阅读说明：本技术 由多芳族重原料制备材料的方法 (Method for producing materials from polyaromatic heavy feedstocks ) 是由 H·周 A·卢斯蒂格尔 V·德弗洛里奥 S·拉贾戈帕兰 T·D·沙弗 D·N·舒尔茨 于 2019-03-25 设计创作，主要内容包括：本公开涉及由重原料制备材料的方法。特别地,本公开提供了一种化学方法,其将主要具有多芳烃分子或物质的重原料(包括石油化学精炼或提取的残余物)转化成热固性或热塑性材料,其可以单独使用或用作复合材料中的组分。(The present disclosure relates to a method of preparing a material from a heavy feedstock. In particular, the present disclosure provides a chemical process that converts heavy feedstocks (including petrochemical refinery or extraction residues) having primarily polyaromatic molecules or species into thermoset or thermoplastic materials that can be used alone or as components in composites.)

1. A process for preparing a thermoplastic or thermoset material from a heavy feedstock comprising the steps of:

contacting the linking agent and catalyst with a heavy feedstock;

reacting the linking agent with the molecules in the heavy feedstock with mixing to form a reaction mixture; and

curing the reaction mixture to form a thermoplastic or thermoset material, wherein the linking agent comprises at least two functional groups that can react with molecules in the heavy feedstock.

2. The method of claim 1, wherein the linker has the structure of formula 1:

wherein FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof; each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group; n is an integer of 1 to 5.

3. The method of claim 1, wherein the linker has the structure of formula 2 a:

wherein FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group;

n is an integer of 1 to 5; and

m is an integer of 2 to 10000;

the polymer skeleton has a molecular weight of 1000-1000000 g/mol.

4. The method of claim 1, wherein the linker has the structure of formula 2 b:

wherein FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

x is a covalent bond, alkyl, cycloalkyl or aryl;

m is an integer of 2 to 10000;

the polymer skeleton has a molecular weight of 1000-1000000 g/mol.

5. The method of claim 1, wherein the linker is a molecule or derivative thereof having the structure

6. The method of claim 1, wherein the linking agent is sulfur or a sulfur compound.

7. The method of claim 1, wherein the catalyst and the linking agent are present on the same polymer backbone.

8. The method of claim 1, wherein the catalyst comprises an Acid Group (AG), the linking agent comprises a Functional Group (FG), having the structure:

wherein FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

AG (acid group) is phosphoric acid, sulfonic acid, carboxylic acid or a combination thereof;

X₁and X₂Independently a covalent bond, an alkyl, cycloalkyl, or aryl group;

m₁and m₂Are respectively an integer of 1-10000;

the polymer had a molecular weight of 1000-1000000 g/mol.

9. The method of any one of claims 1, wherein the linking agent comprises diene functionality.

10. The method of any one of claims 1-9, further comprising oxidizing molecules in the heavy feedstock.

11. The method of any one of claims 1-10, wherein molecules in the heavy feedstock are oxidized to increase molecular weight or functionality.

12. The method of any one of claims 1-11, wherein the molecules in the heavy feedstock are in concentrated H₂SO₄And oxidation under hydrogen peroxide conditions.

13. The method of any one of claims 1-12, wherein the linker comprises a naphthalene, pyrene, or biphenyl molecule linked to more than one functional group selected from aldehyde, vinyl, halogen, alcohol, acyl halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof.

14. The process of any one of claims 1-13, wherein the catalyst is selected from the group consisting of inorganic acids, organic acids, or lewis acids.

15. A process according to any one of claims 1 to 14, wherein the catalyst is selected from aluminium chloride, trifluoromethanesulphonic acid, p-toluenesulphonic acid, sulphuric acid, phosphoric acid, polyphosphoric acids, solid acids such as tungstic acid, polyoxometallates and other acids having the following structure. These acids may be used alone or in combination.

16. The process of claim 1 wherein the catalyst is

Wherein the AG (acid group) is phosphoric acid, sulfonic acid, carboxylic acid, methanesulfonic acid, p-toluenesulfonic acid, or a combination thereof; each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group; and

n is an integer of 0 to 5.

17. The method of any one of claims 1-16, wherein the amount of linking agent is 0.1% -100% w/w of the total weight of the heavy feedstock.

