Composition obtained from depolymerization of polyurethane, process for its preparation and bituminous composition comprising it

Abstract

This disclosure relates to a polyol composition obtained by depolymerization of polyurethane, a method for its preparation, and its use in asphalt compositions. The polyol composition comprises, based on its total weight, 10% to 50%, preferably 25% to 45% by weight, of a polyol as component (A); and 15% to 80%, preferably 20% to 70% by weight, of an amine as component (B). This polyol composition is available from recycled polyurethane (PU) materials and can be used as an additive in asphalt compositions to obtain improved properties, particularly as an additive in paving asphalt compositions, to obtain improved properties such as rutting resistance and aging resistance, and an expanded temperature range for paving the asphalt composition.

Description

Technical Field

[0001] This invention relates to a polyol composition obtained by depolymerization of polyurethane, its uses, and asphalt compositions comprising it. Additionally, this invention relates to a method for depolymerizing polyurethane. Preferably, the polyurethane can be polyurethane waste available in industrial and / or everyday life. Background Technology

[0002] Recycling polyurethane (PU) materials can save raw materials and reduce costs, and is important in modern industry. As an important pathway for the recycling of polyurethane (PU) materials, depolymerization of polyurethane (PU) materials, including hydrolysis, glycolysis, and ammonolysis, has been researched and developed in this field. Furthermore, various applications of the products obtained from the depolymerization of polyurethane (PU) materials have been developed.

[0003] In addition, asphalt compositions typically contain one or more additives, such as warm mix agents, to improve the suitability of the asphalt composition, for example, to reduce the high-temperature viscosity of the asphalt composition and change its viscosity-temperature profile, thereby expanding the temperature range in which the asphalt composition can be applied.

[0004] There is a need in the art to provide a method for depolymerizing polyurethane (PU) materials, which is simple and easy to perform, wherein the product obtained by the method can be used as an additive in asphalt compositions, which expands the application temperature range of the asphalt compositions and improves the properties of the asphalt compositions, such as rutting resistance and aging resistance.

[0005] Furthermore, there is a need in the art for a composition that is obtained by depolymerizing polyurethane (PU) materials and can be used as an additive in asphalt compositions to obtain improved properties, particularly as an additive for road paving materials, to obtain improved properties such as rutting resistance and aging resistance, as well as an expanded temperature range for paving asphalt compositions. Summary of the Invention

[0006] The object of the present invention is to provide a polyol composition that is available from the recycling of polyurethane (PU) materials and can be used as an additive in asphalt compositions to obtain improved properties, particularly as an additive in paving asphalt compositions to obtain improved properties such as rutting resistance and aging resistance, as well as an expanded temperature range for paving asphalt compositions.

[0007] Another object of the present invention is to provide a method for depolymerizing polyurethane (PU) materials, which is simple and easy to carry out, wherein the product obtained by the method can be used as an additive in asphalt compositions.

[0008] Another object of the present invention is to provide an asphalt composition comprising the polyol composition of the present invention.

[0009] Another object of the present invention is to provide a method for preparing the asphalt composition of the present invention, the method comprising heating the polyol composition of the present invention and blending the heated polyol composition into base asphalt.

[0010] It has been unexpectedly discovered that the above objectives can be achieved through the following embodiments:

[0011] 1. A polyol composition obtained by depolymerization of a polyurethane-based product, the polyol composition comprising, based on the total weight of the polyol composition:

[0012] The polyol comprising 10% to 50%, preferably 25% to 45% by weight, as component (A); and

[0013] The amine comprises 15% to 80%, preferably 20% to 70% by weight as component (B), wherein component (B) contains aromatic amines.

[0014] 2. The polyol composition according to Example 1, wherein component (B) is composed of the aromatic amine.

[0015] 3. The polyol composition according to Example 1 or 2, wherein the polyurethane has a polyol portion, and the polyol portion is a polyester polyol portion and / or a polyether polyol portion, preferably a poly(oxyalkylene) polyol portion having an oxyalkylene group having 2 to 4 carbon atoms, more preferably a poly(oxyalkylene) polyol portion containing at least one unit selected from oxyethylene, oxypropylene, oxybutylene and oxytetramethylene.

[0016] 4. The polyol composition according to any one of Examples 1 to 3, wherein component (A) comprises component (A1) of a poly(oxyethylene) polyol portion derived from the polyurethane and component (A2) of a poly(oxypropylene) polyol portion derived from the polyurethane, preferably the molar ratio of component (A1) to component (A2) is in the range of 0:1 to 5:1, more preferably 0.1:1 to 4:1.

[0017] 5. The polyol composition according to any one of Examples 1 to 4, wherein the aromatic amine comprises an aromatic polyamine, such as a diamine or its polymeric form, preferably polymerized diphenylmethylenediamine, diphenylmethylenediamine, toluenediamine, phenylenediamine, naphthyldiamine, tetrahydronaphthyldiamine, benzidine, dimethylbenzidine, or any combination thereof, more preferably diphenylmethylenediamine and toluenediamine.

[0018] 6. The polyol composition according to any one of Examples 1 to 5, wherein the aromatic amine comprises 2,4-toluenediamine, 2,6-toluenediamine, 4,4′-diphenylmethanediamine and / or 2,4′-diphenylmethanediamine, preferably the aromatic amine comprises 4,4′-diphenylmethanediamine and 2,4′-diphenylmethanediamine, wherein the molar ratio of 2,4′-diphenylmethanediamine to 4,4′-diphenylmethanediamine is in the range of 0:1 to 1:1, preferably 0.1:1 to 0.5:1.

[0019] 7. The polyol composition according to any one of Examples 1 to 6, wherein the polyol composition further comprises:

[0020] The styrene-based polymer, preferably a styrene-acrylonitrile copolymer, is preferably in an amount of 0% to 50% by weight, preferably 3% to 45%, based on the total weight of the polyol composition.

[0021] 8. The polyol composition according to any one of Examples 1 to 7, wherein the polyol composition further comprises a diol (C), preferably diethylene glycol, which is not component (A), in an amount of 0% to 8% by weight, preferably 0% to 4% by weight, based on the total weight of the polyol composition.

[0022] 9. The polyol composition according to any one of Examples 1 to 8, which is obtained by depolymerization of polyurethane foam, preferably flexible polyurethane foam.

[0023] 10. The polyol composition according to any one of Examples 1 to 9, obtained by depolymerizing the polyurethane-based product to form a depolymerization product system, and distilling the depolymerization product system at a temperature of 160°C to 240°C and a pressure of 10 to 100 mbar.

[0024] 11. A method for producing a polyol composition as described in any one of Examples 1 to 10, the method comprising:

[0025] (1) Depolymerizing polyurethane-based products using a depolymerizing agent to form a depolymerization product system, and

[0026] (2) The depolymerization product system obtained in step (1) is distilled to obtain the polyol composition.

[0027] 12. The method as described in Example 11, wherein the depolymerizing agent is selected from: water; a compound having an OH value of at least 300 mg KOH / g, preferably C1-C. 20 -diol, C1-C 20 -triol, C1-C 20 -amine, or C1-C20 -Alkanolamines, more preferably ethylene glycol, diethylene glycol, triethylene glycol, PEG 300-600, propylene glycol, dipropylene glycol, diethanolamine, triethanolamine, or glycerol; compounds having an amine value of at least 300 mgKOH / g, preferably ammonia, C1-C 20 - Alkylene diamines, more preferably ammonia, ethylenediamine, propylenediamine, butanediamine; or any combination thereof.

[0028] 13. The method as described in Example 11 or 12, wherein, in step (1), the weight ratio of the polyurethane-based product to be depolymerized to the depolymerizing agent is 3:1 to 1:2, preferably 3:1 to 1:1.

[0029] 14. The method as described in any one of Examples 11 to 13, wherein step (2) is performed at a temperature of 160°C to 240°C and a pressure of 10 to 100 mbar.

[0030] 15. The method of any one of Examples 11 to 14, wherein the polyol composition is obtained from distillation residue.

[0031] 16. An asphalt composition comprising:

[0032] (a) Base bitumen; and

[0033] (b) A polyol composition as described in any one of Examples 1 to 10 or prepared by any one of Examples 11 to 15.

[0034] 17. The bitumen composition as described in Example 16, wherein,

[0035] The amount of the base asphalt is in the range of 60% to 95% by weight, preferably 70% to 95% by weight, and more preferably 80% to 95% by weight, based on the total weight of the asphalt composition.

[0036] The amount of the polyol composition is in the range of 5% to 25% by weight, preferably 5% to 20% by weight, and more preferably 5% to 15% by weight, based on the total weight of the bitumen composition.

[0037] 18. A method for producing an asphalt composition as described in any one of Examples 16 to 17, the method comprising:

[0038] (1-i) Heating a polyol composition as described in any one of Examples 1 to 10 or prepared by any one of Examples 11 to 15 at a temperature in the range of about 100°C to about 200°C, such as 150°C, and

[0039] (1-ii) The heated polyol composition is blended with the base bitumen at a process temperature in the range of about 100°C to about 200°C, such as about 130°C to about 165°C, preferably about 140°C to about 160°C, to obtain the bitumen composition.

[0040] 19. The method as described in Example 18, further comprising milling the polyol composition prior to step (1-i).

[0041] 20. A method for producing an asphalt composition as described in any one of Examples 16 to 17, the method comprising:

[0042] (2-i) Heating the base asphalt to a temperature in the range of about 100°C to about 200°C, such as 130°C to about 150°C, and

[0043] (2-ii) The heated base bitumen is mixed with the polyol composition of the present invention for a period of time ranging from about 5 min to 3 hours at a shear rate, preferably 2000 rpm, in the range of about 100°C to about 200°C, such as 130°C to about 150°C.

