Colophony ester-based compositions

Abstract

Rosin ester comprising the reaction product of a rosin and one or more aliphatic polyols having a structure of general formula (I), general formula (II) or a mixture thereof: wherein each n and m is independent of each other ≥ 0 and the sum of n + m is ≥ 1; Each o, p, q and r is independent of each other and ≥ 0; each R 1 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 13 , R 14 , R 19 and R 20 regardless of whether it is composed of H, CH3, CH2CH3, OH or CH2OH; and each R 2 , R 6 , R 10 , R 11 , R 12 , R 15, R 16 , R 17 , R 18 , R 21 , R 22 and R 23independent of whether it is made of H or CH3; wherein the aliphatic polyol has a ratio of the number of carbon atoms to the number of oxygen atoms of ≥ 2; and wherein the rosin ester has: an acid number of < 50 mg KOH / g, preferably < 40 mg KOH / g; particularly preferably < 30 mg KOH / g; a weight-average molecular weight of < 6000 g / mol, preferably < 5000 g / mol, particularly preferably < 4000 g / mol; and a glass transition temperature (T g ) from -40 to 100°C, measured according to ASTM D 6604.

Description

AREA

[0001] The disclosure relates to a composition based on rosin esters, which contains a rosin ester produced with an aliphatic polyol, as well as to methods for its preparation and applications thereof. BACKGROUND

[0002] Rosin esters are used in a wide variety of industrial and consumer applications, such as adhesives, printing inks, coatings, tires, personal care products, road markings, textile finishing, agricultural formulations, and fuel additives. In many of these applications, rosin esters are incorporated into adhesives as tackifiers in combination with a polymer. For an adhesive to function reliably, the components must be compatible and not undergo phase separation, both under ambient conditions and at the elevated temperatures typically encountered during application.

[0003] The use of raw materials from renewable resources, which can reduce dependence on petroleum-based raw materials and are biodegradable or, in some cases, industrially compostable, has become increasingly important. To be suitable for use in adhesive compositions, such renewable components must be compatible with conventional adhesive polymers. For example, adhesive compositions are often formulated with ethylene vinyl acetate (EVA), metallocene-catalyzed polyolefins (mPOs), or amorphous polyolefins (APOs). Conventional rosin esters are sometimes modified with aliphatic monomers to improve their compatibility with these polyolefin polymers.

[0004] There is still a need for rosin esters that are compatible with various polymer components for use in different applications. SUMMARY

[0005] According to one aspect, the disclosure relates to a rosin ester comprising the reaction product of a rosin and one or more aliphatic polyols. The rosin ester has: an acid number of < 50 mg KOH / g, preferably < 40 mg KOH / g; particularly preferably < 30 mg KOH / g; a weight-average molecular weight of < 6000 g / mol, preferably < 5000 g / mol; particularly preferably < 4000 g / mol; and a glass transition temperature (Tg) of -40 to 100 °C as measured according to ASTM D 6604.

[0006] According to one aspect, an adhesive composition is disclosed. The adhesive composition comprises: 10-60 wt% of the rosin ester, 20-70 wt% of a polymer selected from the group consisting of ethylene-vinyl acetate copolymers, metallocene-catalyzed poly-α-olefin elastomers, metallocene-catalyzed poly-α-olefin plastomers, and amorphous poly-α-olefins, and 0-40 wt% of a plasticizer. The adhesive composition has a cloud point of less than 160 °C as determined by ASTM D6045 and a melt viscosity at 180 °C of less than 50,000 mPa·s as measured by a Brookfield rotational viscometer with a Thermosel heater according to ASTM D3236.

[0007] According to one aspect, a pressure-sensitive adhesive composition is disclosed. The pressure-sensitive adhesive composition comprises: 10-60 wt.% of rosin ester, 10-40 wt.% of a styrene block copolymer, and 10-40 wt.% of a plasticizer. The pressure-sensitive adhesive composition exhibits a 180° peel-off strength of at least 5 N / 25 mm, measured on a stainless steel substrate at a peel-off speed of 300 mm / min according to ASTM D3330, and a shear bond strength of at least 1000 minutes at 23 °C, determined on a 25 mm × 25 mm overlap joint under a load of 1 kg according to ASTM D365.

[0008] According to one aspect, a tire composition is disclosed. The tire composition comprises: (i) a rubber component selected from the group consisting of natural rubber, synthetic polyisoprene, polybutadiene, styrene-butadiene rubber and mixtures thereof, and, based on 100 parts by weight (phr) of the rubber component, (ii) 30 to 200 phr of a filler and 5 to 75 phr of rosin ester. DESCRIPTION

[0009] The following terms are used throughout the patent specification.

[0010] “Consisting essentially of” means that the composition primarily contains the aforementioned components and may additionally contain one or more components that do not substantially affect the novel properties or the intended function of the invention. In embodiments, such additional components are present in amounts of < 30 wt.%, < 20 wt.%, or < 10 wt.%, relative to the total weight of the composition.

[0011] "Consisting of" refers to a composition that contains only the expressly listed components and excludes other components that significantly influence the technical solution or the respective function of the invention. However, the presence of other components in small quantities that do not significantly impair the technical effect of the invention is not excluded, e.g., stabilizers, process residues, or solvents used in the manufacturing process, in trace amounts.

[0012] “At least one of [a group such as A, B and C]” or “one of [a group such as A, B and C]” means a single member of the group, more than one member of the group, or a combination of members of the group. For example, “at least one of A, B and C” includes only A, only B, or only C, as well as A and B, A and C, B and C; or A, B and C, or any other combination of A, B and C.

[0013] A list of embodiments presented as “A, B or C” shall be understood to include the embodiments only A, only B, only C, “A or B”, “A or C”, “B or C” or “A, B or C”.

[0014] “One of A, B or C” refers to an option from A, B or C.

[0015] “One of A, B and C” refers to one or more options from A, B and C.

[0016] “Molecular weight” or M w refers to the equivalent molecular weight in kg / mol of polystyrene of a polymer block or block copolymer. M w It can be measured by gel permeation chromatography (GPC) using polystyrene calibration standards, such as those specified in ASTM 5296. The GPC detector can be an ultraviolet or refractive index detector, or a combination thereof. The chromatograph is calibrated using commercially available polystyrene molecular weight standards. The M wof polymers measured with GPC under such calibration are equivalent molecular weights with respect to polystyrene or apparent molecular weight.

[0017] “Acid value” or “Neutralization number” or “Acid number” or “Acid content” are used synonymously and are measured according to ASTM D465-05 (2010).

[0018] The "Gardner color scale" refers to a scale used to measure the intensity of the yellow color in liquid samples. A lighter (i.e., less intense) yellow corresponds to a lower Gardner color value.

[0019] “PAN number” refers to the sum of the weight percentages of palustric, abietic and neoabietic acid components as obtained by hydrolysis of the rosin ester.

[0020] “Oxygen content” refers to the weight percentage of oxygen atoms in relation to the total molecular weight of the compound, as determined by 13Determined by C-NMR or elemental analysis.

[0021] “Elastomer” is used synonymously with the term “rubber” and refers to any polymer or combination of polymers as defined by ASTM D1566.

[0022] “phr” refers to parts by weight per hundred parts of elastomer / rubber (the sum of the elastomers if multiple elastomers / rubbers are present).

[0023] “Long-chain branching” or LKV refers to the presence of extended side chains or branches along a polymer backbone, expressed as the number of LKVs per 1,000,000 carbons, LKV / 10 6 Carbons, measured using GPC and / or NMR techniques.

[0024] Short-chain branching (CCV) refers to the presence of shorter side chains or branches attached to a polymer backbone. These branches consist of fewer repeating units than the polymer backbone. CKV is formed when a comonomer, e.g., 1-butene, copolymerizes with the main olefin monomer, e.g., ethylene. The comonomer units disrupt the regularity of the polymer backbone by introducing branches at relatively regular intervals. The main difference between long-chain branching (LCV) and CKV is that in LKV, the long-chain branches consist of multiple repeating units and are relatively longer, e.g., more than a few dozen (>36) to several thousand repeating units long. "A few" here means "3" as a unit. In contrast, in CKV, the short-chain branches are shorter or have a lower number of repeating units, e.g., a few to a few dozen.2, 5, 10, 20, 30, < 36 repetition units. The CKV can be measured using the GPC-IR method.