18. The method of any one of claims 1-17, wherein the amount of linking agent is 20% -80% w/w of the total weight of the heavy feedstock.

19. The method of any one of claims 1-18, wherein the amount of catalyst is 0.1% -10% w/w of the total weight of the linking agent and the heavy feedstock.

20. The method of any one of claims 1-19, wherein no solvent is used.

21. The method of any one of claims 1-20, wherein a solvent is used, and the solvent is selected from chlorobenzene, dichlorobenzene, trichlorobenzene, other halogenated aromatic compounds, or combinations thereof.

22. The method of any one of claims 1-21, wherein the linker and the molecule in the heavy feedstock are reacted at a temperature of from room temperature to 400 ℃.

23. The method of any one of claims 1-22, wherein the linker and the molecule in the heavy feedstock react at a temperature of 80 ℃ to 200 ℃.

24. A thermoset produced according to claims 1-23.

25. A composition comprising a thermoset or thermoset material produced according to claims 1-23.

Disclosure of Invention

The present disclosure relates to a novel process for preparing materials from heavy feedstocks. In particular, the present disclosure provides a chemical process that converts heavy feedstocks (including residues of petrochemical refining or extraction) having aromatic hydrocarbon molecules or substances into thermoset or thermoplastic materials that can be used alone or as components in composites.

Thus, in one aspect, the present specification provides a method of making a thermoplastic or thermoset material from a heavy feedstock using a linking agent, with or without a catalyst. In one embodiment, the heavy feedstock comprises at least one selected from the group consisting of vacuum residuum, FCC main column bottoms (slurry oil, main column bottoms), steam cracker tar, asphaltenes, C3-C5 rocks (C3-C5rock), bitumen, K-still bottoms, lube oil extracts, various streams from refinery processes, and other synthetic aromatics.

In one aspect, the present description provides a method for preparing a thermoplastic or thermoset material from a polyaromatic feedstock using a linking agent, with or without a catalyst.

In one aspect, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock using a linking agent having one of the following general chemical structures.

Type I linker-aromatic molecule.

FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group;

n is an integer of 0 to 5.

In other alternative embodiments, the benzene nucleus of the type I linker may also be substituted with a polyaromatic nucleus (e.g., naphthalene, pyrene, biphenyl, etc.) or a saturated group.

Type II linker-linkers act as pendant groups in the polymer chain.

FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group;

n is an integer from 1 to 5;

m is an integer of 1 to 10000.

The polymer skeleton has a molecular weight of 1000-1000000 g/mol.

In other alternative embodiments, the benzene nucleus of the type II linker may also be substituted with a polyaromatic nucleus (e.g., naphthalene, pyrene, biphenyl, etc.) or a saturated group.

In another embodiment, the type II linker has a functional group attached to the polymer chain by a covalent bond, an alkyl group, or an aryl group, having the following structure.

FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

x is a covalent bond, alkyl, cycloalkyl or aryl;

m is an integer of 1 to 10000.

The polymer had a molecular weight of 1000-1000000 g/mol.

Type III linker-sulfur, including inorganic sulfur and organic sulfur compounds, selected from the group consisting of thiols, organic sulfides, organic disulfides, organic polysulfides, and mixtures thereof.

Type IV linker-dicyclopentadiene, having the structure below.

In one aspect, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock using a linking agent in the absence of a catalyst.

In another aspect, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock using a linking agent in the presence of a catalyst.

In one embodiment, the catalyst is selected from different kinds of inorganic, organic, bronsted or lewis acids, such as aluminum chloride, hypophosphorous acid, hydrochloric acid, hydrogen iodide, phosphoric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, phosphoric acid, polyphosphoric acid, solid acids such as tungstic acid, polyoxometallate, and others. These acids may be used alone or in combination.

In another embodiment, the catalyst is an acid having the general structure.

AG (acid group) is phosphoric acid, sulfonic acid, carboxylic acid or a combination thereof;

each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group;

n is an integer of 0 to 5.

In other alternative embodiments, the benzene nucleus of catalyst formula 3 may also be replaced by a polyaromatic nucleus (e.g., naphthalene, pyrene, biphenyl, etc.) or a saturated group.

