 by placing a freshly-mixed sample of the disclosed roof coatitig composition into a metal tube (c.g., a <-i;«ar tube), storing the tube vertically in a 182 ':C ( 360 '5F) oven for 24 hours, removing and. cool? ng the tubs, cutting it into several (ag: , throe or more) sections, a?idmeasuring the softening temperature of each section. Ak<conipatible blend” exhibits less than a 5.5 (10 °F) temperature difiereiice I .'M eet the sections having the highest and lowest observed softening points in the Compu 'd u Test

[0095] The suitability and recyelabffity into asphalt pavement of post-consumer waste containing the disclosed roofing materials may be evaluated using a variety of tests including N-Design by AASHTO R 35; low temperaftue thermal cracking (!’«) using the Asphah Binder Cracktiu; Deb tee and AASHTO T 'S“-W; flexibfi iy in the Hlinoss Flexibility fades Test tl-HTj by AASHTO T393-21 ; the indirect tensile asphalt cracking test (IDEAL CT} by ASTM D8225* 11 and the Texas overlay test per TEX*»F.

[0096] The disclosed conipositioiis and methods are further illustrated in the Ibllowihg non-limiting examples. Various modifications and al terations of the disclosed compositions and methods will be apparent to those skilled in the art without departing from the scope of this disclosure;Example 1 Roof Coating Asplial ts

[0097] Two nomoxidized roof coating asphalt compositions identified as “MOCA ”and “NOC-2’' were prepared by heatfag and mixing together m a low shear mixer the ingredients shown below in Table 1:Table

[0098] The properties of compositions NOG-1 and NOC-2 are shown below in Table 2, together with properties of aeonvctitiohal roof coating asphalt composition from a major roofingmanufachirer containing air-blown asphalt binder. The compositions werealso evaluated for various BBR values in both an imaged condition and after 20 hour PA V aging:Table 2.

[0099] The penctntii.ro value for NOC- 1 was 14 decimfilmieiurs (dram), which is above the 12 du mt minimum specified in ASTM D312 for asphalts used in waterproofitig or as an adhesive in:roofing applications, and slightly below the IS dmm minimum specified in ASTM D346249 for asphalt binder roofing shingles. The 14 dmm value could be raised (vfe. , the NOCT eonipusitiqn could be made softer) by decreasing tlie amount of solvent deasphalted pitch relative io the amormtof paving grade asphalt, or by decreasing sng or both of foc polymer or partial ester amounts in the NfXTi formula, The penetration val ue for NOC-2 was 15 dram and thus met the specified minimum for both ASTM D312 and ASTM D3462-I9. The softening point for NOG- 1 was within the 99 to 107i:C Qlti to 325 °F) range specified for Type IV asphalts in ASTM D312. Thesoftening pointe for both NOG compnfetism; were within the h8 to 160 °C (190 to 320 ° F) range specified in ASTM B346249. The CorapatMity Test values for both NOG compositions were below the alwe-meiriioned 5.5 “G (10 ®F) temperaWe difference limit.