[0044] The polyol compositions of the present invention can be used as additives in asphalt compositions. They improve the properties of asphalt compositions in a cost-effective manner. In particular, the polyol compositions of the present invention can be used as novel warm mix additives in asphalt compositions, especially paving asphalt compositions, to expand the temperature range for paving asphalt compositions while maintaining or optimizing asphalt properties, such as improved rutting resistance and anti-aging properties, and lowering the operating temperature for paving asphalt compositions, which is desirable for applications such as road / bridge paving.

[0045] Furthermore, the polyol compositions of the present invention can be obtained by the method of the present invention. The method of the present invention is simple and easy to perform, providing an effective and sustainable solution for the recycling of waste / end-of-life polyurethane materials, especially polyether polyol-based polyurethane materials, such as polyether polyol-based polyurethane flexible foam materials, and achieving a quality-balanced solution for carbon footprint. Attached Figure Description

[0046] Figure 1 The curves from the RAI test are shown. Detailed Implementation

[0047] Unless otherwise defined, all technical and scientific terms used herein have the meanings commonly understood by one of ordinary skill in the art to which this invention pertains. As used herein, unless otherwise stated, the following terms have the meanings assigned to them as follows.

[0048] The articles “a”, “an” and “the” mean one or more substances represented by the term following the article.

[0049] In the context of this disclosure, any specific value mentioned for a feature (including specific values ​​mentioned as endpoints in a range) may be recombinated to form a new range.

[0050] Further embodiments of the invention can be seen from the claims, description, and examples. It should be understood that the foregoing features of the subject matter of the invention and the features to be elaborated below can be used not only in the specific combinations indicated, but also in other combinations without departing from the scope of the invention.

[0051] Polyol Composition

[0052] One aspect of the present invention relates to a polyol composition obtained by depolymerization of a polyurethane-based product, the polyol composition comprising, based on the total weight of the polyol composition:

[0053] The polyol comprising 10% to 50%, preferably 25% to 45% by weight, as component (A); and

[0054] The amine comprises 15% to 80%, preferably 20% to 70% by weight as component (B), wherein component (B) contains aromatic amines.

[0055] The polyol compositions of the present invention are obtained by depolymerization of polyurethane-based products, wherein the polyurethane comprises a polyol portion derived from the polyol used to form the polyurethane and an isocyanate portion derived from the isocyanate used to form the polyurethane. The polyurethane may be in the form of polyurethane foam, preferably flexible polyurethane foam. Preferably, the polyurethane may include polyurethane waste, such as that available from industry or from people's daily lives.

[0056] Polyol component (A)

[0057] The polyol component (A) of the present invention is obtained by depolymerization of a polyurethane-based product. Preferably, the polyol component (A) is a polyol derived from the polyol portion of a polyurethane.

[0058] In the examples, the polyol used as component (A) is a polymeric polyol.

[0059] The polyol portion of polyurethane is derived from the polyol used to form polyurethane. As the polyol used to form polyurethane, compounds commonly referred to as isocyanate reactive compounds can be used. Specifically, the polyol used to form polyurethane can be selected from the group consisting of polyester polyols, polyether polyols, and any mixtures thereof.

[0060] Polyester polyols can be prepared by condensing a polyfunctional alcohol having 2 to 12 carbon atoms with a polyfunctional carboxylic acid having 2 to 12 carbon atoms. The polyfunctional alcohol or carboxylic acid can have a functionality of approximately 2. Examples of polyfunctional alcohols include ethylene glycol, diethylene glycol, butanediol, or combinations thereof. Examples of polyfunctional carboxylic acids include succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, isomers of naphthalenedicarboxylic acid, or esters or anhydrides of the aforementioned acids.

[0061] In a preferred embodiment of the invention, the polyol used to form the polyurethane is a polyether polyol.

[0062] Polyether polyols can be obtained by known methods, for example by polymerizing epoxides in the presence of a catalyst by adding at least one starting molecule containing 2 to 8, preferably 2 to 6, reactive hydrogen atoms. As catalysts, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, or alkali metal alkoxides such as sodium methoxide, sodium ethoxide or potassium ethoxide, or potassium isopropoxide, or in the case of cationic polymerization, Lewis acids such as antimony pentachloride, boron trifluoride ether, or bleaching earth can be used. Alternatively, bimetallic cyanide compounds (known as DMC catalysts) can also be used as catalysts.

[0063] As an alkylene oxide, one or more compounds having 2 to 4 carbon atoms in the alkylene group are preferred, such as ethylene oxide, 1,3-epoxypropane, tetrahydrofuran, 1,2- or 2,3-epoxybutane, in each case alone or in mixtures, and preferably ethylene oxide, 1,2-epoxypropane and / or tetrahydrofuran, with tetrahydrofuran being the most preferred.

[0064] Possible starting molecules include, for example, ethylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, sugar derivatives such as sucrose, sugar alcohols such as sorbitol, methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluenediamine, naphthylamine, ethylenediamine, diethylenetriamine, 4,4'-methylenediphenylamine, 1,3-propanediamine, 1,6-hexanediamine, ethanolamine, diethanolamine, triethanolamine, and other di- or polyols or monofunctional or polyfunctional amines.

[0065] Examples of polyether polyols may also include ring-opening polymers of tetrahydrofuran (polytetramethylene glycol, PTMEG), natural oil-based polyether polyols such as alkoxylated castor oil or other natural oil or fat-based polyether polyols (e.g., those obtained by ring-opening reactions of epoxidized unsaturated vegetable oils), and sugar-based polyether polyols.

[0066] In a preferred embodiment of the invention, the polyol portion of the polyurethane is a poly(oxyalkylene) polyol portion, such as a poly(oxyalkylene) polyol portion having an oxyalkylene group having 2 to 4 carbon atoms, more preferably a poly(oxyalkylene) polyol portion containing at least one unit selected from oxyethylene, oxypropylene, oxybutylene and oxytetramethylene. Preferably, in this invention, the polyol portion of the polyurethane has a number-average molecular weight in the range of 500 to 10,000 g / mol, such as 800 g / mol, 1,000 g / mol, 2,000 g / mol, 3,000 g / mol, 4,000 g / mol, 5,000 g / mol, 6,000 g / mol, 7,000 g / mol, 8,000 g / mol, 9,000 g / mol, 10,000 g / mol, or any number-average molecular weight between these values, preferably in the range of 1,000 to 8,000 g / mol and more preferably in the range of 2,000 to 8,000 g / mol. In this context, the alkylene group (e.g., the alkylene group in an oxyalkylene group) may contain 2 to 10, or 2 to 8, or 2 to 6, or 2, 3, or 4 carbon atoms.

[0067] In a preferred embodiment of the invention, the polyol component (A) comprises a polyol component (A1) of poly(oxyethylene) polyol derived from polyurethane and a polyol component (A2) of poly(oxypropylene) polyol derived from polyurethane. Preferably, the molar ratio of polyol component (A1) to polyol component (A2) is in the range of 0:1 to 5:1, for example, 0.05:1, or 0.1:1, or 0.2:1, or 0.4:1, or 0.6:1, or 0.8:1, or 1:1, or 1.2:1, or 1.4:1, or 1.6:1, or 1.8:1, or 2.0:1, or 2.2:1, or 2.4:1, or 2.6:1, or 2.8:1, or 3.0:1. 1, or 3.2:1, or 3.4:1, or 3.6:1, or 3.8:1, or 4:1, or 4.3:1, or 4.6:1, or 4.8:1, or any molar ratio between these values, such as 0.051:1 to 5:1, preferably 0.1:1 to 5:1, more preferably 0.1:1 to 4:1, such as 0.1:1 to 3:1, or 0.1:1 to 1:1.

[0068] Preferably, the polyol component (A) of the present invention is a bifunctional or multifunctional polyol component. For example, the hydroxyl functionality of the polyol component (A) is equal to or greater than 2, such as 3 or greater, 4 or greater, 5 or greater, 6 or greater, 7 or greater, 8 or greater, 9 or greater, or 10 or greater. In a preferred embodiment, the hydroxyl functionality of the polyol component (A) can be in the range of 2 to 10, such as 2 to 6.

[0069] The amount of polyol component (A) can be in the range of 10% to 50% by weight of the polyol composition based on the present invention, for example, 10%, 12%, 15%, 18%, 20%, 23%, 25%, 27%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, or 50% by weight, or can be any amount between these values, such as 15% to 50% by weight, preferably 20% to 50% by weight, more preferably 25% to 45% by weight.

[0070] Amine component (B)

[0071] The amine component (B) is obtained by depolymerization of a polyurethane-based product. In this invention, the amine component (B) comprises an aromatic amine.

[0072] Preferably, the amine component (B) is an amine derived from the isocyanate portion of the polyurethane. The isocyanate portion of the polyurethane is derived from the isocyanate used to form the polyurethane.

[0073] Isocyanates used to form polyurethanes can be selected from the group consisting of any organic compound having two or more isocyanate groups per molecule, such as diisocyanates, including not only those in which isocyanate groups are attached to hydrocarbon groups, but also those in which isocyanate groups are attached to groups comprising heteroatoms such as oxygen or nitrogen (e.g., as part of ester groups, ether groups, etc.), and combinations thereof.

[0074] The isocyanate used to form polyurethane can be an aliphatic, araliphatic, alicyclic, or aromatic polyisocyanate, such as an aliphatic diisocyanate, or an araliphatic diisocyanate, or an alicyclic diisocyanate, or an aromatic diisocyanate, including isocyanate monomers and / or isocyanate prepolymers.