In other alternative embodiments, the catalyst and the linking agent are present on the same polymer backbone. For example, the catalyst contains an Acid Group (AG), and the linking agent contains a Functional Group (FG), having the following structure.

FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

AG (acid group) is phosphoric acid, sulfonic acid, carboxylic acid or a combination thereof;

x1 and X2 are independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group;

m1 and m2 are independently integers of 1 to 10000;

the polymer had a molecular weight of 1000-1000000 g/mol.

In some embodiments, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock without the addition of a solvent.

In some embodiments, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock in the presence of a solvent, such as tetrahydrofuran or a mixture of solvents. In some particular embodiments, the solvent is selected from chlorobenzene, dichlorobenzene, trichlorobenzene, polychlorinated biphenyls, and other halogenated aromatic compounds.

In one aspect, the present description provides thermoplastic or thermoset materials produced using the methods described herein.

In another aspect, the present description provides compositions comprising materials produced by the methods described herein.

Other aspects, features and advantages of the present disclosure will become apparent to those of ordinary skill in the art upon examination and reading of the following detailed description of the preferred embodiments.

Brief description of the drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the invention and together with the description, serve to explain the principles of the invention. The drawings are only for purposes of illustrating embodiments of the invention and are not to be construed as limiting the invention. Other objects, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings which illustrate exemplary embodiments of the invention, and in which:

FIG. 1 illustrates FTICR-MS data for FCC Main Column Bottoms (MCB) and steam cracker tar.

FIGS. 2a, 2b and 2c illustrate FTICR-MS data before and after a reaction using MCB as the polyaromatic starting material and a monofunctional vinyl molecule as the linking agent: (a) composition diagrams of all substances, (b) composition diagram of 1S substance, and (c) composition diagram of 1N substance.

Fig. 3a, 3b and 3c illustrate FTICR-MS data before and after a reaction using (a) a vacuum residuum, (b) a steam cracker tar and (c) AR200 as a heavy feedstock starting material and a monofunctional vinyl molecule as a linking agent.

Fig. 4 illustrates the tensile properties of epoxy resins and cured products from AR200 heavy feed starting materials and p-divinylbenzene ("DVB") linking agents, which reaction produces thermosets.

Fig. 5 illustrates the tensile properties of the strain-stress curves of epoxy resins and cured products from AR200 heavy feedstock starting materials and polyvinyl chloride linkers, this reaction producing a thermoplastic material that is elastic with low stiffness.

Detailed Description

The following detailed description is provided to assist those skilled in the art in practicing the present disclosure. Modifications and variations of the embodiments described herein may be made by those of ordinary skill in the art without departing from the spirit or scope of the disclosure. All publications, patent applications, patents, figures, and other references mentioned herein are expressly incorporated by reference in their entirety.

The present specification provides improved processes for converting heavy feedstocks, including residues of petrochemical refining or extraction, into thermoset or thermoplastic materials.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.

Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range (e.g., in the case of a group containing multiple carbon atoms, in which case each carbon atom falling within that range is provided), and any other stated or intervening value in that stated range, is encompassed within the disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges is also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where a stated range includes one or both of the limits, ranges excluding either of those included limits are also included in the disclosure.

The following terminology is used to describe the present disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used in the description is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.

The articles "a" and "an" as used herein and in the appended claims are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article, unless the context clearly dictates otherwise. For example, "an element" refers to one element or more than one element.

As used herein in the specification and claims, the phrase "and/or" should be understood to mean "one or two" of the elements so connected, i.e., elements that exist together in some cases and separately in other cases. Multiple elements listed with "and/or" should be interpreted in the same manner, i.e., "one or more" of the elements so connected. In addition to elements explicitly identified by the "and/or" clause, other elements may optionally be present, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, when used in conjunction with open language (e.g., "comprising"), reference to "a and/or B" may refer in one embodiment to a alone (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than a); in yet another embodiment, to a and B (optionally including other elements); and the like.