[0025] "Compatible" refers to a combination of polymer and rosin ester that does not undergo visible phase separation upon static heating. Compatibility can be determined using the Compatibility Test Method. In this test, a mixture of the rosin ester and the polymer (usually 1:1 by weight unless otherwise specified) is heated to a processing temperature between 100 and 200 °C (chosen to correspond to the intended use of the composition), held for 24 hours, and then examined with the naked eye against a black and white background. If no visible phase separation is observed after 24 hours, the polymer and rosin ester are considered compatible under these conditions. Compatibility can also be determined using the Cloud Point Compatibility Test Method.This procedure is essentially the same as ASTM D7638-20, but is adapted for polymer / rosin ester mixtures. In this test, a 1:1 (wt / wt) mixture of rosin ester and polymer is heated to 180–200 °C with stirring until a homogeneous, transparent melt is obtained. The melt is then cooled from 200 °C to 25 °C at approximately 2 °C / min while the optical clarity is monitored (visually or, if instrumented, at a specific light transmission threshold, e.g., 80% T). The cloud point is the temperature at which haze or cloudiness is first observed upon cooling. Lower cloud points indicate better compatibility of the rosin ester with the polymer.

[0026] The new carbon content test method refers to ASTM D6866-22, Method B (AMS), entitled "Standard Test Methods for Determining the Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis." This method determines the percentage of biogenic carbon in a sample based on radiocarbon analysis. 14 C), expressed as % biogenic carbon in relation to the total carbon content of the sample.

[0027] “Rophonium ester-based composition” refers to a composition containing the rosin ester and a polymer.

[0028] The disclosure relates to a composition containing a rosin ester obtained as a reaction product of rosin and an aliphatic polyol. The rosin ester is characterized by its compatibility with a range of polymers and is suitable for numerous applications, including hot melt adhesives and tires.

[0029] (Rophonium ester): The rosin ester is obtained by reacting a rosin with an aliphatic polyol and optionally with carboxylic acids, and in embodiments without the need for any additional modification of the rosin ester.

[0030] (Rosin raw material): Here, rosin refers to rosin acid or resin acid. In some formulations, the rosin contains a mixture of resin acids, the composition of which varies depending on the plant species. Resin acids are C 20Monocarboxylic acids with fused rings, e.g., abietic acid, neoabietic acid, dehydroabietic acid, dihydroabietic acid, pimaric acid, levopimaric acid, sandaracopimaric acid, isopimaric acid, and palustric acid. Rosin can be obtained from balsam resin, wood rosin, and tall oil rosin (TOR). TOR generally has a higher proportion of pimarane-type acids (e.g., isopimaric acid, sandaracopimaric acid) than balsam resin, which can affect the softening point and ester compatibility.

[0031] In some embodiments, the rosin is a balsam resin used as a base material for the production of rosin ester derivatives. Balsam resin can be esterified with polyols to form a rosin ester. Chemically, balsam resin consists of resin acids such as abietic acid, neoabietic acid, palustric acid, and levopimarinic acid. The melting point of balsam resin is between 75 and 95°C. In some embodiments, the balsam resin has a resin acid content of 70–90%, 65–98%, > 65%, or < 98%, depending on the specific formulation.

[0032] In embodiments, the rosin is hydrogenated rosin. The hydrogenation can be partial or complete and is detected by a lower iodine number, reduced UV absorption in the 240–300 nm range, and reduced olefinic signals in FTIR / NMR. In embodiments, the rosin has residual C=C double bonds of < 40%, < 20%, < 15%, < 10%, < 5%, > 1%, 1% to 20%, or 1% to 10%, calculated based on the total content of original double bonds. Hydrogenation generally lightens the color and improves the thermal / oxidative stability of the raw material and the derived esters. The choice of the degree of hydrogenation can serve to establish a balance between stability and desired compatibility.When using hydrogenated rosin, the resulting rosin esters can exhibit lower cloud points and better blending homogeneity with certain polymers (e.g., low-VA EVA, metallocene polyolefin elastomers) compared to esters from unhydrogenated rosin. Hydrogenated rosin esters may also exhibit slower heat yellowing, a lower viscosity increase, and longer shelf life under storage and usage conditions.

[0033] In some embodiments, the rosin is disproportionated, increasing the levels of dehydroabietic and dihydroabietic acids at the expense of abietic / neoabietic acids. This disproportionation generally results in improved color stability, a lower iodine value, and a raw material suitable for esters requiring better thermal color.

[0034] In some embodiments, the rosin is enriched. Enrichment involves chemically modifying the conjugated double bond system of resin acids in the rosin to obtain a rosin with a lower PAN number (sum of palustrine + abietin + neoabietin, wt.%, e.g., < 25, < 20, etc.) and a higher molecular weight than the rosin before enrichment. The PAN number used here is the sum of the percentages of resin acids in the rosin, namely palustric acid, abietic acid, and neoabietic acid. Enriched rosin can be prepared by reacting rosin with maleic anhydride, fumaric acid, acrylic acid, or other unsaturated carboxylic acids.

[0035] In embodiments, the rosin comprises dehydroabietic acid in amounts of ≥ 35%, 35% to 60%, or 40% to 55% by weight, based on the total weight of the rosin. In embodiments, the weight ratio of dehydroabietic acid to dihydroabietic acid in the rosin is in the range of 1:0.80 to 1:0.25, 1:0.70 to 1:0.35, or 1:0.55 to 1:0.40.

[0036] In embodiments, the rosin raw material is refined to such an extent that the neutral components (unsaponifiable components, sterols, hydrocarbons) are reduced to less than 10 wt.%, e.g. less than 5 wt.% or less than 2 wt.%, of the total rosin.

[0037] In embodiments, the rosin has an acid number of 120 to 190 or 150 to 185 or 170 to 182 mg KOH / gram.

[0038] In embodiments, the rosin is added in amounts, based on the total weight of the reactants, of 15 to 93 or 55 to 90 or 20 to 60 or 25 to 75 wt.% to produce the rosin ester.

[0039] (Aliphatic polyol): In embodiments, the aliphatic polyol is a linear, branched, saturated, unsaturated or partially saturated polyol.

[0040] In embodiments, the aliphatic polyol has a general formula (I) or (II) and includes both linear / branched frameworks and quaternary carbons of the neopentyl type, which have hydroxyl substituents:

[0041] In structures (I) and (II), each n and m is independent ≥ 0, where the sum of n + m ≥ 1; each o, p, q and r is independent ≥ 0; each R 1 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 13 , R 14 , R 19and R 20 independent of one of H, CH3, CH2CH3, OH or CH2OH, where CH2OH is a terminal hydroxymethyl substituent; and each R 2 , R 6 , R 10 , R 11 , R 12 , R 15, R 16 , R 17 , R 18 , R 21 , R 22 and R 23 regardless of whether it is made of H or CH3.

[0042] In embodiments, the aliphatic polyol is selected from the group consisting of methylpropanediol, butylethylpropanediol (2-butyl-2-ethyl-1,3-propanediol), neopentyl glycol, trimethylpentanediol, trimethylolpropane, ditrimethylolpropane and mixtures thereof.

[0043] In embodiments, the aliphatic polyol comprises, in addition to the two or more hydroxyl moieties, one or more additional functional groups. Examples of such groups include alkoxy, haloalkyl, keto, and combinations thereof. In embodiments, these additional functional groups are non-interfering, i.e., they do not significantly hinder or prevent the esterification of the hydroxyl groups with resin acids.

[0044] In embodiments, the aliphatic polyol also contains one or more heteroatoms, e.g. sulfur or nitrogen, which are incorporated into the molecular structure.

[0045] In embodiments, the aliphatic polyol has an average hydroxyl functionality of 2 to 10, 2 to 7, or 3 to 5, determined as the number of reactive hydroxyl groups per molecule. The hydroxyl functionality can be determined by 1H-NMR incorporation of hydroxyl-containing methylene or methine protons and confirmed by hydroxyl number titration according to ASTM E222.