[0075] Suitable isocyanate prepolymers for use in this invention can be obtained by reacting the NCO functional groups of an isocyanate component with a material containing active hydrogen at a temperature, for example, 30°C to 200°C, preferably about 50°C to 180°C, to obtain an isocyanate-terminated prepolymer having two or more free isocyanate groups. For example, suitable isocyanate prepolymers for use in this invention include diisocyanate oligomers produced by reacting at least one diisocyanate monomer with at least one diol or diamine. The diisocyanate monomer can be selected from those listed above.

[0076] In some embodiments, the material containing active hydrogen may be selected from the group consisting of polyester glycols, polyether glycols, polycarbonate glycols, and diamines. In some embodiments, the material containing active hydrogen is a polyether glycol. In some embodiments, the material containing active hydrogen is a polyester glycol. In some embodiments, the material containing active hydrogen is a mixture of one or more polyester glycols and one or more polyether glycols.

[0077] For example, suitable isocyanate prepolymers for use in the present invention can be diisocyanate prepolymers based on polyester diols, diisocyanate prepolymers based on polyether diols, diisocyanate prepolymers based on polycarbonate diols, and diisocyanate prepolymers based on diamines.

[0078] The polyester glycol preferably comprises alternating acid and alcohol units. As the acid component, succinic acid, adipic acid, phthalic anhydride, phthalic acid, or a mixture of the aforementioned acids and / or anhydrides are preferred. The alcohol component used may be ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, or a mixture of the aforementioned alcohols.

[0079] As a polyether glycol, a polyether glycol composed of repeating ethylene oxide and propylene oxide units is preferred, preferably having a proportion of 35% to 100% propylene oxide units on a molar basis, and particularly preferably having a proportion of 50% to 100% propylene oxide units on a molar basis. These can be random copolymers, gradient copolymers, alternating copolymers, or block copolymers of ethylene oxide and propylene oxide. Suitable polyether glycols can also be polytetrahydrofuran glycol.

[0080] Suitable polycarbonate diols may include products obtained by reacting diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, or tetraethylene glycol with diaryl carbonates such as diphenyl carbonate or with phosgene.

[0081] Suitable diamines include diaminoethane, diaminopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophorone diamine, IPDA), 4,4'-diaminodicyclohexyl-methane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, and hydrazine hydrate.

[0082] Polyurethane prepolymers having two or more free isocyanate groups, polyurea prepolymers having two or more free isocyanate groups, and combinations thereof may also be used as isocyanates suitable for use in the present invention.

[0083] In this invention, the isocyanate used to form the polyurethane comprises an aromatic isocyanate. In a preferred embodiment of the invention, the isocyanate used to form the polyurethane is an aromatic isocyanate.

[0084] Aromatic isocyanates used to form polyurethanes can correspond to the formula R′(NCO)z, where R′ is aromatic and z is an integer representing the valence of R′. Typically, z is at least di. Suitable examples of aromatic isocyanates include, but are not limited to, tetramethylbenzene dimethyl diisocyanate (TMXDI), 1,4-diisocyanobenzene, 1,3-diisocyano-o-xylene, 1,3-diisocyano-p-xylene, 1,3-diisocyano-m-xylene, 2,4-diisocyano-1-chlorobenzene, 2,4-diisocyano-1-nitro-benzene, 2,5-diisocyano-1-nitrobenzene, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4- Toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanates, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-biphenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate Esters, triisocyanates such as 4,4′,4″-triphenylmethane triisocyanate and 2,4,6-toluene triisocyanate, tetraisocyanates such as 4,4′-dimethyl-2,2′-5,5′-diphenylmethane tetraisocyanate, toluene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (4,4′-methylene diphenylisocyanate), polymethylene polyphenylene polyisocyanate, and their effects on... The isocyanate may be an isomeric mixture or combination thereof. Alternatively, the aromatic isocyanate may be or include a triisocyanate product of m-TMXDI and 1,1,1-trimethylolpropane, a reaction product of toluene diisocyanate and 1,1,1-trimethylolpropane, or combinations thereof. In one embodiment, the isocyanate used to form the polyurethane is or includes a diisocyanate selected from the group consisting of methylene diphenyl diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, H12MDI, or combinations thereof.

[0085] In a preferred embodiment of the invention, the amine component (B) of the polyol composition comprises or is an aromatic polyamine, such as a diamine and its polymeric form, preferably polymerized diphenylmethylenediamine, diphenylmethylenediamine, toluenediamine, phenylenediamine, naphthyldiamine, tetrahydronaphthyldiamine, benzidine, dimethylbenzidine, or any combination thereof, more preferably diphenylmethylenediamine and toluenediamine.

[0086] Preferably, the amine component (B) of the polyol composition comprises or is an aromatic amine. Preferably, the aromatic amine comprises 2,4-toluenediamine, 2,6-toluenediamine, 4,4′-diphenylmethanediamine, and / or 2,4′-diphenylmethanediamine, and preferably amine component (B) comprises 4,4′-diphenylmethanediamine and 2,4′-diphenylmethanediamine, wherein the molar ratio of 2,4′-diphenylmethanediamine to 4,4′-diphenylmethanediamine is in the range of 0:1 to 1:1, for example, 0.1:1, or 0.2:1, or 0.3:1, or 0.4:1, or 0.5:1, or 0.6:1, or 0.7:1, or 0.8:1, or 0.9:1, or 1:1, or between these values, such as 0.1:1 to 0.8:1, preferably 0.1:1 to 0.6:1. 1. More preferably, any molar ratio from 0.1:1 to 0.5:1.

[0087] Preferably, the amine component (B) of the present invention is a bifunctional or polyfunctional amine component. For example, the amine functionality of the amine component (B) is equal to or greater than 2, such as 3 or greater, 4 or greater, 5 or greater. In a preferred embodiment, the amine functionality of the amine component (B) can be in the range of 2 to 10, such as 2 to 6, or 2 to 4.

[0088] The amount of the amine component (B) of the present invention may be in the range of 15% to 80% by weight of the polyol composition based on the present invention, for example, 15% by weight, 18% by weight, 20% by weight, 24% by weight, 28% by weight, 30% by weight, 32% by weight, 35% by weight, 38% by weight, 40% by weight, 42% by weight, 45% by weight, 48% by weight, 50% by weight, 53% by weight, 55% by weight, 57% by weight, 60% by weight, 62% by weight, 65% by weight, 68% by weight, 70% by weight, 72% by weight, 75% by weight, 78% by weight, 80% by weight, or may be any amount between these values, such as 20% to 70% by weight, preferably 20% to 50% by weight, more preferably 25% to 45% by weight.

[0089] Other components

[0090] Optionally, the polyol compositions of the present invention may further comprise one or more other components. Preferably, the polyol compositions of the present invention may further comprise styrene-based polymers and / or diols.

[0091] Polymers based on styrene should be understood herein to include all homopolymers or copolymers resulting from the polymerization of styrene and / or styrene derivatives. Styrene derivatives are, for example, alkylstyrene, such as α-methylstyrene, o-, m-, p-methylstyrene, p-butylstyrene, especially p-tert-butylstyrene, and alkoxystyrene such as p-methoxystyrene, p-butoxystyrene, and p-tert-butoxystyrene.

[0092] Typically, suitable styrene-based polymers have Mn content of 10,000 to 1,000,000 g / mol (determined by GPC), preferably 20,000 to 750,000 g / mol, and more preferably 30,000 to 500,000 g / mol.

[0093] In a preferred embodiment, the styrene-based polymer in the polyol composition of the present invention may consist substantially or entirely of homopolymers of styrene or styrene derivatives.

[0094] In another preferred embodiment of the invention, the styrene-based polymer in the polyol composition of the invention may consist substantially or entirely of a styrene copolymer, which is also considered a styrene-based polymer in the context of this application. The styrene copolymer may contain, for example, butadiene, acrylonitrile, maleic anhydride, vinylcarbazole, or esters of acrylic acid, methacrylic acid, or itaconic acid as comonomers. Suitable styrene copolymers typically contain at least 20% styrene by weight, preferably at least 40%, and more preferably at least 60% styrene by weight. In another embodiment, they contain at least 90% styrene by weight. Preferred styrene copolymers are styrene-acrylonitrile copolymer (SAN) and acrylonitrile-butadiene-styrene copolymer (ABS), styrene-1,1′-diphenylethylene copolymer, acrylate-styrene-acrylonitrile copolymer (ASA), and methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS).

[0095] Another preferred styrene-based polymer is styrene-acrylonitrile copolymer (SAN), preferably wherein the molar ratio of styrene monomer units to acrylonitrile monomer units is in the range of 4:1 to 1:1, for example 4:1, or 3:1, or 2:1, or 1:1, or any molar ratio between these values.

[0096] Styrene homopolymers or copolymers can be prepared, for example, by free radical polymerization, cationic polymerization, anionic polymerization, or under the influence of organometallic catalysts (e.g., Ziegler-Natta catalysis). This can produce isotactic, syndiotactic, and atactic styrene-based polymers or copolymers. They are preferably prepared by free radical polymerization. Polymerization can be carried out as suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization.

[0097] The preparation of suitable styrene-based polymers is described, for example, in Oscar Nuyken, Polystyrenes and Other Aromatic Polyvinyl Compounds, Kricheldorf, Nuyken, Swift, New York 2005, pp. 73-150, and the references cited therein; and in Elias, Macromolecules, Weinheim 2007, pp. 269-275.