As used herein in the specification and claims, "or" should be understood to have the same meaning as "and/or" as defined above. For example, when items in a list are separated by "or" and/or "should be interpreted as being inclusive, i.e., including at least one of a plurality or series of elements, but also including more than one, and optionally other unlisted items. Only terms of the contrary, such as "only one" or "exactly one," or "consisting of … …" when used in the claims, are explicitly indicated to include only one element of the plurality or series of elements. In general, the term "or" as used herein should only be interpreted when preceded by an exclusive term (e.g., "one," only one, "or" exactly one ") to mean exclusively selected (i.e.," one or the other, but not both at the same time).

In the claims, as well as in the specification above, all transitional phrases such as "comprising," "including," "carrying," "having," "containing," "involving," "holding," "consisting of," and the like are to be understood to be open-ended, i.e., to mean including but not limited to. As described in the us patent office patent inspection program manual section 2111.03, only the transition phrases "consisting of … …" and "consisting essentially of … …" should be closed or semi-closed transition phrases, respectively.

As used herein in the specification and claims, the phrase "at least one," when referring to a series of one or more elements, should be understood to mean at least one element selected from any one or more of the series of elements, but not necessarily including at least one of each element specifically listed in the series of elements, and not excluding any combinations of elements in the series. This definition also allows that elements may optionally be present other than the elements specifically identified in the series of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, "at least one of a and B" (or, equivalently, "at least one of a or B," or, equivalently "at least one of a and/or B") can refer in one embodiment to at least one a, optionally including more than one a, but not the presence of B (optionally including elements other than B); in another embodiment, to at least one B, optionally including more than one B, but in the absence of a (optionally including elements other than a); in yet another embodiment, to at least one a, optionally including more than one a, and at least one B, optionally including more than one B (optionally including other elements); and the like.

It should also be understood that in certain methods described herein that include more than one step or action, the order of the steps or actions of the method is not necessarily limited to the order of the steps or actions of the method, unless the context indicates otherwise.

As used herein, the term "heavy feedstock" is to be understood in a broad sense from refining operations, such as heavy molecules in crude oil or complex molecules produced in petrochemical processes, including polyaromatics ("PAHs") and aromatics with heteroatoms. Heavy feedstocks can be residues of petrochemical refining or extraction, such as vacuum residuum, fluid catalytic cracking ("FCC") bottoms (slurry oil, main column bottoms ("MCB")), steam cracker tar, asphaltenes, C3-C5 rocks, bitumen, K tank bottoms, lube oil extracts, various streams from refining processes, and other synthetic aromatics.

In an exemplary embodiment, the heavy feedstock is an FCC bottoms product comprising one or a mixture of the following molecules:

in one aspect, the present disclosure provides methods for attaching molecules in heavy feedstocks by using Friedel-Crafts reactions, condensation reactions with formaldehyde (or other aldehydes/ketones), oxidation reactions, sulfur reactions, and/or Diels-Alder reactions.

Friedel-Crafts alkylation (or acylation) involves the alkylation (or acylation) of an aromatic ring with an alkyl (or acyl) halide using an acid catalyst.

Condensation reactions with formaldehyde have been used in reactions to form phenolic resins and can be used to link polyaromatic molecules in heavy feedstocks.

The oxidation reaction can be used to pretreat the aromatic material and used in combination with other linking chemistries. Or they may be used to introduce functional groups into the aromatic material to allow further crosslinking reactions to occur. One non-limiting example of such an oxidation reaction is a mild oxidative coupling reaction via blowing air/oxygen at elevated temperatures. Aromatics that have undergone such treatment have higher molecular weights and higher oxygen contents, which can accelerate the linking reaction and/or produce materials with better mechanical properties. Aromatic hydrocarbons can also be oxidized under harsh conditions such as concentrated sulfuric acid and hydrogen peroxide to introduce various functional groups such as epoxy, alcohol, aldehyde, or carboxylic acid, which can then be used for the linking reaction.

The polymerization of sulfur (including organic and inorganic sulfur compounds selected from the group consisting of mercaptans, organic sulfides, organic disulfides, organic polysulfides, and mixtures thereof) with aromatic hydrocarbon molecules can be accomplished by heating the aromatic hydrocarbon with sulfur.

The Diels-Alder reaction is an organic chemical reaction (particularly a [4+2] cycloaddition) between a conjugated diene and a substituted olefin (commonly referred to as a dienophile) to form a substituted cyclohexene derivative. Although simple aromatic molecules are rarely used as dienes in the Diels-Alder reaction, under certain conditions one can attach polyaromatic molecules by the Diels-Alder reaction.