[0046] In embodiments, the aliphatic polyol has a ratio of the number of carbon atoms to oxygen of ≥ 2 or > 2.1 or > 2.2 or < 8 or 2 to 8 or 2.1 to 7.5 or 2 to 7.

[0047] In embodiments, the aliphatic polyol has an oxygen content of > 50 wt.% or > 55 wt.% or > 60 wt.% or 50 to 150 wt.% or 55 to 120 wt.% or 60 to 110 wt.% or 50 to 130 wt.%, measured by means of 13 The oxygen content can be determined by ¹³C NMR spectral analysis or by elemental analysis. To eliminate any doubt, the term "oxygen content" refers to the percentage of oxygen atoms in relation to the total molecular weight of the polyol.

[0048] The aliphatic polyol is commercially available from petrochemical or bio-based sources. In some embodiments, the aliphatic polyols useful for the production of the rosin ester are obtained from renewable carbohydrate feedstocks. Methylpropanediol, for example, can be obtained by fermentation of sugars such as glucose or sucrose followed by hydrogenation. Neopentyl glycol and trimethylpentanediol can be produced from bio-isobutanol obtained by fermentation of sugars, in combination with renewable methanol or formaldehyde. Trimethylolpropane and ditrimethylolpropane can also be synthesized from renewable butanol, e.g., bio-butanol produced by fermentation of carbohydrates, and renewable methanol.In some embodiments, glycerin, a byproduct of biodiesel production, is used as an intermediate raw material for the production of trimethylolpropane or ditrimethylolpropane. Accordingly, the rosin ester can be produced essentially from renewable resources.

[0049] In embodiments, the aliphatic polyol is added in amounts of 7 to 85 or 10 to 45 or 40 to 80 or 25 to 65 wt.% to produce the rosin ester, based on the total weight of the reactants.

[0050] (Optional carboxylic acids): In embodiments, the reaction forming the rosin ester also includes at least one carboxylic acid. The carboxylic acid can be selected from monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, and mixtures thereof.

[0051] Examples of carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidonic acid, behenic acid, cerotic acid, benzoic acid, phenylacetic acid, cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, linoleic acid, alpha-linolenic acid, elaidic acid, sapienic acid, arachidonic acid, myristoleic acid, palmitoleic acid, oleic acid, isostearic acid, tall oil fatty acid, adipic acid, 3-methyladipic acid, succinic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,2-cyclopentanedicarboxylic acid. 1,3-Cyclopentanedicarboxylic acid, isophthalic acid, terephthalic acid, phthalic acid, TOFA dimer, hydrogenated TOFA dimer, 2-(2-Carboxyphenyl)benzoic acid, 2,5-furandicarboxylic acid, camphoric acid, cis-norbornen-endo-2,3-dicarboxylic acid, trimellitic acid, 2,6-naphthalenedicarboxylic acid, oxalic acidMalonic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, brassylic acid, dodecanedioic acid, thamic acid, trimesic acid and mixtures thereof.

[0052] In embodiments, if added, the carboxylic acid is present in an amount of 15-75 wt% based on the total weight of the reactants, e.g., 30-70 wt%, 40-65 wt%, 20-50 wt%, 6-40 wt%, 7-30 wt%, or 8-22 wt%. In embodiments, a dicarboxylic acid (e.g., adipic acid, succinic acid, sebacic acid, phthalic acid) is used at 5-25 wt% to adjust the molecular weight, softening point, and compatibility; a monocarboxylic acid (e.g., stearic acid, benzoic acid, tall oleic acid) is used at 0.5-5 wt% as a chain stopper to control the hydroxyl number and limit branching. and a polycarboxylic acid (e.g. trimellitic acid, trimesic acid) is used at 0.5-8 wt% to introduce limited branching while avoiding gelation.

[0053] (Characteristics / Properties of rosin ester): In embodiments, the rosin ester formed has a cyclic carbon content of less than 50% or 20-40% or 25-35% or an aliphatic carbon content of 50-98% or 55-95% or 60-90% or 65-95% or more generally of more than 60% and up to 100%, based on the total carbon atoms present, as determined by 13 determined by C-NMR.

[0054] In embodiments, the formed rosin ester has a weight-average molecular weight of 300-7000 g / mol or 1500-6000 g / mol or 2000-5000 g / mol or < 6000 or < 5500 or < 5000 or < 4000 or < 3000 or < 2000 g / mol, as determined by gel permeation chromatography (GPC).

[0055] In embodiments where the rosin raw material is unhydrogenated or fractionally enriched, the rosin ester has a dehydroabietic acid (DHA) content of more than 35 wt.% or 35-65 wt.% or 38-55 wt.%, based on the total weight of the rosin ester.

[0056] In embodiments where the rosin raw material is hydrogenated, the rosin ester has a DHA content of less than 35 wt.% or less than 30 wt.% or 10-30 wt.%.

[0057] In embodiments, the rosin ester has a Gardner color of < 3 or < 2 or < 1 or > 0.001 as measured according to ASTM D1544-04 (2010).

[0058] In embodiments, the rosin ester has a hydroxyl number measured according to ASTM E222 of < 50 or < 40 or < 30 or < 20 or < 10 or < 6 or < 3 mg / KOH / g.

[0059] In embodiments, the rosin ester has an acid number measured according to ASTM D465 of < 40 or < 30 or < 20 or < 15 or < 10 or < 5 mg / KOH / g.

[0060] In embodiments, the rosin ester has a glass transition temperature (Tg) determined by differential dynamic calorimetry (DDK) according to ASTM D6604. g ) from -80 to 100 °C or -30 to 80 °C or -40 to 30 °C or -20 to 10 °C or 0 to 70 °C.

[0061] In embodiments, the rosin ester has a softening point of 0 to 150 °C, 50 to 130 °C or 70 to 120 °C, measured according to the ring-and-ball method according to ASTM E28.

[0062] In embodiments, the rosin ester has a structure formed by means of 13 C-NMR spectroscopy or elemental analysis determined oxygen content of 2-15% or < 10% or < 8% or < 6% or 2 to 15% or 3 to 12% or 2 to 10% or 3 to 7% or > 2% or < 9%.

[0063] In embodiments, the rosin ester has a melt viscosity at 150 °C of 12,000 to 15,000 mPa·s; or > 12,500 mPa·s; or < 14,500 mPa·s or 5,000-12,000 mPa·s, as measured with a Brookfield RTV viscometer at a spindle speed of 3 rpm at 150 °C.

[0064] In one embodiment, the rosin ester has a refractive index > 1.52 or > 1.55 measured at 20 °C with an Abbe refractometer according to ASTM D1218 and a Brookfield viscosity (ASTM D-3236) of 50 to 25,000 mPa.s at 177 °C measured at 3 rpm according to ASTM D 3236.

[0065] In embodiments using renewable polyol feedstock, the resulting rosin esters are characterized by a high renewable carbon content. The rosin ester contains at least 80%, 85%, 90%, or 95% biogenic carbon as determined by ASTM D6866 (New Carbon Content Test Method). These values ​​demonstrate that the compositions are substantially derived from renewable resources while exhibiting compatibility and performance characteristics comparable to those of conventional petroleum-derived tackifiers.

[0066] (Rophonium ester-based composition): The rosin ester is further characterized by its compatibility with a range of polymers, forming a rosin ester-based composition that is useful, for example, as a tackifier in adhesives, sealants, elastomers, tire compounds, and similar applications. Compatibility is determined by the Compatibility Test Method for Phase Separation or by the cloud point in the Cloud Point Compatibility Test Method.

[0067] In embodiments, the rosin ester is compatible with polymers such as ethylene vinyl acetate (EVA), metallocene polyolefins (mPOE), functional polyolefins, amorphous α-olefins (APO), styrene block copolymers, polybutadiene polymers, polylactic acid polymers, polyesters, thermoplastic polyurethanes, acrylates, polyhydroxyalkanoates and mixtures thereof.