[0098] The amount of styrene-based polymer in the polyol composition of the present invention can be in the range of 0% to 50% by weight of the polyol composition of the present invention, for example, 2% by weight, 4% by weight, 6% by weight, 8% by weight, 10% by weight, 15% by weight, 20% by weight, 22% by weight, 25% by weight, 28% by weight, 30% by weight, 33% by weight, 35% by weight, 37% by weight, 40% by weight, 42% by weight, 45% by weight, 48% by weight, or 50% by weight, or can be any amount between these values, such as 0% to 45% by weight, preferably 3% to 45% by weight.

[0099] The polyol compositions of the present invention may further comprise a diol (C) that is not a component (A) of the polyol compositions of the present invention. For example, it may be an unreacted diol hydrolysate. The diol (C) may contain 2 to 10, 2 to 8, 2 to 6, 2 to 4, or 2, 3, or 4 carbon atoms. Preferred examples of the diol (C) include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,1-dimethyl-1,2-ethylenediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentanediol, 1,6-hexanediol, 2-methyl-1,5-pentanediol, 2-ethyl-1,4-butanediol, and 1,4-dihydroxymethyl-cyclohexane. Preferably, the diol (C) contained in the polyol compositions of the present invention is diethylene glycol.

[0100] The amount of diol (C) in the polyol composition of the present invention may be in the range of 0% to 8% by weight based on the polyol composition of the present invention, for example 0.01%, 0.03%, 0.05%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% by weight, or may be any amount between these values, such as 0% to 6% by weight, preferably 0% to 4% by weight.

[0101] Preferred embodiments of polyol compositions

[0102] The polyol composition of the present invention is preferably obtained by depolymerization of polyurethane foam, preferably polyurethane foam based on polyether polyol, and more preferably flexible polyurethane foam based on polyether polyol. Preferably, these polyurethanes and polyurethane foams can be waste or scrap polyurethane materials.

[0103] Preferably, the polyol compositions of the present invention have a hydroxyl value (OH value) in the range of 10 to 1000 mg KOH / g, for example 15 mg KOH / g, 20 mg KOH / g, 30 mg KOH / g, 40 mg KOH / g, 50 mg KOH / g, 60 mg KOH / g, 70 mg KOH / g, 80 mg KOH / g, 90 mg KOH / g, 100 mg KOH / g, 120 mg KOH / g, 150 mg KOH / g, 170 mg KOH / g, 190 mg KOH / g, 200 mg KOH / g, 210 mg KOH / g, 230 mg KOH / g, 300 mg KOH / g, 500 mg KOH / g, 800 mg KOH / g, 900 mg KOH / g, 1000 mg KOH / g, or have values ​​between these, preferably between 50 and 900 mg. Any OH value within the range of KOH / g, or within the range of 100 to 900 mg KOH / g, or within the range of 150 to 850 mg KOH / g, or within the range of 200 to 850 mg KOH / g. The OH value can be measured according to the method provided in the examples.

[0104] Preferably, the polyol compositions of the present invention have a number-average molecular weight in the range of 100 to 1500 g / mol, such as 100 g / mol, 200 g / mol, 300 g / mol, 400 g / mol, 500 g / mol, 600 g / mol, 700 g / mol, 800 g / mol, 900 g / mol, 1000 g / mol, 1100 g / mol, 1200 g / mol, 1300 g / mol, 1400 g / mol, 1500 g / mol, or any number-average molecular weight between these values, preferably in the range of 120-1000 g / mol, more preferably in the range of 220-800 g / mol. The molecular weight can be measured according to the methods provided in the examples.

[0105] Preferably, the polyol composition of the present invention has a polymer dispersion index (PDI) in the range of 3.0 to 6.0, more preferably in the range of 4.0 to 5.0. The PDI can be measured according to the method provided in the examples.

[0106] In one embodiment, the polyol composition of the present invention comprises, based on the total weight of the polyol composition:

[0107] Polyols comprising 10% to 50% by weight as component (A); and

[0108] Amines comprising 15% to 80% by weight as component (B),

[0109] Optionally, 3% to 45% by weight of a styrene-based polymer, preferably a styrene-acrylonitrile copolymer.

[0110] Optionally, 0.01% to 6% by weight of glycol (C), preferably diethylene glycol,

[0111] The polyurethane has a polyol portion, and the polyol portion is a polyether polyol portion, preferably a poly(oxyalkylene) polyol portion, more preferably a poly(oxyalkylene) polyol portion containing at least one unit selected from oxyethylene, oxypropylene, oxybutylene, and oxytetramethylene.

[0112] The polyurethane has an isocyanate portion, and the isocyanate portion is an aromatic isocyanate portion.

[0113] In one embodiment, the polyol composition of the present invention comprises, based on the total weight of the polyol composition:

[0114] 25% to 45% by weight of polyols as component (A); and

[0115] Amines comprising 20% ​​to 70% by weight as component (B),

[0116] Optionally, 3% to 45% by weight of a styrene-based polymer, preferably a styrene-acrylonitrile copolymer.

[0117] Optionally, 0.01% to 6% by weight of glycol (C), preferably diethylene glycol,

[0118] The polyurethane has a polyol portion, and the polyol portion is a polyether polyol portion, preferably a poly(oxyalkylene) polyol portion, more preferably a poly(oxyalkylene) polyol portion containing at least one unit selected from oxyethylene, oxypropylene, oxybutylene, and oxytetramethylene.

[0119] The polyurethane has an isocyanate portion, and the isocyanate portion is an aromatic isocyanate portion.

[0120] In one embodiment, the polyol composition of the present invention comprises, based on the total weight of the polyol composition:

[0121] Polyols comprising 10% to 50% by weight as component (A); and

[0122] Amines comprising 15% to 80% by weight as component (B),

[0123] Optionally, 3% to 45% by weight of a styrene-based polymer, preferably a styrene-acrylonitrile copolymer.

[0124] Optionally, 0.01% to 6% by weight of glycol (C), preferably diethylene glycol,

[0125] Component (A) comprises component (A1) of a poly(oxyethylene) polyol derived from polyurethane and component (A2) of a poly(oxypropylene) polyol derived from polyurethane. Preferably, the molar ratio of component (A1) to component (A2) is in the range of 0:1 to 5:1, more preferably 0.1:1 to 4:1.

[0126] Component (B) may contain or be an aromatic polyamine, such as a diamine or its polymeric form, preferably polymerized diphenylmethylene diamine, diphenylmethylene diamine, toluene diamine, phenylenediamine, naphthyldiamine, tetrahydronaphthyldiamine, benzidine, dimethylbenzidine, or any combination thereof, more preferably diphenylmethylene diamine and toluene diamine.

[0127] In one embodiment, the polyol composition of the present invention comprises, based on the total weight of the polyol composition:

[0128] 25% to 45% by weight of polyols as component (A); and

[0129] Amines comprising 20% ​​to 70% by weight as component (B),

[0130] Optionally, 3% to 45% by weight of a styrene-based polymer, preferably a styrene-acrylonitrile copolymer.

[0131] Optionally, 0.01% to 6% by weight of glycol (C), preferably diethylene glycol,

[0132] Component (A) comprises component (A1) of a poly(oxyethylene) polyol derived from polyurethane and component (A2) of a poly(oxypropylene) polyol derived from polyurethane. Preferably, the molar ratio of component (A1) to component (A2) is in the range of 0:1 to 5:1, more preferably 0.1:1 to 4:1.

[0133] Component (B) may contain or be an aromatic polyamine, such as a diamine or its polymeric form, preferably polymerized diphenylmethylene diamine, diphenylmethylene diamine, toluene diamine, phenylenediamine, naphthyldiamine, tetrahydronaphthyldiamine, benzidine, dimethylbenzidine, or any combination thereof, more preferably diphenylmethylene diamine and toluene diamine.

[0134] In one embodiment, the polyol composition of the present invention comprises, based on the total weight of the polyol composition:

[0135] Polyols comprising 10% to 50% by weight as component (A); and

[0136] Amines comprising 15% to 80% by weight as component (B),

[0137] Optionally, 3% to 45% by weight of a styrene-based polymer, preferably a styrene-acrylonitrile copolymer.

[0138] Optionally, 0.01% to 6% by weight of glycol (C), preferably diethylene glycol,

[0139] Component (A) comprises component (A1) of a poly(oxyethylene) polyol derived from polyurethane and component (A2) of a poly(oxypropylene) polyol derived from polyurethane. Preferably, the molar ratio of component (A1) to component (A2) is in the range of 0:1 to 5:1, more preferably 0.1:1 to 4:1.

[0140] Component (B) comprises or consists of 2,4-toluenediamine, 2,6-toluenediamine, 4,4′-diphenylmethanediamine and / or 2,4′-diphenylmethanediamine, preferably Component (B) comprises 4,4′-diphenylmethanediamine and 2,4′-diphenylmethanediamine, wherein the molar ratio of 2,4′-diphenylmethanediamine to 4,4′-diphenylmethanediamine is in the range of 0:1 to 1:1, preferably 0.1:1 to 0.5:1.

[0141] In one embodiment, the polyol composition of the present invention comprises, based on the total weight of the polyol composition:

[0142] 25% to 45% by weight of polyols as component (A); and

[0143] Amines comprising 20% ​​to 70% by weight as component (B),

[0144] Optionally, 12% to 30% by weight of a styrene-based polymer, preferably a styrene-acrylonitrile copolymer.

[0145] Optionally, 0.01% to 6% by weight of glycol (C), preferably diethylene glycol,

[0146] Component (A) comprises component (A1) of a poly(oxyethylene) polyol derived from polyurethane and component (A2) of a poly(oxypropylene) polyol derived from polyurethane. Preferably, the molar ratio of component (A1) to component (A2) is in the range of 0:1 to 5:1, more preferably 0.1:1 to 4:1.