[0100] The remaining data in. Table 2 shows especially clear advant.nx\ '.tr the NOC compositions. The > 20 cm ductility of fee N0C cnmposidons at 2$ °C (7"TI ) was sigtiificaatiy greatei h n the 2 cm ductility of the air-blowri asphalt conipusiticii, indicating that the Nut- compositions are more flexible and should better resist cracking than air-bio* r< asphalt at intermediate temperature conditions. The viscosity values for the NOC commit VIA were much lower than the viscosity of the air-blown asphalt composition, and the Equisiscous Temperatures for NOC-1 and NQC-2 were respectively about 62 °G (129 *F) and 56 °C (100 °F) lower than the air-blown asphalt composition. Gssnseqaently, the disclosed non-oxidized asphalt compositions should enable a significant reduction in production (vff., mixbig and. coating) temperatures, thus lowering energy consumption and eniissioRS, while creating safer operating conditions. BBR stiffness values provide aii indication ofshear modulus, and were significantly higher for the NOG compositions than for rhe air-blown asphalt composition. BBR m-valuesprovide an indication of the asphalt relaxation potential, with higher in-vfeues indicating belter relaxation At -6 °C, the NOC- 1 and NOC -2 eomposidons show better relaxation potent ial than the air-blow composition, and also have high stiffness. This indicates that at lower exposure temperatures, the NOG compositions should have better crack resistance properties than the tor-blown asphalt composition, as the MOG compositions can relax more readily white maintaining high stiffness to resist cracking. furthermore, when the coating asphalt compositions were laboratory aged using fee PAV aging method for 40 hours, the art-blown coattog was too stiff to be- poured even when heated to 232S'C (450° F In ccMra-i (Ik \()( v’Umxwitsm-; *,"c whi ff p.xhatH,' ti k>s Hi. n .\rt I '4(10 H and showed acecptablc stiffness and m-values after PAV aging. The NOG compusi tions thus appear to have better properties post aging and increased potential recyclability.

[0101] eferring to the Drawing,, Fig. .1 and .Fig. 2 respectively show -cbtopfex modulus vs, frequency curves and phase angle vs. frequency rheology curves for fee NOC-1 and NOG -2 compositions arid the air-blown asphalt (‘‘Oxidized’') Composition at a reference temperature of 25 *C, fer samples feat are unaged (“UA”) or PAV aged for 40 hours (“2P AV”). The shift in shear modulus from the iitiaged to aged condition is less forthe NOC eompositlons than for alt-blown asphalt. This change in Shift is indicative of the asphalt aging potential with a. lower shift indioaimg a lower aging fate. Both the shear modulus and phase angle theology master curves also indicate lower aging potential for theNOC eompositions and lesser degradation ofthe NOC compositians over time compared to air-blown asphaltExample 2 Shingle Fabrication

[0102] Filled coating samples were prepared by mixing I part of the roof coating asphalt compositions with 2 parts of limestone filler Laboratory prepared asphalt roofing shingles were made using the filled . coating and light grey colored granules. The lab prepared shingles were ctit to size and tested for granule adhesion using a method similar io ASTM-D4977M-2O, but using a 38 mm x W mm (I Sin x 3.5m) brush with 18 holes containing bristles: made of 0.3(15 mm (0.012 in.i dismeter tempered steel wire, wi th 30 Wires per hole set rising epoxy. The applied load was 1 Kg + 50g 'The mass loss amounts for the NOC» 1 and NOC-2 compositions affor 11)0 eyefes of scrabbling under the I Kg load were 2.3 and 3.3 grams, respectively, whereas the mass loss for lab shingles made using the air-blown coatfog Composition was 5,0 grams. The greater fog mass loss, the poorer foe adhesion properties. The disclosed noiwidized roof coating asphalt compositions consequently provide significantly improved adhesion compared to a convemfonal airblown binder, ffoetos of the shingles after the adfcesion rest are shown in Fig. 3., and they further illustrate the improved .granule reten tion for shingles made using foe NGC-'l and NOC-2 compositions, as more of the underlying roof coating is visible for foe shingle made using the air-blown coating.Example 3 PAV Aging

[0103] Using the method of Example 1, a non-oxidized roof coating asphalt composition identified, asivNOC'3” ws prepared by heating and mixing together in a low shear mixer the ingredients shown below in Table 3;Table d

[0104] The MOC-3 composition was mixed with limestone filler in ratio of 1 part roofCoating asphalt to 2 parts limestone fiber. The resulting filled coating was aged under laboratory conditions in a pressure aging vessel (PA.V) for 80 hours (“Long-Term Aging”) under compressed air at 2.1 MPa. The lab-aged, filled coating was then granulated io a size finer than a #10. sieve (2.0 nifty and mixed with coating granules in a fixed proportioti to replicate the composition of recycled sliitigles for use in asphalt paving mixtiires;. Similarly, an air-blown asphalt coating was subjected to similar L AV aging, followed by grinding and mixing with granules to provide lab aged, : recycled ait-btown shingfe granules for use in asphalt paying mixture.Example 4 Paving Mixtures