[0068] In embodiments of mixtures with polymers determined by the cloud point compatibility test method, the rosin esters exhibit cloud points that, under the specified test conditions, are associated with good solubility of the tackifier. In embodiments, a homogeneous 1:1 (wt / wt) melt of the rosin ester and the polymer, prepared at 180–200 °C with stirring, exhibits a cloud point of less than 150 °C or 40–140 °C at an optical transmission threshold of 80% T upon cooling (≈ 2 °C / min). Lower cloud points indicate higher compatibility for a particular polymer-resin pair.

[0069] In embodiments, the rosin ester in a 1:1 (wt / wt) mixture with ethylene vinyl acetate (EVA) copolymers for EVA types containing ∼ 18-33 wt% vinyl acetate exhibits a cloud point (80% T criterion) of about 80-140 °C; the mixture exhibits a cloud point of about 40-110 °C in a 1:1 (wt / wt) mixture with metallocene-catalyzed poly-α-olefins (mPO; e.g., ethylene / 1-octene elastomers); and the mixture exhibits a cloud point of about 70-120 °C in a 1:1 (wt / wt) mixture with amorphous poly-α-olefins (APAO).

[0070] In embodiments, the use of hydrogenated rosin raw material typically lowers the cloud point of the polymer / rosin ester mixture by approximately 20–60 °C for EVA, mPO, and APAO systems compared to the corresponding ester prepared from unhydrogenated rosin, under the specified test conditions. Without citing a theory, this improvement is attributed to the lower aromaticity / unsaturation (lower DHA content) and the associated shift in solubility parameters resulting from the hydrogenation of the rosin component.

[0071] In embodiments, the compatible polymer / tackifier ratios include 60 / 40 or 55 / 45 or 50 / 50 (wt / wt) polymer / rosin ester at processing temperatures of 100-200 °C, wherein the mixtures remain substantially free of visible phase separation according to the compatibility test procedure and exhibit cloud points within the ranges mentioned herein according to the cloud point compatibility test procedure.

[0072] In embodiments, the compatible polymer is an ethylene-vinyl acetate copolymer (EVA). Useful EVA copolymers are those with a vinyl acetate content of more than 24 wt.%, more than 28 wt.%, or 25 to 55 wt.%, based on the total weight of the copolymer.

[0073] In embodiments, the compatible polymer is a metallocene-catalyzed polyolefin (mPO). The mPO is selected from the group consisting of a metallocene-catalyzed polyolefin elastomer (mPOE), a metallocene-catalyzed polyolefin plastomer (mPOP), and mixtures thereof. In embodiments, the mPO is a copolymer of ethylene and at least one C3-C 20 -α-olefin and contains ethylene in amounts of > 50 or > 60 or > 70 or > 80 or > 90 or < 95 wt%, based on the total weight of the copolymer. Examples of C3-C 20α-olefins include propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and mixtures thereof. Examples of mPO include ethylene / butene copolymers, ethylene / hexene-1 copolymers, ethylene / octene copolymers, modified ethylene / α-olefin / diene interpolymers (e.g., modified ethylene / propylene / diene interpolymers, ethylene / propylene / octene terpolymers, etc.), ethylene / propylene copolymer, propylene / 1-butene copolymers, propylene / 1-hexene copolymers, propylene / 4-methyl-1-pentene copolymers, propylene / 1-octene copolymers, propylene / ethylene / 1-butene copolymers, propylene / ethylene / ethylidenenorbornene copolymers, propylene / ethylene / 1-hexene copolymers, propylene / ethylene / 1-octene copolymers, and propylene / styrene copolymers. Propylene / ethylene / styrene copolymers. In embodiments, the mPO further comprises C4-C 18 -Diolefin and / or alkenylbenzene.

[0074] In embodiments, the compatible polymer is an amorphous polyolefin (APO). The APO is used instead of or in addition to the mPO. APO is a polymer obtained from the polymerization of α-olefins, e.g., ethylene, propylene, butene, etc. In embodiments, the APO is characterized by its amorphous (non-crystalline) structure, in which molecular chains are arranged randomly rather than in a highly ordered pattern. In embodiments, the APO is selected from the group consisting of polyethylene (PE); polypropylene (PP); polybutylene (PB); copolymers of propylene and ethylene; copolymers of propylene and 1-butene or other higher α-olefins; terpolymers of ethylene, propylene, and 1-butene; ethylene-propylene rubber; and mixtures thereof. In embodiments, the APO comprises propylene-based polymers selected from linear propylene homopolymers and propylene copolymers.Propylene-based polymers can have a propylene content of at least 50% and can be produced using Ziegler-Natta or metallocene catalysts.

[0075] Examples of rosin ester-based formulations containing rosin ester include hot melt adhesive formulations where the compatible polymer is added in amounts of 10-90 wt% (e.g., 50-80 wt% EVA, mPO, or APO), the rosin ester is added in amounts of 20-50 wt%, and at least one additive (e.g., wax, plasticizer, stabilizer) is present in amounts of up to 50 wt%.

[0076] Other rosin ester-based formulations include tire and rubber compounds. For example, a formulation containing: (i) a rubber component comprising at least one diene elastomer and, per 100 parts by weight (phr) of the rubber component: ii) 1–75 phr of the rosin ester as a tackifier; (iii) 30–200 phr of a filler; (iv) 0–50 phr of a plasticizer; and (v) 0–90 phr of an optional additive. The rubber component may contain natural rubber, synthetic polyisoprene, polybutadiene, styrene-butadiene rubber, or copolymers thereof.

[0077] In embodiments, the rosin ester is used in pressure-sensitive adhesives (PSAs), the composition comprising the rosin ester at 10-60 wt% in combination with one or more styrene block copolymers (e.g., styrene-isoprene-styrene or styrene-ethylene-butylene-styrene) and a plasticizer, optionally with other resins, oils, and stabilizers. The PSA formulations can be applied to adhesive tapes, labels, or hygiene products. The adhesive performance can be characterized by PSTC or FINAT methods, including 180° peel strength, loop tack, and shear adhesion. For example, representative PSA compositions containing the rosin esters can exhibit a peel strength of at least 5 N / 25 mm and a shear adhesion of at least 1000 minutes at 23°C.

[0078] In embodiments, the rosin ester is incorporated into sealants or construction adhesives containing 5-40 wt.% of rosin ester, 30-70 wt.% of polymer such as EVA or polyolefin, 10-60 wt.% of filler and 0-20 wt.% of plasticizer such as wax or oil.

[0079] In embodiments, the rosin ester is mixed with bioplastics such as polylactic acid (PLA) in amounts of 10-40 wt.% to improve adhesion, flexibility and toughness.

[0080] In embodiments, the rosin ester is incorporated together with film-forming polymers and solvents into coating compositions such as varnishes or alkyd-based systems at a concentration of 20-60% by weight. In embodiments, the rosin ester is melt- or solution-compatible with at least one film-forming polymer selected from acrylic or styrene-acrylate copolymers, vinyl polymers including polyvinyl acetate and polyvinyl butyral, alkyd resins, and saturated or unsaturated polyesters; and in further embodiments, it is miscible with polyurethane-, phenol-, epoxy-, or cellulose-based systems under conventional solvent or melt-mixing conditions.

[0081] Examples of fillers include calcium carbonate, carbon nanotubes, clay, mica, silica, silicates, talc, titanium dioxide, aluminum oxide, zinc oxide, starch, wood flour, carbon black, and mixtures thereof. Examples of plasticizers include aliphatic acid esters, hydrocarbon processing oils, tall oil pitch, modified tall oil pitch, and mixtures thereof.Examples of additives include activators, hardening agents, stabilizers, neutralizing agents, thickeners, coalescing agents, lubricants, release agents, antimicrobial agents, surfactants, flame retardants, antioxidants, antiozonants, color-changing pH indicators, plasticizers, film-forming additives, colorants, pigments, UV stabilizers, UV absorbers, catalysts, viscosity modifiers, deaerators, tougheners, adhesion promoters, dyes, heat stabilizers, lubricants, flow modifiers, anti-drip agents, antiblocking agents, antistatic agents, waxes, processing aids, and stress-relieving additives.