[0147] Component (B) comprises or consists of 2,4-toluenediamine, 2,6-toluenediamine, 4,4′-diphenylmethanediamine and / or 2,4′-diphenylmethanediamine, preferably Component (B) comprises 4,4′-diphenylmethanediamine and 2,4′-diphenylmethanediamine, wherein the molar ratio of 2,4′-diphenylmethanediamine to 4,4′-diphenylmethanediamine is in the range of 0:1 to 1:1, preferably 0.1:1 to 0.5:1.

[0148] Method for producing polyol compositions

[0149] One aspect of the present invention relates to a method for producing the polyol composition of the present invention, the method comprising:

[0150] (1) Depolymerizing polyurethane-based products using a depolymerizing agent to form a depolymerization product system, and

[0151] (2) The depolymerization product system obtained in step (1) is distilled to obtain a polyol composition.

[0152] The polyurethane used in the method of the present invention comprises a polyol portion and an isocyanate portion. For example, the polyurethane may comprise the reaction product of an isocyanate and a polyol.

[0153] The isocyanate used to form the polyurethane of the present invention can be any of those mentioned above. In the present invention, the isocyanate used to form the polyurethane comprises an aromatic isocyanate. In a preferred embodiment of the present invention, the isocyanate used to form the polyurethane is an aromatic isocyanate.

[0154] Aromatic isocyanates used to form polyurethanes can correspond to the formula R′(NCO)z, where R′ is aromatic and z is an integer representing the valence of R′. Typically, z is at least di. Suitable examples of aromatic isocyanates include, but are not limited to, tetramethylbenzene dimethyl diisocyanate (TMXDI), 1,4-diisocyanobenzene, 1,3-diisocyano-o-xylene, 1,3-diisocyano-p-xylene, 1,3-diisocyano-m-xylene, 2,4-diisocyano-1-chlorobenzene, 2,4-diisocyano-1-nitro-benzene, 2,5-diisocyano-1-nitrobenzene, m-phenylene diisocyanate, p-phenylene diisocyanate, and 2,4-toluene diisocyanate. Isocyanates, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanates, 1,5-naphthalene diisocyanate, 1-methoxy-2,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-biphenylene diisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, triisocyanates Examples of polyisocyanates include 4,4′,4″-triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and 2,4,6-toluene triisocyanate; tetraisocyanates such as 4,4′-dimethyl-2,2′-5,5′-diphenylmethane tetraisocyanate, toluene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (4,4′-methylene diphenyl isocyanate), and polymethylene polyphenyl isocyanate. The corresponding isomeric mixtures, and combinations thereof. Alternatively, the aromatic isocyanate may be or include a triisocyanate product of m-TMXDI and 1,1,1-trimethylolpropane, a reaction product of toluene diisocyanate and 1,1,1-trimethylolpropane, and combinations thereof. In one embodiment, the isocyanate used to form the polyurethane is or includes a diisocyanate selected from the group consisting of methylene diphenyl diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, H12MDI, and combinations thereof.

[0155] In a preferred embodiment of the invention, the isocyanate used to form the polyurethane comprises an aromatic diisocyanate, preferably diphenylmethylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, naphthalene diisocyanate, tetrahydronaphthalene diisocyanate, biphenylene diisocyanate, dimethyl biphenylene diisocyanate, or any combination thereof, more preferably diphenylmethylene diisocyanate and toluene diisocyanate.

[0156] Preferably, the isocyanate used to form the polyurethane comprises or consists of the following: 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate and / or 2,4′-diphenylmethane diisocyanate. More preferably, the isocyanate used to form the polyurethane comprises 4,4′-diphenylmethane diisocyanate and 2,4′-diphenylmethane diisocyanate, wherein the molar ratio of 2,4′-diphenylmethane diisocyanate to 4,4′-diphenylmethane diisocyanate is in the range of 0:1 to 1:1, for example, 0.1:1, or 0.2:1, or 0.3:1, or 0.4:1, or 0.5:1, or 0.6:1, or 0.7:1, or 0.8:1, or 0.9:1, or 1:1, or between these values, such as 0.1. Any molar ratio of 1 to 0.8:1, preferably 0.1:1 to 0.6:1, and more preferably 0.1:1 to 0.5:1.

[0157] The polyols used to form the polyurethane of the present invention can be those mentioned above. In a preferred embodiment of the present invention, the polyol used is a polyether polyol.

[0158] As an alkylene oxide, one or more compounds having 2 to 4 carbon atoms in the alkylene group are preferred, such as ethylene oxide, 1,3-epoxypropane, tetrahydrofuran, 1,2- or 2,3-epoxybutane, in each case alone or in mixtures, and preferably ethylene oxide, 1,2-epoxypropane and / or tetrahydrofuran, with tetrahydrofuran being the most preferred.

[0159] Possible starting molecules include, for example, ethylene glycol, diethylene glycol, glycerol, trimethylolpropane, pentaerythritol, sugar derivatives such as sucrose, sugar alcohols such as sorbitol, methylamine, ethylamine, isopropylamine, butylamine, benzylamine, aniline, toluidine, toluenediamine, naphthylamine, ethylenediamine, diethylenetriamine, 4,4'-methylenediphenylamine, 1,3-propanediamine, 1,6-hexanediamine, ethanolamine, diethanolamine, triethanolamine, and other di- or polyols or monofunctional or polyfunctional amines.

[0160] Examples of polyether polyols may also include ring-opening polymers of tetrahydrofuran (polytetramethylene glycol, PTMEG), natural oil-based polyether polyols such as alkoxylated castor oil or other natural oil or fat-based polyether polyols (e.g., those obtained by ring-opening reactions of epoxidized unsaturated vegetable oils), and sugar-based polyether polyols.

[0161] In a preferred embodiment of the invention, the polyol portion of the polyurethane is a poly(oxyalkylene) polyol portion, such as a poly(oxyalkylene) polyol portion having an oxyalkylene group having 2 to 4 carbon atoms, more preferably a poly(oxyalkylene) polyol portion containing at least one unit selected from oxyethylene, oxypropylene, oxybutylene and oxytetramethylene. Preferably, in this invention, the polyol portion of the polyurethane has a number-average molecular weight in the range of 500 to 10,000 g / mol, such as 800 g / mol, 1,000 g / mol, 2,000 g / mol, 3,000 g / mol, 4,000 g / mol, 5,000 g / mol, 6,000 g / mol, 7,000 g / mol, 8,000 g / mol, 9,000 g / mol, 10,000 g / mol, or any number-average molecular weight between these values, preferably in the range of 1,000 to 8,000 g / mol and more preferably in the range of 2,000 to 8,000 g / mol.

[0162] In a preferred embodiment of the present invention, the polyurethane used in the method of the present invention comprises a poly(oxyethylene) polyol portion and a poly(oxypropylene) polyol portion. Preferably, the molar ratio of the poly(oxyethylene) polyol portion to the poly(oxypropylene) polyol portion is in the range of 0:1 to 5:1, for example, 0.05:1, or 0.1:1, or 0.2:1, or 0.4:1, or 0.6:1, or 0.8:1, or 1:1, or 1.2:1, or 1.4:1, or 1.6:1, or 1.8:1, or 2.0:1, or 2.2:1, or 2.4:1, or 2.6:1, or 2.8:1, or 3.0:1, or 3.2:1, or 3.4:1, or 3.6:1. 1, or 3.8:1, or 4:1, or 4.3:1, or 4.6:1, or 4.8:1, or any molar ratio between these values, such as 0.051:1 to 5:1, preferably 0.1:1 to 5:1, more preferably 0.1:1 to 4:1, and most preferably 0.1:1 to 3:1.

[0163] The polyurethane used in this invention can further employ a chain extender as one of the raw materials.

[0164] Suitable chain extenders can be selected by those skilled in the art and can include aliphatic, aryliphatic, aromatic, and / or alicyclic compounds having two or three functional groups. For example, chain extenders suitable for use in the polyurethanes of this invention can be selected from bifunctional or trifunctional amines and alcohols, particularly diols, triols, or both, such as diamines and / or alkyldiols having 2 to 10 carbon atoms in an alkylene group.

[0165] Examples of chain extenders suitable for use in this invention include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,10-decanediol, 1,2-dihydroxycyclohexane, 1,3-dihydroxycyclohexane, 1,4-dihydroxycyclohexane, diethylene glycol and triethylene glycol, dipropylene glycol and tripropylene glycol, 1,6-hexanediol and bis(2-hydroxyethyl)hydroquinone; triols such as 1,2,4-trihydroxycyclohexane, 1,3,5-trihydroxycyclohexane, glycerol and trimethylolpropane. Particularly preferred chain extenders include 1,3-propanediol, 1,4-butanediol, or 1,6-hexanediol. In some cases, mixtures of two chain extenders may be used.

[0166] The depolymerizing agent used in step (1) of the method of the present invention can be selected by a technician based on actual operation and application. In a preferred embodiment of the present invention, the depolymerizing agent is selected from the group consisting of: water, compounds having an OH value of at least 300 mg KOH / g, and compounds having an amine value of at least 300 mg KOH / g.