[0105] Laboratory asphalt paving mixtures were prepared with and without recycled shingle material. A control niixturecentaihcd only virgin binder, and was used to make a mix having an K -design of 75 with 12.5 mm nominal maximum aggregate size (NMAS), 5,8% total asphalt cmuer1by weight of the mix and target air voids of4.0%, The completed vor.tr >1 mi x h.tc 16 I’ m o«k in tm .era.filled with asphalt (VF A), Recycled mixtures combining granulated shingles predated using either the nonoxidwd NOC- 3 cocposition of Example 3 or a cdnvpntioml a«- blown asphalt binder were also made withan N-destgft of 75. 12.5 rmti NMAS. total asphalt of 5.7'X ' F \ v. e tght of foe m ix and target air voids of 4,0%. The completed recycled ffiixtures had a 1570a VMA and 74.5% ATA.

[0106] Asphalt paving mixture test samples were prepared for pertmaance testing at target air voids of7.(H);5%. Three asphalt cracking tests were conducted to evaluate thecracking potential Of the virgin and recycled mixes. Set out betaw in Table 4 -is a summary of results fern the Illinois Flexibility Index Test (1-FIT):Table 4Illinois Flexibility Index Test Summary

[0107] 1-FIT is a mpnptonie fractitre test conducted at a displacement rate of 50 mm / m in at 25 ° C. Thedie flexibility i\kx t i l k j nataBiete) th.u relates to cracking ^erfomtanee of the asphalt mixture. Tlx greater the bi, the better the resistance to Ctosking. Additional parameters obtained fem the test include fracture energy, post peak slope, and strength. Fracture energy is an indicator of the -total energy required to initiate a crack and propagate the, crack until failure. Post peak slope indicates Err i. lie of < rack prep.yran-ra I ke higher lhe ahst'luie v alue oi'ihe po st peak slope, thr fester the crafe raws. Strength indicates the potential to initiate a crack. The higher the strength, the greater the effort required to initiate the crack.

[0108] As shown in Table 4, the Flexibility Index and Strength for the NOC-3 composition We respectively about 1(1% ata about 30% greater than the Flexibility Index and strength for the air-blown composition, this indicating that the NOC-3 eoniposition has beter potential to resist cracking. Furthermore, the short-term aging fracture energy for the NOC-3 composition was more than 40% greater than the start-term aging fracture energy for the lab aged air-blown mix, thus again indicating greater potential fracture insistence following short-term aging compared to the air-blown composition. However, the virgin control mix showed even higher Statute energy after short-term aging than the recycled mixes. That fracture energy disparitydiappeared afterlotigdenn siding The -NOC-3 mixture had about 3 l% higher fracture energy, about 27% greater FT and about 9% greater strength than the alr-felowti tnix thus: suggesting better long-term Cracking resistance. The fracture energy and strength were also well above the conespondiugvalues for the virgin mix.

[0109] The results from Table 4 suggest that pavement made using aged, recycled shingles containing the disclosed wnoxidized roof coating asphalt should provide much better cracking tcsistm-ce than paven»n.t made using aged, recycled shingles containing a conventional air-blown costing asphalt. Hence, the disclosed noaoxidized roof coating asphalt compositions should have higher potential for recycling than conventional airblown coating asphalts. Recovered or extracted binders from such nonoxidized roof coating asphalt compositions should also be useful as hard asphalts in new roof coating opcmtiottS;

[0110] In a further evaluation of recyclability, asphalt paving mixtures like those described above were subjected to: the Texas Overlay Test per Ac :specifeatan Tex-240. The results ®re shown below jn Table 5;Table sTexas Overlay Test