[0082] Rosin ester-based compositions can be produced by conventional mixing methods. In some embodiments, the rosin ester and the polymer are combined in a heated vessel, extruder, or internal mixer at 100–200 °C until homogeneous, with fillers, waxes, oils, or stabilizers being incorporated under shear. The homogeneous mixture is then discharged and processed into pellets or sheets, or applied directly as a hot melt adhesive, rubber compound, sealant, or coating.

[0083] (Properties of rosin ester-based compositions): When used as an adhesive in formulations, rosin ester is highly compatible with a range of polymers, resulting in stable, smooth, and clear compositions in which no phase separation occurs. Rosin ester-based compositions also offer lower melt viscosity, higher specific adhesion properties, and improved heat resistance.

[0084] In embodiments, a hot melt adhesive composition containing the rosin ester as a tackifier has a Brookfield viscosity of 500-20,000 mPa.s, 800-15,000 mPa.s or 1,000-12,000 mPa.s as measured at 160 °C according to ASTM D3236.

[0085] In embodiments, the hot melt adhesive composition exhibits a peel strength of ≥ 1.5 N / cm, ≥ 2.0 N / cm, or ≥ 2.5 N / cm, as measured on polyethylene or polypropylene film substrates according to ASTM D903. The shear adhesion failure temperature (SAFT) is ≥ 70 °C, ≥ 80 °C, or ≥ 90 °C, as measured by bonding kraft paper strips and subjecting them to shear stress until the bond fails.

[0086] In embodiments, the hot melt adhesive composition exhibits a peel-off adhesive failure temperature (PAFT) of ≥50 °C, ≥60 °C, or ≥70 °C as measured according to ASTM D4498. The adhesive retains its cohesive integrity and bond strength even at elevated service temperatures, reflecting the contribution of the aliphatic polyol rosin ester to thermal stability.

[0087] In embodiments, a hot melt adhesive composition containing the rosin ester shows a biodegradation of at least 20%, at least 50%, or at least 90% in a test according to ASTM D5338-15 (“Biodegradation Test Method”) after 60 days.

[0088] (Production of rosin esters): The rosin ester can be produced by the processes described in US Patent No. 11034858, which is incorporated herein by reference.

[0089] In embodiments, the rosin ester is prepared by reacting the rosin, the aliphatic polyol, optionally a carboxylic acid, and optionally in the presence of an esterification catalyst at a temperature of 150 to 300 °C for 2 to 18 hours, typically with continuous removal of water under reduced pressure or using an azeotropic solvent to complete the esterification. In some cases, the rosin ester is a liquid (e.g., a viscous liquid) at 20 °C and 1 atm pressure.

[0090] Suitable esterification catalysts include Lewis acids and Brønsted-Lowry acids. Examples include acetic acid, p-toluenesulfonic acid, methanesulfonic acid, hypophosphoric acid, boric acid, sulfuric acid, triphenyl phosphite, calcium hydroxide, cation exchange resins, metal oxides on SiO₂ and Al₂O₃ supports, calcium oxide, magnesium oxide, zinc oxide, aluminum oxide, iron chloride, calcium formate, calcium phosphonates, and mixtures thereof.

[0091] In some embodiments, a co-catalyst is used in the esterification reaction. Examples of co-catalysts include acridone, anthrone, 9-fluorenone, thioxanthone, xanthone, derivatives, and combinations thereof.

[0092] A disproportionation catalyst, also known as a rosin stabilizer, can be incorporated into the esterification reaction. The disproportionation catalyst can be selected from 2,2'-thiobisphenols, 3,3'-thiobisphenols, 4,4'-thiobis(resorcinol), 1,1'-thiobis(pyrogallol), 4,4'-thiobis(6-t-butyl-m-cresol), 4,4'-thiobis(6-t-butyl-o-cresol), thiobisnaphthols, 2,2'-thiobisphenols, 3,3'-thiobisphenols, palladium, nickel, platinum, Pd / C, iodine, iodides, sulfides, poly-t-butylphenol disulfide, 4,4'-thiobis(2-t-butyl-5-methylphenol), nonylphenol disulfide oligomers, amylphenol disulfide polymer and mixtures thereof.

[0093] In some embodiments, the rosin ester undergoes secondary processing, such as hydrogenation and / or disproportionation, which reduces the dehydroabietic acid (DHA) content, for example, to < 35 wt.% or < 30 wt.%. In other embodiments, the secondary processing consists of dehydrogenation or oxidation, which increases the DHA content or forms DHA-like aromatic structures. In still other embodiments, the rosin ester is used without secondary processing, maintaining compatibility with polymers such as ethylene vinyl acetate (EVA), metallocene polyolefins, amorphous poly-α-olefins (APAO), styrene block copolymers, and related elastomeric or thermoplastic polymers.

[0094] (Applications): Due to its compatibility with a range of polymers, the rosin ester composition, when used as an adhesive, exhibits improved adhesion to a wide variety of surfaces, from low-polarity to high-polarity, as well as to very smooth substrates such as film, paper, etc. The rosin ester can be used in packaging, bookbinding, labeling, adhesive tapes, labels and stickers, protective films, sealants, diapers and sanitary napkins, edge banding, shoe soles, leather goods, electronic assembly, protective coatings, trim and panel bonding, headliners, interlinings, etc.

[0095] As a tackifier, rosin ester can be used in hot melt and pressure-sensitive adhesives, adhesive dispersions such as aqueous adhesive dispersions, modifiers for rubbers and various plastics, emulsifiers for synthetic rubber, base materials for chewing gum, resins in coating compositions, printing inks, sizing agents for papermaking, asphalt markings, road markings, thermoplastic road markings, printing inks, coatings, rubbers (e.g., tires and tire treads), sealants, and plasticizers.

[0096] Hot melt adhesives containing rosin esters are suitable for sealing boxes and cartons, forming trays, and for bookbinding applications. In such applications, the compositions are applied in molten form and offer strong bonds over a wide temperature range, including cooled and hot-filled conditions. Compositions containing the rosin esters described here can achieve shear adhesion failure temperatures (SAFT) of at least 80°C and open times of 20–120 seconds, depending on the formulation. The adhesives are particularly suitable for packaging materials such as kraft paper, recycled cardboard, particleboard, coated board, and multilayer laminates, including aluminum foil and polymer films.

[0097] Adhesives containing rosin ester are suitable for the manufacture of absorbent articles such as diapers, training pants, feminine hygiene products, and adult incontinence products. In such applications, the adhesives can be used as assembly adhesives, positioning adhesives, and elastic fixing adhesives. Representative formulations contain 20–50 wt% rosin ester adhesive with 50–80 wt% polyolefin or block copolymer base polymer. The adhesives can be applied in fiber or bead form and provide a secure bond while maintaining the softness and flexibility of the article.

[0098] Rosin ester compositions can also be used in adhesives for woodworking, furniture, flooring, and panel laminating. In such applications, the adhesives are typically formulated with polyolefin polymers and waxes to achieve a viscosity of 5,000–200,000 mPa·s at 200 °C, suitable for extrusion or roller application. These compositions are capable of bonding wood, wood-based materials, particleboard, and composite panels with strong adhesion and creep resistance, even at elevated temperatures and humidity.

[0099] Rosin ester can also be used in a variety of other applications, e.g., as a softening and plasticizing agent in chewing gum bases, as a weighting and opacifying agent in beverages, as a surfactant, surface activity modulator or dispersant, as an additive in waxes and wax-based polishes, as a modifying agent in skin products and cosmetic formulations (e.g., mascara), in the electrical industry as insulators, as drying oils in the manufacture of paints and other wood treatment products, in the treatment of wooden boat hulls, in soaps, in candles, as a lubricant in motor vehicle applications and engine lubricants, for the production of biodiesel, for the production of biodegradable hydraulic fluids, in metal processing and other industrial applications, as a phase change material, or as a hardening agent in concrete.