[0167] Examples of compounds having an OH value of at least 300 mg KOH / g can be diols preferably having 2 to 25 or 2 to 12 carbon atoms, such as C1-C4. 20 - Diols and corresponding dialkylene glycols and polyalkylene glycols, such as C1-C 15 -alkylene glycols, C1-C 10 - Alkylene glycols and corresponding dialkylene glycols and polyalkylene glycols, particularly 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, diethylene glycol, 2,2,4-trimethylpentane-1,5-diol, 2,2-dimethylpropane-1,3-diol, 1,4-dihydroxymethylcyclohexane, 1,6-dihydroxymethylcyclohexane, 2,2-bis(4-hydroxyphenyl)-propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol C), dipropylene glycol and polyethylene glycol, preferably ethylene glycol, diethylene glycol, triethylene glycol, and PEG. 300-600, propylene glycol, dipropylene glycol.

[0168] As a compound having an OH value of at least 300 mg KOH / g, examples may further include more alcohols, such as triols, tetraols and / or pentaols, including but not limited to glycerol, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, sorbitol, etc., with glycerol being preferred.

[0169] Further examples of compounds having an OH value of at least 300 mg KOH / g may include amino alcohols such as ethanolamine, diethanolamine and triethanolamine, preferably diethanolamine and triethanolamine.

[0170] As compounds having an amine value of at least 300 mgKOH / g, preferred examples include ammonia, C1-C... 20 -amines, such as C1-C 20 -alkylene diamines, such as C1-C 15 -alkylene diamine, C1-C 10 - Alkylene diamines, more preferably ammonia, ethylenediamine, propylenediamine, or butanediamine.

[0171] Combinations of two or more of these depolymerizing agents can also be used in the method of the present invention.

[0172] In the method of the present invention, the amounts of depolymerizing agent and polyurethane-based product used in step (1) can be determined by a technician based on actual operation. For example, the amount of depolymerizing agent can be determined based on the amount of polyurethane-based product used in step (1). In a preferred embodiment of the present invention, in step (1), the weight ratio of the polyurethane-based product to be depolymerized to the added depolymerizing agent is in the range of 3:1 to 1:2, for example, 3:1, 2:1, 1:1, 1:2, or any ratio between these values. Preferably, in step (1), the weight ratio of the polyurethane-based product to be depolymerized to the added depolymerizing agent is in the range of 3:1 to 1:1.

[0173] Step (1) of the method of the present invention can be carried out in the presence of a catalyst. In some embodiments of the present invention, the catalyst may be selected from the group consisting of amines such as tertiary amines, titanium or tin-based catalysts, alkali metal acetates such as potassium acetate, and alkali metal hydroxides such as KOH and NaOH. Preferably, the catalyst is selected from alkali metal hydroxides.

[0174] Examples of tertiary amine catalysts may include, but are not limited to: triethylamine, tributylamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-cyclohexylmorpholine, N,N,N′,N′-tetramethylethylenediamine, N,N,N′,N′-tetramethylbutanediamine, N,N,N′,N′-tetramethylhexanediamine, pentamethyldiethylenetriamine, bis(dimethylaminoethyl) ether, bis(dimethylaminopropyl)urea, dimethylpiperazine, 1,2-dimethylimidazolium, 1-azabicyclo[3.3.0]octane and 1,4-diazabicyclo[2.2.2]octane.

[0175] Examples of tin-based catalysts may include, but are not limited to: tin(II) salts of organic carboxylic acids, such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate, and tin(II) laurate, and dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate.

[0176] In step (1) of the method of the present invention, the amount of catalyst used is in the range of 0.1% to 2% by weight based on the total weight of the polyurethane-based product, depolymerizer and catalyst used in step (1), for example 0.1%, 0.2%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.6%, 1.8%, 2% by weight, or any amount between these values, preferably in the range of 0.1% to 1.5% by weight, more preferably in the range of 0.1% to 1% by weight.

[0177] The temperature used for step (1) of the method of the present invention can be determined by a person skilled in the art based on actual operation. For example, step (1) of the method of the present invention can be performed at a temperature in the range of 160°C to 240°C, such as at 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, or between these values, preferably in the range of 170°C to 230°C, preferably in the range of 180°C to 220°C, and more preferably in the range of 190°C to 220°C.

[0178] The time for step (1) of the method of the present invention can be determined by a person skilled in the art based on the actual application. Preferably, step (1) can be performed over a period of 2 to 24 hours.

[0179] Step (1) of the method of the present invention can be carried out in a protective atmosphere and environmental pressure such as a nitrogen protective atmosphere and atmospheric pressure.

[0180] The method of the present invention further includes step (2), wherein the depolymerization product system obtained in step (1) is further distilled.

[0181] In the method of the present invention, the entire system obtained in step (1) can be used as a depolymerization product system for further distillation in step (2) of the method. Preferably, in the case of phase separation occurring in the system obtained in step (1), the product collected from the bottom phase of the system can be used as a depolymerization product system for further distillation in step (2) of the method.

[0182] Preferably, step (2) of the method of the present invention is performed at a temperature in the range of 160°C to 240°C, for example at 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, or between these values, preferably in the range of 170°C to 230°C, preferably in the range of 180°C to 220°C, and more preferably in the range of 190°C to 220°C.

[0183] Preferably, step (2) of the method of the present invention is performed at a pressure in the range of 10 to 100 millibars, for example at 10 millibars, 20 millibars, 30 millibars, 40 millibars, 50 millibars, 60 millibars, 70 millibars, 80 millibars, 90 millibars, 100 millibars, or between these values, preferably in the range of 20 to 80 millibars, preferably in the range of 30 to 70 millibars, and more preferably in the range of 40 to 60 millibars.

[0184] In an embodiment of the present invention, the distillation residue from step (2) is the polyol composition of the present invention.

[0185] In one embodiment of the present invention, the method of the present invention includes the following steps:

[0186] (1) Depolymerizing polyurethane-based products using a depolymerizing agent to form a depolymerization product system, and

[0187] (2) The depolymerization product system obtained in step (1) is distilled to obtain a polyol composition.

[0188] The depolymerizing agent is selected from:

[0189] water;

[0190] Compounds having an OH value of at least 300 mg KOH / g, preferably C1-C 20 -diol, C1-C 20 -triol or C1-C 20 -Alkylamine;

[0191] Compounds having an amine value of at least 300 mgKOH / g, preferably ammonia, C1-C 20 -amines, such as C1-C 20 -alkylene diamine;

[0192] Or any combination thereof.

[0193] In one embodiment of the present invention, the method of the present invention includes the following steps:

[0194] (1) Depolymerizing polyurethane-based products using a depolymerizing agent to form a depolymerization product system, and

[0195] (2) The depolymerization product system obtained in step (1) is distilled to obtain a polyol composition.

[0196] The depolymerizing agent is selected from:

[0197] water;

[0198] A compound having an OH value of at least 300 mg KOH / g, selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, PEG 300-600, propylene glycol, dipropylene glycol, diethanolamine, triethanolamine, and glycerol;

[0199] A compound having an amine value of at least 300 mgKOH / g, selected from the group consisting of: ammonia, ethylenediamine, propylenediamine, and butylenediamine;

[0200] Or any combination thereof.

[0201] In one embodiment of the present invention, the method of the present invention includes the following steps:

[0202] (1) Depolymerizing polyurethane-based products using a depolymerizing agent to form a depolymerization product system, and

[0203] (2) The depolymerization product system obtained in step (1) is distilled to obtain a polyol composition.

[0204] The depolymerizing agent is selected from:

[0205] water;

[0206] Compounds having an OH value of at least 300 mg KOH / g, preferably C1-C 20 -diol, C1-C 20 -triol or C1-C 20 -Alkylamine;

[0207] Compounds having an amine value of at least 300 mgKOH / g, preferably ammonia, C1-C 20 -amines, such as C1-C20 -alkylene diamine;

[0208] or any combination thereof,

[0209] In step (1), the weight ratio of the polyurethane-based product to be depolymerized to the depolymerizing agent is 3:1 to 1:2.

[0210] In one embodiment of the present invention, the method of the present invention includes the following steps:

[0211] (1) Depolymerizing polyurethane-based products using a depolymerizing agent to form a depolymerization product system, and

[0212] (2) The depolymerization product system obtained in step (1) is distilled to obtain a polyol composition.

[0213] The depolymerizing agent is selected from:

[0214] water;

[0215] A compound having an OH value of at least 300 mg KOH / g, selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, PEG 300-600, propylene glycol, dipropylene glycol, diethanolamine, triethanolamine, and glycerol;

[0216] A compound having an amine value of at least 300 mgKOH / g, selected from the group consisting of: ammonia, ethylenediamine, propylenediamine, and butylenediamine;

[0217] or any combination thereof,

[0218] In step (1), the weight ratio of the polyurethane-based product to be depolymerized to the depolymerizing agent is 3:1 to 1:2.

[0219] In one embodiment of the present invention, the method of the present invention includes the following steps:

[0220] (1) Depolymerizing polyurethane-based products using a depolymerizing agent to form a depolymerization product system, and

[0221] (2) The depolymerization product system obtained in step (1) is distilled to obtain a polyol composition.

[0222] The depolymerizing agent is selected from:

[0223] water;

[0224] Compounds having an OH value of at least 300 mg KOH / g, preferably C1-C 20 -diol, C1-C 20 -triol or C1-C 20 -Alkylamine;

[0225] Compounds having an amine value of at least 300 mgKOH / g, preferably ammonia, C1-C 20 -amines, such as C1-C 20 -alkylene diamine;

[0226] or any combination thereof,

[0227] In step (1), the weight ratio of the polyurethane-based product to be depolymerized to the depolymerizing agent is 3:1 to 1:2.

[0228] Step (2) is carried out at a temperature of 160°C-240°C and a pressure of 10 to 100 millibars, and

[0229] The polyol composition is derived from the distillation residue of step (2).