[0111] The Texas Overlay Test is a displacemeiit comrctlled cyclic direct tensile fracture test with a displacement of 0,06 c:tp and a lopdmg frequency afO.1 Hz at 25 °C, The cycles to reach a 93% load reduction or the % load reduction at 12W cycles are reported whichever occurs &st. As show in Table 5, all the samples reached 1200 cycles l-ek K re-uebiou a ''3’* - loud cdm, i>'o he l>>? es flu, lead redt uwi the bett<.n ft e resistance to cracking caused by cycling tensile loading. The TlOC-3 sample -reached 1200 cycles at 88,5% load reduction -while the air-btewii sample reached 90.6% load reduction. This suggests more damage was caused m the air-blwh sample than in the NOC-3 suirpk It s. x ig u vuntxnl artpL >> ’>>x' v j thereduction at 1200 cycles. The results in Table 5 implement the Table 4 J-F1T testresults,indicating teat the NOC-3 composition has better cracking resistance than the air-blown coating asphalt composition. In addition, tee WC-o sample exhibited about 7% greater maximum load than the air-blown, sample, thus demonstrating greater strength.

[0112] In an: additional cvalaatiort of recyclability, asphalt paving mixtures like those described above were subjected to an Indirect Tensile Cracking Test (IDEAL-CT) per ASTM 1%225- lte Tire ic^ult> are strewn Irelow in Tabic t«TabledIDEAL CT Test Summary

[0113] The IDEAL-CT test is a monotonic cracking test with displacement control and a loading rate of 50 imiVmin tested at 25 °C. The samples arc tested until failure. The outcome of the test is a cracking parameter, the CT Index, obtained using: the load displacement curve. The greater the CT index, the better the cracking resistance. The samples were aged for short and long-term aging Conditions. As shown in Table 6, the NOC-3 sample CT index was more than 60% greater than that of the air-blown sample after sJwt-tenn aging, and more than 70% greater than that of the air-bfow sample after long-term aging. These results indicate that the NOC-3 binder has greater potential recyclability than the air-blow binder, as the. NOC-3 binder has better resistance to crackingE sample 5Roof C »»t mg AspMts

[0114] two more tiomoxidizcd roof coating asphalt composition;, idcmified asl'NOC’ 4rand “NOC-VM’ were prepared by beating and mixing the ingredient' shown below in Table 7 under low shear ceaditu »u The \OC-Vkl composition included a viscosity modifier, but had the same relative proportion of al! other ingredients.

[0115] The properties of compositions NOCM and NOC-VM are shown below in Table S, The compositions were also evaluated for various BBR values in both an imaged eoriditien and after dS-hw.PAV aging: tables

[0116] The penetration values for NOC-4 and NOC-VM at 25 X (77 X) were 18 deciiniiltmeieis (dmm) and 16 decimillimeters (dram), wspectivdy. which are above the12 drum minimum specified in ASTM D312 for asphalts used m waterproofing or as anadhesive in rwsfmg applications, and above the 15 dram -misimum specified in ASTM D3462- 19 for asphalt b inifer roofing shingles. The penetration values at 46 °C (LI 5 ®F) were 52 decimi IHmcters (dmm) and 43 deeimilfinteters (dmm) for NOC-4 and NOC-VM, respectively. The penetration values showed that NOC-VM was slightly stiffer than NOV- 4. The softening points for NOG4 and NOC-VM had the same value of 114 ®C (2M9F) and were higher than the 99 to 107 °C (210 to 225 °F) range specified for Type IV asphalts tn ASTM 'D3.12, The softening points for both NOC compositions were also « sthtr t >e 88 to1 60 ° C (19 0 t o 320 ,-ngc st retfied in \8TM D34»w-i o

[0117] The ducfility of .NOCM .(> 30 cm) was significantly greater than NOC-VM (>I 5 cm) at 23 *C (77 T j, which shows that NOC-VM is less flex ible than NOC-4, However, both NOC-4 and NOC-VM had significantly greater ductility than the 2.5 cm requirement in ASTM D312. This indicates that both NOC-4 and NOC-VM are more flexible and should beter resist cracking than an air-bfowri asphalt coating compositimrat it; termed iate temperature conditions .