In one aspect, the present description provides a method for preparing a thermoplastic or thermoset material from a polyaromatic feedstock using a linking agent, with or without a catalyst.

In one aspect, the present specification provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock using a linking agent or a mixture of linking agents having one of the following general chemical structures.

In one aspect, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock using a type I linker, which is an aromatic molecule having the following structure.

FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group;

n is an integer of 0 to 5.

In other alternative embodiments, the benzene nucleus of the type I linker may also be substituted with a polyaromatic nucleus (e.g., naphthalene, pyrene, biphenyl, etc.) or a saturated group.

In one embodiment, a type I linker comprises an aromatic/aliphatic molecule with more than one functional group attached, which need not be the same. In one non-limiting embodiment, the type I linker is selected from at least one of the following molecules, wherein the two functional groups are in the para position:

alternatively, two functional groups are located at ortho or meta positions, or are attached to naphthalene, pyrene or biphenyl:

in another aspect, the present specification provides a method of making a thermoplastic or thermoset material from a heavy feedstock using a polymeric type II linking agent, wherein the linking agent serves as a pendant group in the polymer chain. In one embodiment, the type II linker has a functional group attached to the polymer chain through benzene (formula 2a) or an aromatic molecule.

FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group;

n is an integer of 1 to 5;

m is an integer of 1 to 10000.

The polymer skeleton has a molecular weight of 1000-1000000 g/mol.

In other alternative embodiments, the benzene nucleus of formula 2a may also be substituted with a polyaromatic nucleus (e.g., naphthalene, pyrene, biphenyl, etc.) or a saturated group.

In another embodiment, the type II linker has a functional group attached to the polymer chain by a covalent bond, an alkyl group, or an aryl group, having the following structure.

FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

x is a covalent bond, alkyl, cycloalkyl or aryl;

m is an integer of 2 to 10000.

The polymer skeleton has a molecular weight of 1000-1000000 g/mol.

In certain embodiments, the type II linker has the following structure:

in another aspect, the present description provides a method of making a thermoplastic or thermoset material from a heavy feedstock using a sulfur type III coupling agent.

In another aspect, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock using dicyclopentadiene, a diene type IV connector having the structure.

Wherein the diene is capable of linking molecules in the heavy feedstock via a Friedel-Crafts reaction.

In some embodiments, the amount of linking agent is from 0.1% to 100% w/w of the total weight of the heavy feedstock. In some particular embodiments, the amount of linking agent is from about 20% to about 100% w/w of the total weight of the starting materials. For example, the linking agent may be present in an amount of about 20% to about 90%, about 20% to about 80%, about 20% to about 70%, about 20% to about 65%, about 20% to about 50%, about 20% to about 40%, about 20% to about 30%, about 30% to about 90%, about 30% to about 80%, about 30% to about 70%, about 30% to about 60%, about 30% to about 50%, about 30% to about 40%, about 40% to about 90%, about 40% to about 80%, about 40% to about 70%, about 40% to about 60%, about 40% to about 50%, about 50% to about 90%, about 50% to about 80%, about 50% to about 70%, about 50% to about 60%, about 60% to about 90%, about 60% to about 80%, about 60% to about 70%, from about 70% to about 90%, from about 70% to about 80%, from about 80% to about 90% w/w.

In one aspect, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock using a linking agent in the absence of a catalyst.

In another aspect, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock using a linking agent in the presence of a catalyst.

In one embodiment, the catalyst is selected from different kinds of inorganic, organic or lewis acids, such as aluminum chloride, trifluoromethanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, phosphoric acid, polyphosphoric acids, solid acids such as tungstic acid, polyoxometallates and other acids having the following structure. These acids may be used alone or in combination.

In another embodiment, the catalyst is an acid having the general structure.

AG (acid group) is phosphoric acid, sulfonic acid, carboxylic acid, methanesulfonic acid, p-toluenesulfonic acid, or a combination thereof;

each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group;

n is an integer of 0 to 5.

In other alternative embodiments, the benzene nucleus of catalyst formula 3 may also be replaced by a polyaromatic nucleus (e.g., naphthalene, pyrene, biphenyl, etc.) or a saturated group.