[0230] In one embodiment of the present invention, the method of the present invention includes the following steps:

[0231] (1) Depolymerizing polyurethane-based products using a depolymerizing agent to form a depolymerization product system, and

[0232] (2) The depolymerization product system obtained in step (1) is distilled to obtain a polyol composition.

[0233] The depolymerizing agent is selected from:

[0234] water;

[0235] A compound having an OH value of at least 300 mg KOH / g, selected from the group consisting of: ethylene glycol, diethylene glycol, triethylene glycol, PEG 300-600, propylene glycol, dipropylene glycol, diethanolamine, triethanolamine, and glycerol;

[0236] A compound having an amine value of at least 300 mgKOH / g, selected from the group consisting of: ammonia, ethylenediamine, propylenediamine, and butylenediamine;

[0237] or any combination thereof,

[0238] In step (1), the weight ratio of the polyurethane-based product to be depolymerized to the depolymerizing agent is 3:1 to 1:2.

[0239] Step (2) is carried out at a temperature of 160°C-240°C and a pressure of 10 to 100 millibars, and

[0240] The polyol composition is derived from the distillation residue of step (2).

[0241] application

[0242] The polyol compositions of the present invention and those produced by the method of the present invention can be obtained by depolymerizing polyurethane (PU) materials and can be widely used in various fields. In particular, the polyol compositions of the present invention and those produced by the method of the present invention can be used as additives in asphalt compositions to obtain improved properties, especially as additives in paving asphalt compositions to obtain improved properties such as rutting resistance and aging resistance, as well as an expanded temperature range for paving asphalt compositions.

[0243] Asphalt composition

[0244] The present invention further relates to an asphalt composition comprising:

[0245] (a) Base bitumen; and

[0246] (b) The polyol composition of the present invention or the polyol composition produced by the method of the present invention.

[0247] In this invention, as component (a), "base bitumen" refers to bitumen without the addition of component (b). The term "bitumen" encompasses the concept of the term "bitumen mixture." Suitable bitumen or bitumen mixtures according to the invention are disclosed, for example, in U.S. Patent Nos. 4,247,335 and 5,473,000.

[0248] Asphalt and asphalt mixtures are typically solid, semi-solid, or viscous liquid materials at normal atmospheric temperatures. Such asphalt mixtures and asphalt are mixtures of hydrocarbons of natural or pyrolytic origin, and are typically derived from petroleum or coal, but can exist in nature as is. The definition of asphalt and asphalt mixtures also includes road oils and road tar. For example, synthetic rubber-modified asphalt mixtures used for paving can also be used as component (a) in this invention. Modified asphalt mixtures are disclosed, for example, in U.S. Patent No. 5,473,000. The synthetic rubber is, for example, styrene-butadiene rubber.

[0249] The asphalt compositions of the present invention are particularly suitable for road paving or roofing materials. The asphalt compositions of the present invention can be used, for example, as a binder with mineral aggregates, fillers, or fibrous materials, in which case processing is typically carried out using a melt process.

[0250] Preferably, the amount of component (a) in the asphalt composition of the present invention can be in the range of 60% to 95% by weight based on the total weight of the asphalt composition, for example 60% by weight, 63% by weight, 65% by weight, 68% by weight, 70% by weight, 73% by weight, 75% by weight, 78% by weight, 80% by weight, 83% by weight, 85% by weight, 88% by weight, 90% by weight, 93% by weight, 95% by weight, preferably 70% to 95% by weight, more preferably 80% to 95% by weight.

[0251] Preferably, the amount of component (b) in the asphalt composition of the present invention can be in the range of 5% to 25% by weight based on the total weight of the asphalt composition, for example 5% by weight, 6% by weight, 8% by weight, 10% by weight, 13% by weight, 15% by weight, 18% by weight, 20% by weight, 23% by weight, 25% by weight, preferably 5% to 20% by weight, and more preferably 5% to 15% by weight.

[0252] Method for producing asphalt compositions

[0253] One aspect of the present invention relates to a method for producing the asphalt composition of the present invention.

[0254] The asphalt composition of the present invention can be prepared by a technician based on actual operation. In an embodiment of the present invention, the asphalt composition can be prepared by first heating the polyol composition of the present invention at a temperature in the range of about 100°C to about 200°C, such as 150°C, and then blending the heated polyol composition into base asphalt at a fixed process temperature to obtain a homogeneous mixture. The homogeneous mixture is then ready for further use.

[0255] In embodiments of the present invention, the asphalt composition of the present invention can be prepared by a method comprising the following steps:

[0256] (1-i) Heating the polyol composition of the present invention at a temperature in the range of about 100°C to about 200°C, such as 150°C, and

[0257] (1-ii) The heated polyol composition is blended into the base bitumen at a fixed process temperature in the range of about 100°C to about 200°C, such as about 130°C to about 165°C, preferably about 140°C to about 160°C, to obtain the bitumen composition.

[0258] In another embodiment of the invention, the asphalt composition of the invention can be prepared by first grinding the polyol composition of the invention (e.g., if the polyol composition is solid and non-sticky, it can be ground into powder), and then blending the ground polyol composition into base asphalt at a fixed process temperature to obtain a mixture. The mixture is then ready for further use.

[0259] The fixed process temperature used to blend the polyol composition into the base bitumen can be determined by a technician based on actual operation. For example, it can be a temperature in the range of about 100°C to about 200°C, such as about 130°C to about 165°C, preferably 140°C to about 160°C.

[0260] In embodiments of the present invention, the asphalt composition of the present invention can be prepared by a method comprising the following steps:

[0261] (2-i) Heating the base asphalt to a temperature ranging from about 100°C to about 200°C, and

[0262] (2-ii) The heated base bitumen is mixed with the polyol composition of the present invention at a shear rate, preferably 2000 rpm, in the range of 1000 to 4000 rpm and at a temperature in the range of about 100°C to about 200°C for a period of time in the range of about 5 min to 3 hours.

[0263] In another embodiment of the invention, the asphalt composition of the invention can be prepared by first heating the base asphalt to a temperature in the range of about 100°C to about 200°C, preferably 145°C, and then mixing the heated base asphalt with the polyol composition of the invention at a shear rate in the range of 1000 to 4000 rpm, preferably 2000 rpm, at a temperature in the range of about 130°C to about 150°C, preferably 145°C, for a period of time in the range of about 5 min to 3 hours, preferably 30 min.

[0264] In another embodiment of the invention, the asphalt composition of the invention can be prepared by first heating the base asphalt to a temperature in the range of about 100°C to about 200°C, such as about 130°C to about 150°C, preferably 145°C, and then mixing the heated base asphalt with the polyol composition of the invention at a shear rate in the range of 1000 to 4000 rpm, preferably 2000 rpm, at a temperature in the range of about 100°C to about 200°C, preferably 145°C, for a period of about 5 min to 3 hours, preferably 5-10 min.

[0265] Utilizing the polyol compositions of the present invention, the asphalt compositions of the present invention have significantly improved advantages. For example, they have an expanded temperature range for paving asphalt compositions while maintaining or optimizing asphalt properties, such as improved rutting resistance and aging resistance, and a reduced operating temperature for paving asphalt compositions, which is desirable for applications such as road / bridge pavement. Example

[0266] The invention will be better understood in light of the following non-limiting examples.

[0267] method

[0268] (1) Determination of amine value:

[0269] According to DIN 53176, the amine value is determined by titrating a solution of a polymer in acetic acid with perchloric acid.

[0270] (2) Determination of OH value (hydroxyl value):

[0271] The OH value was determined according to DIN 53240-2 (dated November 2007). The OH group was reacted by acetylation with excess acetic anhydride. Subsequently, the excess acetic anhydride was reacted by adding water to form acetic acid, and the entire acetic acid was back-titrated with alcoholic KOH.

[0272] The OH value indicates the amount of KOH in mg, which is equivalent to the amount of acetic acid bound in the acetylation of 1 g of the compound being analyzed.

[0273] (3) Determination of number-average molecular weight, weight-average molecular weight, and polymer dispersion index (PDI):

[0274] Number-average molecular weight (Mn), weight-average molecular weight (Mw), and polymer dispersion index (PDI) were determined by gel permeation chromatography (GPC) using tetrahydrofuran as the eluent and poly(ethylene glycol) standards, based on DIN 55672-1 (dated August 2007). Styrene-divinylbenzene copolymer was used as the column material.

[0275] (4) Determination of viscosity

[0276] Viscosity was determined at 23°C according to EN 12595.

[0277] (5) Determination of softening point

[0278] The softening point (Vicat softening point) of a standard small sample was determined according to EN 1427 in the range of 28°C to 150°C.

[0279] (6) Determination of penetration degree

[0280] Determine the penetration according to EN 1426.

[0281] (7) MSCR test for rutting resistance

[0282] Rutting resistance was determined in a multi-stress creep recovery (MSCR) test using a rotating film aging oven (RTFO), where the asphalt composition was subjected to 1-second shear creep loads (0.1 kPa and 3.2 kPa), 9-second recovery, and 10 cycles. Recovery strain (%) was reported. A higher average recovery percentage indicates better high-temperature rutting resistance of the asphalt composition.

[0283] (8) RAI test for anti-aging properties

[0284] For each asphalt composition prepared in the examples, dynamic shear rheometer (DSR) tests were performed according to AASHTO T315 to obtain the composite shear modulus (G). For unaged and PAV-aged bitumen compositions ( Figure 1 The unaged and aged adhesives in the sample were subjected to frequency scanning using DSR, and the curves were observed in... Figure 1 Provided by China.