[0118] BBR stiffness values provide an indication of shear modulus and were similar for both NOC-4 and NOC-VM. B.BR m- values provide an indication of the asphalt relaxation potential, with higher m~vates indicating better relaxation. At -fieC, NOC-4 was slightly less stiff than NOC-VM and also had slightly better relaxation potential Furthermore, when the coating asphalt composit ions were laboratory aged using the PAV aging method for 40 hours, the NOC-4 and NOC- VM compositions were both easily pourable at less than 204 °C (400 * Fl and showed acceptable stiffness and m- values after PAV aging. The NOC-4 and NOC-VM conipositions tints appear to have very similar properties in most respects. However, the viscosity value for NOC-VM al 182 ®C (360 AF) was 135 cP, while for NOC-4 it was 80 cP.

[0119] I he mi H :pk stress creep rreoreay ( MSI R > test w a retain c mccs arc of resistance to deformatlQn under creep loading. Lowyr values in foe MSCR test represent filgha' resistance ixi clcfoonation. The results in Table 8 show that the inclusion, of a viscosity modifier tn NOC-VM decreased foe fo value te 0,9 compared to the J® of 2.8 obtained for NOC-4, This rqxreseuts increased resistance to deformatfort for NOC-VM al 76 °C (169,SF).

[0120] Fig, 4 and Fig, 5 respectively show complex modulus vs. frequency curves and phase angle vs. frequency tiwclogy curves for the NOC-4 and NOC-VM compusitiotis at are&rence temperature of 25 ®€, for samples that Wife imaged f'UA”) or PAV aged for 40 hours (M2PAV”). Both formulations es hi biicd similar properties over the Aufo '•aiige of tested temperature and I frequency rati gesExample 6 Shingle Costfog

[0121] Filled coating samples were prepared by liiixing 1 past of the roof coaling asphalt cooqxisitions of Example 5 with 2 parts of limestone filler. The temperatureviscosity profiles for filled NOC4 and NOC-VM were plotted and compared to eohventional air-blown and polymer modified filled coatings. The viscosity of a filled coatings is very important for shingle manufacturing operations. Viscosity that is- too low can result in filler drop off while viscosity that is too high may not flow through a coating line.Therefore, appropriate viscosity for the filled coating is highly desirable for stiecessfitl application of a roof coating asphalt in a shingle maiiufecturing operation.

[0122] Fig.. 6 shows the temperatare-viseosity profiles of the filled coatings A typical range of acceptable coating viscosities may be at* >m 2000 to about 6000 cP. Within ibis range, a -PiMA-based coating may for example be mtable aver & temperature range of about 193 to about 204°C(about 380 to about 400 °F), while an air-bfowri oxidized asphalt-based coating may for •example be coatable over a temperature range of about 218 to about 246 °C (about 42S io about 475°F), It should be noted that depending on the polymer present in foe PM A. some PMA-tased coatings may be coarable at other temperatures, for example at temperatures above about :2Q4 X (400 *Fj.

[0123] The NOC-4 filled coating exhibited a desirable and energy efficient working coating temperature range of about 140 to about 162°C (285 to 325 T"). The NOC-VM composition could be used at higher but still energy efficient coating temperatures up to about 193°C to 80 'T-' i. Therefore, inclusion ot the viscosity mods Her enabled a broadening of the workable coating: tempcratiirc range to about 140 to about 193 X (about 285 to about- 3 8(foF), while still remaining below the temperatures needed for the TMA-bascdadd aii -blown oxidized roofing asphalt edat-ng compositions.