[0100] (Analytical method): The rosin ester described herein is characterized by a unique combination of identifiable features and properties. The aliphatic polyol can be analyzed by 1 Dog 13 Hydroxyl groups can be identified by 13C NMR spectroscopy, with FTIR confirming their presence. Purity can be determined by GC or HPLC. The carbon-to-oxygen ratio is determined from the molecular structure and confirmed by elemental analysis (e.g., ASTM D5291). Hydroxyl functionality can be quantified by the hydroxyl number according to ASTM E222.

[0101] The dehydroabietic acid (DHA) content of the rosin ester is determined by gas chromatography-mass spectrometry (GC-MS) or high-performance liquid chromatography (HPLC) after alkaline hydrolysis of the ester to release resin acid components. DHA is quantified by comparison with authentic standards, and the percentage by weight of DHA is reported as a percentage of the total weight of the detected resin acid components.

[0102] The acid value of the rosin ester can be determined according to ASTM D664. The results are given in milligrams (mg) of potassium hydroxide (KOH) required to neutralize the acidic components in one gram (g) of the sample.

[0103] The weight-mean molecular weight (Mw), number-mean molecular weight (Mn), and polydispersity index (PDI) of the rosin ester can be determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the eluent at 30 °C, with calibration performed using polystyrene standards with a narrow molecular weight distribution. Values ​​are given in grams per mole (g / mol).

[0104] The glass transition temperature of the rosin ester can be determined according to ASTM D6604 or by differential scanning calorimetry (DSC) according to ASTM D3418. The Tg is given as the midpoint of the transition in degrees Celsius (°C).

[0105] The percentage of renewable (biogenic) carbon in the rosin ester is determined according to ASTM D6866, if relevant. The results are reported as the percentage of biogenic carbon relative to the total carbon content.

[0106] When the rosin ester is used in end applications, e.g. hot melt adhesives, tires, etc., its compatibility with the polymer can be determined using the compatibility test methods described above.

[0107] The identity of the polymer in formulations containing the rosin ester can be determined by spectroscopic and thermal analysis methods. Fourier-transform infrared spectroscopy (FTIR) and 1 Dog 13 C) provide characteristic signals that differentiate ethylene vinyl acetate (EVA), amorphous poly-α-olefins (APO), styrene block copolymers (SBC), and polyester-based polymers such as polylactic acid (PLA) and polyhydroxyalkanoates (PHAs). DDK and thermogravimetric analysis (TGA) can also be used to differentiate polymers based on glass transition temperatures (Tg), melting points, and thermal degradation profiles.

[0108] The relative amounts of polymer and rosin ester can be determined by solvent extraction and subsequent analysis of the isolated polymer fraction using FTIR, NMR, DDK, or GPC. Together, these techniques enable reliable identification of the polymers contained in the composition and their relative weight percentages.

[0109] If necessary, the adhesive performance of hot melt adhesive compositions containing rosin ester can be evaluated according to ASTM D1876. The results are given as average peel strength in Newtons per centimeter (N / cm).

[0110] (Examples): The following illustrative examples are not exhaustive. Components used in the examples include, but are not limited to:

[0111] RA 1 is a tall oil rosin product from Kraton Corporation with an acid number in the range of 150–180 mg KOH / g, a softening point (ring and ball) of 68–80 °C, a Gardner color in the range of 5–8, and a specific gravity of 1.05–1.10. The molecular weight (Mw) is in the range of 900–1,500 Da, the number-mean molecular weight (Mn) is 600–800 Da, and the polydispersity (Mw / Mn) is 1.2–1.5. The glass transition temperature (Tg) is below or slightly above ambient temperature (-20 to +10 °C).

[0112] RA 2 is a hydrogenated rosin product derived from balsam resin that has undergone catalytic hydrogenation to reduce the number of conjugated double bonds. This results in improved stability and a lighter color compared to unmodified rosin. It has an acid number in the range of 160 to 175 mg KOH / g, a ring-and-ball softening point of 70–80°C, and a Gardner color of 1–3. The molecular weight (Mw) is generally in the range of 500 to 1,500 Da with a wide distribution, and the glass transition temperature (Tg) is approximately -10 to +10°C.

[0113] Antioxidant 1 is a sterically hindered phenolic antioxidant.

[0114] Antioxidant 2 or Pentaerythritoltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (CAS 6683-19-8) is a high molecular weight, sterically hindered phenolic antioxidant used as a primary antioxidant.

[0115] Stabilizer 1 is a polymeric disulfide derived from tert-butylphenol and acts as a radical scavenger and sulfur donor.

[0116] The polyols used in the examples are listed below in Table 1. Table 1 Kolophoniumester Polyole Anz. derHydroxylgruppen Molmasse(g / mol) ChemischeZusammensetzung(%) C / O-Verhältnis C H O RE-1 Methylpropandiol 2 90,1 53,3 11,2 35,5 2 RE-2 Butylethylpropandiol 2 160,3 67,5 12,6 20,0 4,5 RE-3 Neopentylglykol 2 104,1 57,7 11,6 30,7 2,5 RE-4 Trimethylpentandiol 2 146,2 65,7 12,4 21,9 4 RE-5 Trimethylolpropan 3 134,2 53,7 10,5 35,8 2 RE-6 Ditrimethylolpropan 4 250,3 57,6 10,5 32,0 2,4 RE-7 Glycerin 3 92,1 39,1 8,8 5,2 1 RE-8 Pentaerythrit 4 136,1 44,1 8,9 47,0 1,25 RE-9 Dipentaerythrit 6 254,3 47,2 8,7 44,0 1,4

[0117] The polymer mPoE 1950 is a statistical ethylene-a-olefin copolymer (ethyleneoctene) with a density of approximately 0.874 g / cm³. 3 , a Tg of about -56 °C, a melting point of about 70 °C, a Brookfield viscosity at ∼ 177 °C of about 17,000 mPa.s, a volatile content of < 0.15%, a tensile strength of about 1.7-2.0 MPa, an elongation at break of ∼ 190% and a light Gardner color (≈ 1-2).

[0118] Cloud Point Measurement: The cloud point of a rosin ester / polymer mixture is measured using an optical transmission method analogous to ASTM D2024. A homogeneous molten mixture of rosin ester and polymer in the specified weight ratio is prepared and loaded into an optical cell with a path length of 1 cm. The sample is heated to a clear state to eliminate the thermal history and then cooled at a rate of 2 °C / min while the transmittance is monitored at approximately 600 nm. The cloud point is defined as the temperature at which the transmittance first shows a sustained decrease of at least 5% from the clear baseline, corresponding to the onset of fogging or haze. The cloud point determination is performed analogously to established methods such as ASTM D2500, ASTM D5773, and ISO 3015.

[0119] Example RE-1 - Methylpropanediol (MPD) rosin ester. 1200 g of rosin are placed in a 2-1 four-necked flask under nitrogen and heated to 200 °C with mechanical stirring until completely melted. Methylpropanediol (180 g), Antioxidant 1 (0.3 wt%), and Stabilizer 1 (0.3 wt%) are added. The mixture is heated to 280 °C at 30 °C / h and held for 9 h, allowing the water formed to evaporate. The volatile components are removed by bubbling through the mixture with nitrogen for 2 hours. The batch is cooled to 180 °C and drained off. A clear, pale amber resin is obtained. The rosin ester is expected to have the following properties: Dehydroabietic acid (DHA) ∼ 40 wt%; Acid value ∼ 9–12 mg KOH / g; Mw (GPC, THF, PS standards) ∼ 2600-3000 g / mol; Tg (ASTM D6604 / DSC) ∼ 20-30 °C; Softening point ∼ 70-80 °C.

[0120] A 50:50 (wt / wt) mixture with mPoE 1950 is prepared and tested on a Novomatics Cloud Point Machine; the cloud point is recorded at ≤ 80% transmission (λ ≈ 600 nm). The mixture is expected to have a cloud point of ∼ 145 °C (homogeneous below this temperature at 80% T).

[0121] Example RE-2 -Butylethylpropanediol (BEPD) rosin ester. Example RE-1 is repeated except that 220 g of butylethylpropanediol are used as the polyol, resulting in a clear resin product. The resulting rosin ester is expected to have a dehydroabietic acid (DHA) content of 39–41 wt%, an acid number of about 12–16 mg KOH / g, a weight-mean molecular weight of about 2900–3200 g / mol, a glass transition temperature (Tg) of about 15–25 °C, and a softening point of about 68–78 °C.