Examples of the catalyst include:

in some embodiments, the amount of catalyst is 0.1% to 50% w/w of the total weight of the linking agent and the heavy feedstock. In some particular embodiments, the amount of catalyst is from about 0.1% to about 40% w/w of the total weight of the linking agent and the heavy feedstock. For example, the catalyst may be present at about 0.1% to about 40%, about 0.1% to about 30%, about 0.1% to about 20%, about 0.1% to about 10%, about 0.5% to about 40%, about 0.5% to about 30%, about 0.5% to about 20%, about 0.5% to about 10%, about 1% to about 40%, about 1% to about 30%, about 1% to about 20%, about 1% to about 10% w/w of the total weight of the linking agent and the heavy feedstock.

In other alternative embodiments, the catalyst and the linking agent are present on the same polymer backbone. For example, the catalyst contains an Acid Group (AG), and the linking agent contains a Functional Group (FG), having the following structure.

FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

AG (acid group) is phosphoric acid, sulfonic acid, carboxylic acid or a combination thereof;

x1 and X2 are independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group;

m1 and m2 are independently integers of 1 to 10000;

the polymer had a molecular weight of 1000-1000000 g/mol.

The acid group and the functional group may be selected from any of the examples described above.

In some embodiments, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock without the addition of a solvent.

In some embodiments, the present description provides a method of preparing a thermoplastic or thermoset material from a heavy feedstock in the presence of a solvent. In some particular embodiments, the solvent is selected from chlorobenzene, dichlorobenzene, trichlorobenzene, other halogenated aromatics.

In one aspect, the present description provides thermoplastic or thermoset materials produced using the methods described herein.

In another aspect, the present description provides compositions comprising materials produced by the methods described herein.

Examples

The above embodiments may be further understood by reference to the following examples, among others:

heavy raw material content test

Fourier transform ion cyclotron resonance mass spectrometry ("FTICR-MS") is used to determine the mass-to-charge ratio (m/z) of ions based on the cyclotron frequency of the ions in a fixed magnetic field. The FTICR-MS data obtained in figures 1-3 were generated using the following method:

the sample concentration was 50ppm in toluene

Injector flow rate of 120uL/h

Ionization method APPI (+) (Positive mode atmospheric pressure photoionization)

Mean scan 200

Mass range 150-

Ion accumulation time 0.05s

Calibrating internal, using CH₂Homologous sequences differing in unit

FTICR-MS data for FCC Main Column Bottoms (MCB) and steam cracked tar are presented in FIG. 1. Both MCB and SCT show severe hydrogen deficiency (aromaticity). Thus, both materials are suitable for the ligation chemistry of the present invention. Although SCT showed a higher hydrogen deficiency (higher aromaticity) than MCB.

Heavy raw material under Friedel-Craft condition

Different heavy feedstocks were tested under Friedel-Craft conditions using the following general reaction scheme:

a typical synthetic procedure is described below:

1. in a jar, add 10 grams of MCB, 10 grams of linker and stir the reaction mixture until thoroughly mixed;

2. adding 60mg of acid catalyst p-toluenesulfonic acid, heating the mixture to 60 ℃ to facilitate mixing;

3. the reaction temperature was raised to 130 ℃ and maintained for 5 hours;

4. the reaction mixture was collected for FTICR-MS testing.

FTICR-MS data before and after Friedel-Craft reactions using MCB as starting material are shown in FIGS. 2a, 2b and 2 c. According to FTICR-MS data, more than 90% of the MCB molecules are converted to higher molecular weight species after the Friedel-Craft reaction, and the results also indicate that highly polyaromatic species are more sensitive to the Friedel-Craft reaction.

Additional experiments using vacuum residuum, AR200 and steam cracker tar as starting materials were also performed to test the suitability of different aromatic heavy feedstocks for direct Friedel-Craft reactions, with FTICR-MS data shown in figures 3a, 3b and 3 c. The results show that the Friedel-Craft reaction is effective in increasing the molecular weight of molecules in heavy feedstocks.