[0124] The above description is directed to rhe disclosed methods and is not intended to limit them. Those of skill in the art will readily appreciate that foe teachings found hcreifi may be applied to yet other embodiments within the scope of the attached claims.The complete disclosures of all cited patents, patent documents, and publications arc incorporated herein by reference as i f individually incorporated. However, in case of any inconsistencies the present disclosure, incfofeiig any definitions herein, will prevail.

Claims

Claims1. A roof coating asphalt composition comprising a compatible blend of; a) non-air oxidized paving grade asphalt: hinder, b) asphalt softening point modifier comprising a solvent deasphalted pitch or resin that increases the softening poitri of the paving grade asphalt hinder, c) impaet-madiiying polymer and d) asphalt aftti-agmg additive, the composition being substantially tree of air-blown asphalt binder.

2. A method for making a roof coating asphalt composition comprising the steps of blending under low shear conditions a mixture of a) non-air oxidized paving grade asphalt binder,, b) asphalt softening point modifier comprising a solvent deasphalted pitch or resin that increases the softening point of the paving grade asphalt binder,M finely-di vided impact- modifying solid polymer and d) asphalt anti -aging additive, to form a compatible blend that is substantially free of air-blown asphalt binder.

3. A method for making a rooting material comprising the steps of applying: to a flexible substrate web a roof coating asphalt composition comprising a molten compatible blend of: a) paving grade asphalt binder, b) asphalt softening point modifier comprising a solvent deasphalted pitch or resin that increases the softening point of the paving grade asphalt binder, c) impact-modify ing poly suer and d) asphalt anti-aging additive, the composition being substantially fee of aioblown asphalt binder; followed by applying to the nioltort M end a layer of finely-divided mergsmefoofing granules4. A method for recycling asphalt roofing waste comprising the steps oft providing roofing 'waste containing an asphalt binder comprising; a) non-air oxidized paving grade asphalt binder.b) asphalt Softening point: modifier comprising a solvent deasphalted pitch sr resin that increased the softening point of the paving grade asphalt binder,C) impact-modi lying polymer and d) asphalt anti-aging additive; grinding or otherwise comminuting the roofing waste; mixing the comminuted roofing waste with virgin pavetneat .grade asphalt binder and aggregate; applying the resulting mixture to a pavement substrate; and compacting the resulting applied mixture to - to a pavement,5. A cmpposition according to claim l or medtod according to any one of claims 2 to 4, wherein the paving grade asphalt binder has a PG 70-22, PG 70-lfi, PG 70-10, PG 67-22, PG 67-10. PG 64-22, PG 58-28, PG 58-22, PG 52-34 or PG 46-34 performance grade rating as evaluated using AASH'TO M32(h6. A composition according to claim 1 or method according: to any one of cl aims 2 to 4, wherein the paving grade asphalt binder comprises a polymer-nk'sdificd. asphalt binder.7, A composition according to claim I or method according to any one of claims 2 to 4, wherein the paving grade asphalt binder comprises a binder recovered or extracted from a recycled asphalt binder,8 A composftic'n according: to claim 1 or method accordiiig to any one o f claims 2 to 4, wherein the non-air oxidised paving grade asphalt binder represents at least about 25 wt % and tip to about 40 wt. % of the coating asphalt compos t lion.

0. A composition according to claim 1 or method according to any one of claims 2 to 4, wherein the asphalt softening point modifier comprises a solvent: deasphalted pitch obtained from a liquid Aiquid; extraction process that employs a C3 to C6 aliphatic solvent to separate an asphalt feedstock into deasphalted oil and pitch.

10. A composition according to claim 1. or method according to any one of claims 2 to 4, wherein the asphalt softening point modifier comprises a propane deasphalted asphalt.1 1. A composition according to claim 1 Or method according to any one of claims 2 to 4, wherein rhe asphalt so frening point modifier comprises a natural resin,12. A composition according to claim I or method according to any one of claims 2 to 4, wherein rhe asphalt softening point modifier comprises a rosin or rosin-based resin.