[0122] A 50:50 (wt / wt) mixture of the rosin ester with mPoE 1950 is prepared, and the mixture is expected to have a cloud point of about 140 °C.

[0123] Example RE-3 - Neopentyl glycol (NPG) rosin ester. Example RE-1 is repeated except that 170 g of neopentyl glycol is used as the polyol, yielding a pale solid resin product. The resulting rosin ester is expected to have a dehydroabietic acid (DHA) content of 41–43 wt%; an acid number of ∼ 8–12 mg KOH / g; a molecular weight of ∼ 3000–3300 g / mol; a melting point of ∼ 45–55 °C; and a softening point of ∼ 82–88 °C.

[0124] A 50:50 (wt / wt) mixture of the rosin ester with mPoE 1950 is prepared, and the mixture is expected to have a cloud point of about 140 °C.

[0125] Example RE-4 - Trimethylpentanediol (TMPD) rosin ester. Example RE-1 is repeated except that 200 g of trimethylpentanediol is used as the polyol, yielding a clear, medium-hard resin. The resulting rosin ester is expected to have a DHA content of approximately 40–42 wt%; an acid number of approximately 15–20 mg KOH / g; a molecular weight of approximately 2800–3100 g / mol; a Tg of approximately 30–40 °C; and a softening point of approximately 78–84 °C.

[0126] A 50:50 (wt / wt) mixture of rosin ester with mPoE 1950 is prepared, and the mixture is expected to have a cloud point of ~150 °C.

[0127] Example RE-5 - Trimethylolpropane (TMP) rosin ester. 1200 g of rosin were placed in a 2-1 four-necked flask under nitrogen and heated to 200 °C with mechanical stirring until completely melted. Trimethylolpropane (160 g), Antioxidant 1 (0.3 wt%), and Stabilizer 1 (0.3 wt%) were added. The reaction mixture was heated to 280 °C (30 °C / h) and held at 280 °C for 9 hours under dehydration. The volatile components were stripped during a 2-hour nitrogen replacement, the mixture was cooled to 180 °C, and drained off. The product obtained had a softening point of 83 °C and an acid number of 5.8 mg KOH / g. The DHA content of the product was not measured. Due to the use of a DHA-enriched rosin raw material and the lack of hydrogenation during esterification, the DHA content is expected to be approximately 40-50 wt% of the total resin acids in the ester.

[0128] A 50:50 (wt / wt) mixture of rosin ester with mPoE 1950 was prepared and tested for cloud point using a Novomatics Cloudpoint Machine. At a light transmission of 80%, a cloud point temperature of 155 °C was measured.

[0129] Example RE-6 - Ditrimethylolpropane (Di-TMP) rosin ester: Example RE-1 is repeated except that 250 g of ditrimethylolpropane is used as the polyol, yielding a light-colored, hard resin. The resulting rosin ester is expected to have a DHA content of approximately 43-45 wt%; an acid number of approximately 6-10 mg KOH / g; a molecular weight of approximately 3900-4300 g / mol; a melting point of approximately 55-65 °C; and a softening point of approximately 88-95 °C.

[0130] A 50:50 (wt / wt) mixture of rosin ester with mPoE 1950 is prepared, and the mixture is expected to have a cloud point of ~150 °C.

[0131] Comparative example RE-7 - Glycerol rosin ester. Example RE-1 is repeated with the difference that 150 g of glycerol is used as the polyol. The resulting resin is expected to have a dehydroabietic acid content of about 40 wt%, an acid number of 12 mg KOH / g, a weight-mean molecular weight of 3,000–3,500 g / mol, and a Tg of about 40–50 °C. When mixed 1:1 with mPoE 1950, the product is expected to have a cloud point of approximately 180–190 °C (80% transmission), indicating poor compatibility with polyolefin polymers.

[0132] Comparative example RE-8 - Pentaerythritol rosin ester. Example RE-5 was repeated except that 200 g of pentaerythritol was used as the polyol. The resulting resin has an acid number of approximately 5 mg KOH / g, a Tg of approximately 52 °C, and a softening point of 96–103 °C. When mixed 1:1 with mPoE 1950, the product exhibited a cloud point of approximately 200 °C (80% transmission), indicating poor compatibility.

[0133] Comparative example RE-9 - Dipentaerythritol colophony ester. Example RE-1 is repeated except that 250 g of dipentaerythritol is used as the polyol. The resulting resin is expected to have a dehydroabietic acid content of approximately 40 wt% and an acid number of approximately 4-8 mg KOH / g, a weight-mean molecular weight of 5,500-6,000 g / mol, and a Tg of approximately 80-95 °C. When mixed 1:1 with mPoE 1950, the product is expected to have a cloud point of approximately > 200 °C (80% transmission), indicating poor compatibility.

[0134] Example HMA 1 - EVA hot melt adhesive with TMP rosin ester: A hot melt adhesive composition is prepared by mixing 45 wt% EVA (vinyl acetate content ∼ 28%, MI ∼ 400 g / 10 min), 40 wt% TMP rosin ester (RE-5), 14 wt% paraffin wax, and 1 wt% antioxidant 2 at 170–180 °C until homogeneity is achieved. The resulting adhesive is expected to exhibit a Brookfield viscosity of approximately 4,000–6,000 mPa·s at 160 °C (ASTM D3236) and a cloud point of less than 160 °C according to the optical transmission method (analogous to ASTM D2024), indicating good compatibility between the EVA and the rosin ester. For adhesive bonds on kraft paper, a peel strength of ≥ 2.0 N / cm (ASTM D903) and a SAFT of approximately 85 °C are expected.

[0135] Example HMA 2 - PLA hot melt adhesive with BEPD rosin ester: A composition is formulated with 55 wt% polylactic acid (NatureWorks™ Ingeo 2003D), 35 wt% BEPD rosin ester (RE-2), 9 wt% Fischer-Tropsch wax, and 1 wt% antioxidant. The mixture is blended at 180 °C until homogeneous. The adhesive is expected to have a viscosity of approximately 8,000–10,000 mPa·s at 160 °C and a cloud point of approximately 150 °C (50:50 blend basis). The adhesive is expected to exhibit good compatibility with PLA and maintain a clear, single-phase mixture after 24 hours at 160 °C in the compatibility test procedure. The peel strength on PLA film substrates is expected to be ≥ 1.5 N / cm with fiber breakage. The share of renewable resources is expected to exceed 90% according to ASTM D6866.

[0136] Example HMA 3 - APAO hot melt adhesive with TMPD rosin ester: An adhesive mixture is prepared with 50 wt% amorphous poly-α-olefin (APAO, MI ~ 1,000 g / 10 min), 40 wt% TMPD rosin ester (RE-4), 9 wt% polyethylene wax, and 1 wt% stabilizer. Processing at 180 °C results in a smooth, homogeneous melt. The composition is expected to have a viscosity of approximately 6,000–8,000 mPa·s at 160 °C and a measured cloud point of approximately 145 °C. No visible phase separation is expected after 24 hours at 160 °C, confirming compatibility. The shear adhesion failure temperature (SAFT) is expected to be ~80°C, which is better than a control adhesive containing SYLVALITE™ RE100, which has a cloud point of >200°C.

[0137] Comparative Example HMA 4 - APAO Hot Melt Adhesive with Pentaerythritol Rosin Ester. An adhesive mixture is prepared with 50 wt% amorphous poly-α-olefin (APAO, MI ∼1,000 g / 10 min), 40 wt% pentaerythritol (PE) rosin ester (reference RE-8), 9 wt% polyethylene wax, and 1 wt% stabilizer. Processing at 180 °C results in a homogeneous melt. The composition is expected to have a viscosity of approximately 6,000–8,000 mPa·s at 160 °C (ASTM D3236). When evaluating compatibility with APAO, the adhesive is expected to exhibit a cloud point above 200 °C (80% transmission) according to the optical transmission method (analogous to ASTM D2024), indicating poor miscibility of the PE ester with APAO under these conditions. Visible phase separation is expected during the 24-hour compatibility test procedure using static heat at 160 °C.The shear adhesion failure temperature (SAFT) is expected to be lower than that of the corresponding APAO adhesive seom formulated with the TMPD rosin ester of example HMA-3 (which has a cloud point of about 145 °C and no visible phase separation).