Effect of different linkers under Friedel-Craft conditions and uses thereof

The effect of the linker was evaluated in the following experimental procedure using AR200 as heavy feedstock starting material:

1. in a jar, 10 grams of AR200, 10 grams of linker were added and the reaction mixture was stirred until thoroughly mixed.

2. Adding 60mg of acid catalyst p-toluenesulfonic acid, heating the mixture to 60 ℃ to facilitate mixing;

3. the reaction temperature was raised to 130 ℃ and maintained for 5 hours;

4. the viscous reaction mixture was poured into a mold where the mixture was further cured overnight at 110 ℃.

Different linkers were evaluated and the structure of the linker is listed below:

tensile properties of the cured product were measured using an Instron 5565 tensile tester, where the tensile properties were measured according to ASTM D638: standard test methods for tensile properties of plastics samples of standard shape and size were prepared.

When the linking agent is p-divinylbenzene ("DVB"), a type I linking agent, the reaction produces a rigid thermoset. The strain-stress curves of the different tests were compared with commercially available epoxy materials, as shown in fig. 4 and table 1 below.

The effect of different heavy aromatics was evaluated using MCB as heavy feedstock starting material in the following experimental procedure:

1. in a jar, add 10 grams of MCB, 10 grams of linker and stir the reaction mixture until thoroughly mixed;

2. adding 60mg of acid catalyst p-toluenesulfonic acid, heating the mixture to 60 ℃ to facilitate mixing;

3. the reaction temperature was raised to 130 ℃ and maintained for 5 hours;

4. the viscous reaction mixture was poured into a mold where the mixture was further cured overnight at 110 ℃.

The reaction between MCB and DVB linker produces a rigid thermoset material. The strain-stress curves of MCB-DVB were also compared to commercially available epoxy materials, as shown in table 1 below.

Table 1 tensile properties of cured products of AR200 and MCB heavy stock and commercial epoxy materials using DVB linkers at different molar ratios.

In contrast, when the bonding agent is a polyvinyl chloride type II bonding agent, the resulting thermoplastic material is elastic with low stiffness. The strain-stress curves are shown in fig. 5 and table 2 below. Note that the preliminary results indicate that the cure time also affects the tensile properties.

Table 2 tensile properties of cured products using AR200 heavy ends with polyvinyl chloride linkers.

	E(GPa)	s(MPa)	ef(％)
				Not cured	6E-4	0.5	120
2 hours curing	6E-4	0.5-0.7	180
				4 hours curing	0.05	1.5	100？

The contents of all references, patents, pending patent applications and published patents cited in this application are expressly incorporated herein by reference.

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure described herein. Such equivalents are intended to be encompassed by the following claims. It should be understood that the detailed examples and embodiments described herein are given by way of illustration only, and are not to be construed as limiting the invention in any way. Those skilled in the art will envision various modifications and changes within the spirit and scope of the application and the scope of the claims appended hereto. For example, the relative amounts of the ingredients may be varied to optimize a desired effect, other ingredients may be added, and/or similar ingredients may be substituted for one or more of the ingredients described. Other advantageous features and functions associated with the systems, methods, and processes of the present disclosure will be apparent from the appended claims. Moreover, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure. Such equivalents are intended to be encompassed by the following claims.

Exemplary embodiments

1. A process for preparing a thermoplastic or thermoset material from a heavy feedstock comprising the steps of:

contacting the linking agent and catalyst with a heavy feedstock;

reacting the linking agent with the molecules in the heavy feedstock with mixing to form a reaction mixture; and

curing the reaction mixture to form a thermoplastic or thermoset material, wherein the linking agent comprises at least two functional groups that can react with molecules in the heavy feedstock.

2. The method of claim 1, wherein the linker has the structure of formula 1:

wherein FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof; each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group; n is an integer of 1 to 5.

3. The method of claim 1, wherein the linker has the structure of formula 2 a:

wherein FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group;

n is an integer of 1 to 5; and

m is an integer of 2 to 10000;

the polymer skeleton has a molecular weight of 1000-1000000 g/mol.

4. The method of claim 1, wherein the linker has the structure of formula 2 b:

wherein FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

x is a covalent bond, alkyl, cycloalkyl or aryl;

m is an integer of 2 to 10000;

the polymer skeleton has a molecular weight of 1000-1000000 g/mol.