13. A composition: according to claim 1 oi method according to any one of claims 2 to 4, wherein the asphalt softening point modifier comprises a terpene resin.

14. A composition according to claim I or method according to any one of claims 2 to 4, wherein the asphalt Softening point modifier comprises a fossil resin.

15. A composition according to claim 1 or method according to any one of claims 2 to 4, wherein rhe asphalt softening point modifier comprises a synthetic t< sm16. A compositJon according to claim 1 oi method according: to any one of claims 2 to 4. wherein the asphalt softening point modifier comprises a C5, C9, CIO or pure monomer resin.

17. A composition according to claim I or method according to any one of claims 2 to 44wherein the asphalt softening point modifier comprises a phenolic res iit18 A composition accord ing to claim I or method according to any one of claims 2 to 4, wherein the asphalt softening point modifier comprises a hybrid resin made from a combination of -natural and synthetic resins.19 A composition according io claim 1 or method according to any one of claims 2 to 4, wherein the asphalt softening point modifier represents at least about 25 wt. % and up to about 75 wt. % of the coaling asphalt composition.

20. A composition itccording: to claim 1 or method according to any one of claims 2 to 4, wherein the impact-modilying polymer comprises a homopolymeit copolymer, block copolymer, graft copolymer, wax, rubber, or mixture or blend: thereof.

21. A cotnposilimi according to claim I or method according to any one of claims 2 to 4, wherein the impael-modi tying polymer comprises low-density polyethylene (LDPE),Ii near low-density polyethylene (LLDPEj. verydow-deusify polyethylene (VLDPEX ultradow-deusity polyethylene (ULDPE) or mediwiurtasity polyethylene (MDPE).22, A composition according to claim I or method according to any one of claims 2 to 4, wherein the impact-modifying polymer comprises an elastomerie block copolymer ’with polystynme end blocks and unsaturated elastomeric mid blocks.23, A composition according to claim 1 or method according to any one of claims 2 to 4, wherein the impact-modifyiiig polymer Comprises a storene-butadiene-sty'rene (S.BS) or styrene-isoprene-styrene (SIS) block copolymer,24, A composition according to claim 1 or method aceo"ding to any one of cl aims 2 to 4, wherein the impact-modi lying polymer compr >e> .m cihyterie bis-srearimiide wax (EBS). Fischer -Tropsch wax (FT), oxidized Fischct-Tropsch wax (FTQ), polyolefin waxes, alcohol wx, silicone wax, mferecrystallme wax, pwxffe wax^amifte xvax, amide wax, ester wax, carboxylic acid wax, candelilla wax, carnauba wax, rice Wx, Japan wax jojoba oil, beeswax,whale wax, Montan wax, ozokerite, ceresin wax or mixture thereof25. A composition according to claim 1 or method according io any one of claims 2 to 4; wherein the impact-toodifying polymer comprises rubber26. A composition according to claim 1 or method according to any one of claims 2 to 4. wherein the impact-modi tying polymer comprises a polyisoprene or isobutylcne / isoprene rubber.27, A composition according to claim I or method according io any one of claims 2 to 4, wherein the impact-modifying polymer comprises ground lire rubber.28, A composition according to claim 1 or method aocording to arty one of claims 2 to: 4, wherein the impact-modifying polymer eompia blend of a low-density polyethylene wax and ground tire rubber.

29. A coniposition according io claim I or method according to any one of cl aims 2 to 4, wherein the impact-modifying polymer represents at least about 0. 1 wt. % and up to about 20 wt. % of the coating asphalt composition.

30. A composition according to claim 1 Or method according to any one of claims 2 to 4, wherein rhe asphalt-anti-agirtg additive comprises a partial ester having a hydroxyl number greater than .25 mg KOWg.31 A composition aeeording to claim I or method accmding to any one of claims 2 to 4, wherein the asphalt anti-aging additive comprises a partial ester having a hydroxyl value greater than about: 35 mg / KOHZg and up to about 250 mg KOWg,32. A Composition according to claim 1 or method according to any one of claims 2 to 4, wherein the partial ester is formed by partially reacting a Starting material containing carboxyl groups with sw or more polyols or amine alcohols.