[0138] Example - HR1 - Hydrogenated rosin as a RE raw material: Example RE-1 is repeated except that RA 1 is replaced gram by gram by RA 2, and all other conditions remain the same (nitrogen atmosphere, 200 → 280 °C rise, 9 h holding time, N2 stripping). A clear, very pale resin is obtained. The resulting rosin ester is expected to have the following properties: acid number of 8-12 mg KOH / g, Mw (GPC, THF, PS standards) of 2,600-3,000 g / mol, Tg of 15-25 °C, and softening point of ∼ 65-75 °C. A 50:50 (wt / wt) mixture with mPoE 1950 was prepared and tested on a Novomatics Cloud Point Machine (≤ 80% transmission at 600 nm). The mixture is expected to have a cloud point of 105-115 °C, which is 30-40 °C lower than the corresponding RE-1 based on RA 1, which is consistent with the improved compatibility thanks to the hydrogenated rosin raw material.

[0139] Example - HR2 - Hydrogenated Rosin as RE-3H Raw Material: Example RE-3 is repeated except that RA 1 is replaced gram for gram by RA 2, and all other conditions remain unchanged. A pale, medium-hard resin was obtained. The resulting rosin ester is expected to have an acid number of 7-10 mg KOH / g, a molecular weight of 3,000-3,300 g / mol, a temperature of 35-45°C, and a softening point of 78-86°C. A 50:50 (wt / wt) mixture with mPoE 1950 is prepared and evaluated as described above. The mixture is expected to have a cloud point of 95-110°C, which is 30-45°C lower than that of RA 1-based RE-3, again indicating improved polyolefin compatibility when using RA 2 as the rosin raw material.

Claims

[1] Rosin ester comprising the reaction product of a rosin and one or more aliphatic polyols having a structure of general formula (I), general formula (II) or a mixture thereof: wherein each n and m is independent of each other ≥ 0 and the sum of n + m is ≥ 1; Each o, p, q and r is independent of each other and ≥ 0; each R 1 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 13 , R 14 , R 19 and R 20 regardless of whether it is composed of H, CH3, CH2CH3, OH or CH2OH; and each R 2 , R 6 , R 10 , R 11 , R 12 , R 15, R 16 , R 17 , R 18 , R 21 , R 22 and R 23independent of whether it is made of H or CH3; wherein the aliphatic polyol has a ratio of the number of carbon atoms to the number of oxygen atoms of ≥ 2; and wherein the rosin ester has: an acid number of < 50 mg KOH / g, preferably < 40 mg KOH / g; particularly preferably < 30 mg KOH / g; a weight-average molecular weight of < 6000 g / mol, preferably < 5000 g / mol, particularly preferably < 4000 g / mol; and a glass transition temperature (T g ) from -40 to 100°C, measured according to ASTM D 6604. [2] Rosin ester according to claim 1, wherein the aliphatic polyol is selected from the group consisting of methylpropanediol, butylethylpropanediol, neopentylglycol, trimethylpentanediol, trimethylolpropane, ditrimethylolpropane and mixtures thereof. [3] Rosin ester according to one of claims 1 to 2, wherein the aliphatic polyol has a ratio of the number of carbon atoms to the oxygen atoms of 2 to 8. [4] Rosin ester according to any one of claims 1 to 3, wherein the rosin ester has a dehydroabietic acid content of ≥ 35 wt% based on the total weight of the rosin ester. [5] Rosin ester according to any one of claims 1 to 4, wherein the rosin is hydrogenated and the rosin ester has a dehydroabietic acid content of < 35 wt.%. [6] Rosin ester according to any one of claims 1 to 5, wherein the rosin ester comprises biogenic carbon to at least 80% or at least 50% or at least 20% as determined according to ASTM D6866. [7] Rosin ester according to any one of claims 1 to 6, comprising at least one of: a Gardner color of < 3; a hydroxyl number of < 50 mg KOH / g; a softening point of 70-120 °C; a Brookfield viscosity of 50 to 25,000 mPa·s at 177 °C, measured with the Brookfield Thermosel viscometer spindle SC4-27 at 3 rpm according to ASTM D 3236; and an oxygen content of 2-10 wt.%. [8] Rosin ester according to any one of claims 1 to 7, which, when mixed 1:1 (wt / wt) with a polymer selected from the group consisting of ethylene-vinyl acetate copolymers, metallocene-catalyzed poly-α-olefin elastomers, metallocene-catalyzed poly-α-olefin plastomers, amorphous poly-α-olefins, is free from visible phase separation after 24 hours at 160 °C in a compatibility test. [9] A rosin ester according to any one of claims 1 to 7, which, when mixed 1:1 (wt / wt) with a polymer selected from the group consisting of ethylene-vinyl acetate copolymers, metallocene-catalyzed poly-α-olefin elastomers, metallocene-catalyzed poly-α-olefin plastomers, amorphous poly-α-olefins, forms a mixture which, in the cloud point compatibility test procedure, exhibits a cloud point of ≤ 150 °C (80% transmission). [10] Rosin ester according to any one of claims 1 to 7, which, when mixed 1:1 (wt / wt) with an ethylene-vinyl acetate copolymer containing 18 to 33 wt% vinyl acetate based on the total weight of the copolymer, forms a mixture which exhibits a cloud point of ≤ 140 °C at 80% transmission in the cloud point compatibility test procedure. [11] Rosin ester according to any one of claims 1 to 7, which, when mixed 1:1 (wt / wt) with a metallocene-catalyzed poly-α-olefin elastomer, forms a mixture which exhibits a cloud point of ≤ 110 °C (80 % transmission) in the cloud point compatibility test procedure. [12] Rosin ester according to any one of claims 1 to 7, which, when mixed 1:1 (wt / wt) with a metallocene-catalyzed poly-α-olefin plastomer, forms a mixture which, in the cloud point compatibility test procedure, exhibits a cloud point of ≤ 120 °C at 80 % transmission. [13] Rosin ester according to any one of claims 1 to 7, which, when mixed 1:1 (wt / wt) with an amorphous poly-α-olefin, forms a mixture which, in the cloud point compatibility test procedure, exhibits a cloud point of ≤ 150 °C at 80 % transmission. [14] Adhesive composition comprising: 10-60 wt.% of a rosin ester according to any one of claims 1 to 7; 20-70 wt% of a polymer selected from the group consisting of ethylene-vinyl acetate copolymers, metallocene-catalyzed poly-α-olefin elastomers, metallocene-catalyzed poly-α-olefin plastomers and amorphous poly-α-olefins, and 0-40 wt% of a plasticizer; wherein the adhesive composition has a cloud point of less than 160 °C, determined according to ASTM D6045, and a melt viscosity at 180 °C of less than 50,000 mPa.s, measured using a Brookfield rotational viscometer with Thermosel heater according to ASTM D3236. [15] Adhesive composition comprising: 10-60 wt.% of a rosin ester according to any one of claims 1 to 7, 10-40 wt.% of a styrene block copolymer and 10-40 wt% of a plasticizer, wherein the adhesive composition has a 180° peel strength of at least 5 N / 25 mm, measured on a stainless steel substrate at a peel speed of 300 mm / min according to ASTM D3330, and a shear bond strength of at least 1000 minutes at 23 °C, determined on a 25 mm × 25 mm overlap joint under a load of 1 kg according to ASTM D3654. [16] Tire composition including: (i) a rubber component selected from the group consisting of natural rubber, synthetic polyisoprene, polybutadiene, styrene-butadiene rubber and mixtures thereof, and based on 100 parts by weight (phr) of the rubber component; (ii) 30 to 200 phr of a filler; (iii) 5 to 75 phr of a rosin ester according to any one of claims 1 to 7.