5. The method of claim 1, wherein the linker is a molecule having the structure or a derivative thereof.

6. The method of claim 1, wherein the linking agent is sulfur or a sulfur compound.

7. The method of claim 1, wherein the catalyst and the linking agent are present on the same polymer backbone.

8. The method of claim 1, wherein the catalyst comprises an Acid Group (AG), the linking agent comprises a Functional Group (FG), having the structure:

wherein FG (functional group) is an aldehyde, vinyl, halogen, alcohol, acid halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof;

AG (acid group) is phosphoric acid, sulfonic acid, carboxylic acid or a combination thereof;

X₁and X₂Independently a covalent bond, an alkyl, cycloalkyl, or aryl group;

m₁and m₂Are respectively an integer of 1-10000;

the polymer had a molecular weight of 1000-1000000 g/mol.

9. The method of claim 1, wherein the linking agent comprises diene functionality.

10. The method of any one of claims 1-9, further comprising oxidizing molecules in the heavy feedstock.

11. The method of any one of claims 1-10, wherein molecules in the heavy feedstock are oxidized to increase molecular weight or functionality.

14. The method of any one of claims 1-11, wherein the molecules in the heavy feedstock are in concentrated H₂SO₄And oxidation under hydrogen peroxide conditions.

13. The method of any one of claims 1-12, wherein the linking agent comprises a naphthalene, pyrene, or biphenyl molecule linked to more than one functional group selected from aldehyde, vinyl, halogen, alcohol, acyl halide, tosylate, mesylate, carboxylic acid anhydride, or a combination thereof.

14. The process of any one of claims 1-13, wherein the catalyst is selected from the group consisting of inorganic acids, organic acids, or lewis acids.

15. A process according to any one of claims 1 to 14, wherein the catalyst is selected from aluminium chloride, trifluoromethanesulphonic acid, p-toluenesulphonic acid, sulphuric acid, phosphoric acid, polyphosphoric acids, solid acids such as tungstic acid, polyoxometallates and other acids having the following structure. These acids may be used alone or in combination.

16. The process of claim 1 wherein the catalyst is

Wherein the AG (acid group) is phosphoric acid, sulfonic acid, carboxylic acid, methanesulfonic acid, p-toluenesulfonic acid, or a combination thereof; each X is independently a covalent bond, an alkyl group, a cycloalkyl group, or an aryl group; and

n is an integer of 0 to 5.

17. The method of any one of claims 1-16, wherein the amount of linking agent is 0.1% -100% w/w of the total weight of the heavy feedstock.

18. The method of any one of claims 1-17, wherein the amount of linking agent is 20% -80% w/w of the total weight of the heavy feedstock.

19. The method of any one of claims 1-18, wherein the amount of catalyst is 0.1% -10% w/w of the total weight of the linking agent and the heavy feedstock.

20. The method of any one of claims 1-19, wherein no solvent is used.

21. The method of any one of claims 1-20, wherein a solvent is used, and the solvent is selected from chlorobenzene, dichlorobenzene, trichlorobenzene, other halogenated aromatic compounds, or combinations thereof.

22. The method of any one of claims 1-21, wherein the linker and the molecule in the heavy feedstock are reacted at a temperature of from room temperature to 400 ℃.

23. The method of any one of claims 1-22, wherein the linker and the molecule in the heavy feedstock react at a temperature of 80 ℃ to 200 ℃.

24. A thermoset produced according to claims 1-23.

25. A composition comprising the thermoset or thermoset material produced according to claims 1-23.

Equivalents of the same

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments and methods described herein. Such equivalents are intended to be encompassed by the scope of the appended claims.

It should be understood that the detailed examples and embodiments described herein are given by way of illustration only and are not to be construed as limiting the present disclosure in any way. Those skilled in the art will envision various modifications and changes within the spirit and scope of the application, and are deemed to be within the scope of the claims appended hereto. For example, the relative amounts of the ingredients may be varied to optimize a desired effect, other ingredients may be added, and/or similar ingredients may be substituted for one or more of the ingredients described. Other advantageous features and functions associated with the systems, methods, and processes of the present disclosure will be apparent from the appended claims. Moreover, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the disclosure described herein. Such equivalents are intended to be encompassed by the following claims.