33. A composition according to claim 1 or method according to any o;fo of claims 2 to 4, wherein the partial ester is formed from soybean oil, tall oil or rosin acid,34. A composition according to claim j or method according to any one of cl aims 2 to 4, wherein the partial ester is formed from ethylene glycol, diethylene glycof triethylene glycol, propylene gl yeol, dimethyfolpropionie acid, glycerin, trirnefoyfolpropane. neopentyl glycol . pentaciythritol, di-pentaerythritol, sorbitol, sucrose, polyethylene glycol, polypropylene glycol, methanoiamine, dinreihyletitanolamine, ethanolamine, aminamethyl propanol a polysulftde polyol, a propanolamine, or a mixture thereof35. A composition according to claim I or method according to any one of claims 2 to 4, wherein the aspfeah-and-aging additive comprises a sterol36, A composition according to claim 1 or method according to any one of claims 2 to 4, wherein the asphalt-anti -aging / additive comprises a crude sterol37.cording to claim 1 or method according to any one of claims 2 to 4, where™ the a-->pi\tli-ami-aging additive provides a less negative ATc is aged roof coating asphalt containing the anti -aging additive after 20 hours of PA V aging at 100 degrees Celsius compared to a similafly-aged roof coating asphalt, that does not contain the anti-aging additive.38 A composition according to claim 1 or method according to any one of claims 2 to 4, -wherein the asphalt anti-aging additive provides a ATc of greater than or equal to -3®C in aged roof coating asphalt- containing life mtFaging additive after 2(1 hoots of PAV aging at 100 °C.

30. A composition according to claim I or method according to any one of claims 2 to 4, wherein the asphalt anti-aging additive represents at least about fi.l wt % and up to about 15 wt. % of the roof coating asphalt composition.40, A composition aecordisig to claim 1 or method according to any one of claims 2 to 4. wherein the asphalt composition comprises an asphalt viscosity modifier.41, A composition or method according to claim 40 whc> cm the asphalt viscosity modifier comprises an organoclay, modified ben tonite clay or other modified clay.42, A compost tioii or method according to claim 40, wherein the asphalt viscosity modifier comprises a reactive isocyanate43, A composition or method according to claim 4ft, wherein the asphalt viscosity modifier comprises lignin or other naturally occurring polymer.44, A composition or method according to claim 40, wherein the asphalt viscosity modifier c<3mprises a rcsid er bottom fiac tkm obtained from the processing of re- refined engine oil bottoms.45, A composition according to claim 1 or method according to any one of claims 2 to 4, wherein the roof coating asphalt composition further comprises a mineral filler46, A composition according to claim I or method according to any one of claims 2 to 4, wherein the roof coating composit ion has , before the addition of any m ineral fil ler, af lev. Unn ahem 41'0 cP at '04 “f ,4i'O ! i47. A ceni[X)sifeii according: ip elaim 1 or metlwl according to any one of claims 2 to 4, wherein the roof coating composition has, before the addition of atty mineral filler, a viscosity of less than about 200 cP:at 204 °C (400 °F).4$. A composiiioii according to claim 1 or method according to any one of claims 2 to 4. wherein the roof coating composi tion has. before the addition of any mineral fil ler, a viscosity of fess than about 3(H) cP at 176 °C( 350° F)., A composition according: to claim 1 or method according to any one of claims 2 to 4 wherein rhe roof coating composition has, beta the addition of any mineral filler, an equiviscoiis temperdaife less than about 204 °C (400°F). A pavement cpmpiishtg wyeled asphalt shingles containing a roof coating asphalt exposition: according to any preceding claim.

Images