[0285] The rheological aging index (RAI) is calculated by comparing the long-term aging (PAV) with the original G. The difference in the area under the principal curve is used to determine this:

[0286] .

[0287] Example 1: Preparation of Polyol Compositions

[0288] The polyol composition was obtained by the following method.

[0289] Diethylene glycol (19.7 kg) as a glycololytic agent and potassium hydroxide (0.6 kg) as a catalyst were added to a 100 L reactor and heated under stirring and reflux. The reactor was protected under a nitrogen atmosphere to prevent oxidation of the reactants. When the temperature of the mixture reached 200°C, 19.7 kg of crushed foam waste (based on polyurethane foam from scrap furniture) with a particle size of approximately 1–2 cm was added to the reactor. After feeding, the reaction was continued at 200°C for 2 h. At the end of the reaction, a liquid degradation mixture was obtained. The degradation mixture was then discharged from the reactor when cooled to 80°C.

[0290] The cooled degradation mixture was discharged into a metal container for phase separation by standing at room temperature for 48 h. The degradation mixture separated into three phases: liquid-solid-liquid. After removing the upper layer, the middle and bottom layers were mixed and subjected to distillation to remove diethylene glycol. Distillation was carried out at 235°C for 8 h, with the pressure gradually reduced to approximately 50 mbar. The distilled diethylene glycol was condensed and collected, and the distillation residue was obtained as a polyol composition.

[0291] Polyol compositions 1 to 7 were prepared using polyurethane foams from different sources via this method. The components of each polyol composition were determined by... 13 C10 NMR was determined using CDCl3, and their contents are provided in Table 1. The percentages in Table 1 are weight percentages.

[0292] Table 1

[0293]

[0294] PEOL: Polyether polyol component, which includes polyol components having propylene oxide segments (PO) and polyol components having ethylene oxide segments (EO).

[0295] DEG: Diethylene glycol

[0296] TDA: Toluenediamine

[0297] MDA: Methylenediphenylamine

[0298] SAN: Poly(styrene-co-acrylonitrile)

[0299] Example 2: Preparation of Asphalt Composition

[0300] Several asphalt compositions were prepared by mixing different amounts of the polyol composition 7 prepared in Example 1 with base asphalt. JB70# asphalt (commercially available from Shandong Chambroad Petrochemicals Co., Ltd., Shandong, China) was used as the base asphalt.

[0301] Asphalt compositions 1 to 4 were prepared and their properties were tested. The results are provided in Table 2.

[0302] Each of the asphalt compositions 2 to 4 is prepared by a method comprising the following steps:

[0303] (1) Heat the base asphalt (JB70#) to 145°C, and

[0304] (2) The amount of polyol composition 7 shown in Table 2 is mixed with the base asphalt from step (1), wherein the mixture is stirred for 30 min at a shear rate of 2000 rpm and a temperature of 145°C by a high shear mixer to obtain the asphalt composition.

[0305] The amount of polyol composition 7 is provided in Table 2 as “RPF content”.

[0306] Table 2

[0307]

[0308] A higher average percentage recovery (R) indicates better high-temperature rutting resistance in asphalt. At both 0.1 kPa and 3.2 kPa, asphalt compositions 2 to 4 modified with polyol compositions exhibited better rutting resistance than the base asphalt. This is beneficial. For example, improved rutting resistance will make asphalt pavements more suitable for heavy vehicle traffic or high-speed driving, thus preventing premature pavement deterioration and premature scrapping.

[0309] In asphalt compositions 2 to 4, the RAI was significantly reduced. The thermal oxidative aging resistance of the asphalt was improved.

Claims

1. A polyol composition obtained by depolymerization of a polyurethane-based product, the polyol composition comprising, based on the total weight of the polyol composition: The polyol comprising 10% to 50%, preferably 25% to 45% by weight, as component (A); and The amine comprises 15% to 80%, preferably 20% to 70% by weight as component (B), wherein component (B) contains aromatic amines.

2. The polyol composition according to claim 1, wherein, Component (B) consists of this aromatic amine.

3. The polyol composition according to claim 1 or 2, wherein, The polyurethane has a polyol portion, which is a polyester polyol portion and / or a polyether polyol portion, preferably a poly(oxyalkylene) polyol portion having an oxyalkylene group having 2 to 4 carbon atoms, more preferably a poly(oxyalkylene) polyol portion containing at least one unit selected from oxyethylene, oxypropylene, oxybutylene and oxytetramethylene.

4. The polyol composition according to any one of claims 1 to 3, wherein, Component (A) comprises component (A1) derived from the poly(oxyethylene) polyol portion of the polyurethane and component (A2) derived from the poly(oxypropylene) polyol portion of the polyurethane, preferably the molar ratio of component (A1) to component (A2) is in the range of 0:1 to 5:1, more preferably 0.1:1 to 4:

1.

5. The polyol composition according to any one of claims 1 to 4, wherein, The aromatic amine includes aromatic polyamines, such as diamines and their polymeric forms, preferably polymerized diphenylmethylene diamine, diphenylmethylene diamine, toluene diamine, phenylenediamine, naphthyldiamine, tetrahydronaphthyldiamine, benzidine, dimethylbenzidine, or any combination thereof, more preferably diphenylmethylene diamine and toluene diamine.

6. The polyol composition according to any one of claims 1 to 5, wherein, The aromatic amine comprises 2,4-toluenediamine, 2,6-toluenediamine, 4,4′-diphenylmethanediamine and / or 2,4′-diphenylmethanediamine, preferably comprising 4,4′-diphenylmethanediamine and 2,4′-diphenylmethanediamine, wherein the molar ratio of 2,4′-diphenylmethanediamine to 4,4′-diphenylmethanediamine is in the range of 0:1 to 1:1, preferably 0.1:1 to 0.5:

1.

7. The polyol composition according to any one of claims 1 to 6, wherein, The polyol composition further comprises: The styrene-based polymer, preferably a styrene-acrylonitrile copolymer, is preferably in an amount of 0% to 50% by weight, preferably 3% to 45%, based on the total weight of the polyol composition.

8. The polyol composition according to any one of claims 1 to 7, wherein, The polyol composition further comprises a diol (C), preferably diethylene glycol, which is not component (A), in an amount of 0% to 8% by weight, preferably 0% to 4% by weight, based on the total weight of the polyol composition.

9. The polyol composition according to any one of claims 1 to 8, wherein it is obtained by depolymerization of polyurethane foam, preferably flexible polyurethane foam.

10. The polyol composition according to any one of claims 1 to 9, obtained by depolymerizing the polyurethane-based product to form a depolymerization product system, and distilling the depolymerization product system at a temperature of 160°C to 240°C and a pressure of 10 to 100 mbar.

11. A method for producing a polyol composition according to any one of claims 1 to 10, the method comprising: (1) Depolymerizing polyurethane-based products using a depolymerizing agent to form a depolymerization product system, and (2) The depolymerization product system obtained in step (1) is distilled to obtain the polyol composition.

12. The method according to claim 11, wherein, The depolymerizing agent is selected from the group consisting of: water; a compound having an OH number of at least 300 mgKOH / g, preferably C1-C 20 - diols, C1-C 20 - triols, C1-C 20 - amines, or C1-C 20 - alkanolamines, more preferably ethylene glycol, diethylene glycol, triethylene glycol, PEG 300-600, propylene glycol, dipropylene glycol, diethanolamine, triethanolamine, or glycerol; a compound having an amine number of at least 300 mgKOH / g, preferably ammonia, C1-C 20 - alkylene diamines, more preferably ammonia, ethylenediamine, propylenediamine, butylenediamine; or any combination thereof.

13. The method according to claim 11 or 12, wherein, In step (1), the weight ratio of the polyurethane-based product to be depolymerized to the depolymerizing agent is 3:1 to 1:2, preferably 3:1 to 1:

1.

14. The method according to any one of claims 11 to 13, wherein, Step (2) is carried out at a temperature of 160°C-240°C and a pressure of 10 to 100 mbar.

15. The method according to any one of claims 11 to 14, wherein, This polyol composition was obtained from distillation residue.

16. An asphalt composition comprising: (a) Base asphalt; and (b) A polyol composition according to any one of claims 1 to 10 or prepared by the method according to any one of claims 11 to 15.

17. The bitumen composition according to claim 16, wherein, The amount of the base asphalt is in the range of 60% to 95% by weight, preferably 70% to 95% by weight, and more preferably 80% to 95% by weight, based on the total weight of the asphalt composition. The amount of the polyol composition is in the range of 5% to 25% by weight, preferably 5% to 20% by weight, and more preferably 5% to 15% by weight, based on the total weight of the bitumen composition.

18. A method for producing an asphalt composition according to any one of claims 16 to 17, the method comprising: (1-i) Heating a polyol composition according to any one of claims 1 to 10 or prepared by any one of claims 11 to 15 at a temperature in the range of about 100°C to about 200°C, such as 150°C, and... (1-ii) The heated polyol composition is blended with the base bitumen at a process temperature in the range of about 100°C to about 200°C, such as about 130°C to about 165°C, preferably about 140°C to about 160°C, to obtain the bitumen composition.

19. The method of claim 18, further comprising milling the polyol composition prior to step (1-i).

20. A method for producing an asphalt composition according to any one of claims 16 to 17, the method comprising: (2-i) Heating the base asphalt to a temperature in the range of about 100°C to about 200°C, such as 130°C to about 150°C, and (2-ii) The heated base bitumen is mixed with the polyol composition of the present invention for a period of time ranging from about 5 min to 3 hours at a shear rate, preferably 2000 rpm, in the range of about 100°C to about 200°C, such as 130°C to about 150°C.

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