Bio-based isosorbide itaconic acid derivative compound and preparation method and application thereof

Abstract

The present invention provides a bio-based isosorbide itaconic acid derivative compound and its preparation method and application, the main body of the molecule is formed by isosorbide and itaconic anhydride through carbamate bond compound, specifically by isocyanate reaction of isosorbide with hydroxyl structure and itaconic acid imide substituted. The core group of the molecule is all formed by bio-based isosorbide and itaconic acid and its derivative compound, which reduces or avoids the use of petrochemical products from the source of synthesis, has the dual effect of saving resources and protecting the environment, and the preparation process is simple, easy to implement and control. The double bond in itaconic acid imide in the present invention can participate in free radical polymerization, or it can further react with a sulfhydryl compound or form a polymer structure with polythiol, and has a wide range of applications. It can further undergo photopolymerization with an acrylate photocurable monomer with a double bond, or it can undergo thiol-ene photopolymerization with dithiol or polythiol in the presence of a photoinitiator.

Description

Technical Field

[0001] The present invention belongs to the technical field of new material organic chemicals, and specifically relates to a bio-based isosorbide itaconic acid derivative compound, whose molecular structure contains an itaconic acid-derived carbon-carbon double bond unsaturated group, as well as its preparation method and application, especially its use in click polymerization with dithiol derivatives to prepare polymers and as a monomer in the field of photocurable materials. Background Art

[0002] As petroleum resources become increasingly depleted, finding sustainable, high-quality, and affordable alternatives to petroleum is crucial to the survival and development of the polymer industry. Bio-based polymer materials, primarily derived from renewable resources, reduce the plastics industry's consumption of petrochemical products while also minimizing environmental pollution during the production of petroleum-based raw materials. This represents a key development direction for polymer materials, offering significant practical value and broad potential for growth. Since the beginning of the 21st century, bio-based materials have garnered increasing attention.

[0003] Sorbitol, listed as one of twelve carbohydrate-derived platform compounds by the U.S. Department of Energy in 2004, is found as a sweetener in many berries and fruits. Sorbitol can undergo hydrogenolysis, polymerization, and dehydration to produce a range of high-value-added bio-based chemicals and materials. Among them, isosorbide, the secondary dehydration cyclization product, is an important new bio-based chemical with wide applications in food, cosmetics, and pharmaceuticals.

[0004] Itaconic acid is a small molecule compound with an unsaturated double bond and a terminal carboxyl group. Due to its scalability, sustainability, and non-toxicity, the U.S. Department of Energy's National Renewable Energy Laboratory has designated itaconic acid as one of the top twelve renewable chemicals derived from biomass. Itaconic acid, scientifically known as methylene succinic acid and methylene succinic acid, is the fifth most abundant organic acid in the world (followed by citric acid, gluconic acid, lactic acid, and malic acid). It is an unsaturated dibasic organic acid. Its unsaturated double bond and active chemical properties make it an important chemical raw material. Its preparation methods include chemical and fermentation. The fermentation method is currently the predominant method used both domestically and internationally. The fermentation method uses agricultural byproducts such as starch, sucrose, molasses, sawdust, and straw as raw materials. After two days of fermentation using Aspergillus terreus, it is filtered, concentrated, decolorized, crystallized, and dried. Therefore, itaconic acid is considered a renewable biomass raw material. Its derivative, itaconic anhydride, is similar to maleic anhydride in that it has an active double bond structure and is widely used in the chemical industry.

[0005] Polymer elastomers are very important materials in many fields. Among the many elastic matrices, polyurethane is one of the most representative polymers because of its rich raw material selection, flexible formulation and adjustable mechanical properties. Soft segments with a lower glass transition temperature (Tg) and hard segments with a higher Tg are intermittently distributed on the main chain of polyurethane. In the condensed state, the two thermodynamically incompatible components undergo microphase separation to form soft and hard phases, respectively. The low Tg of the soft phase makes it reversible, while the hard phase has strong hydrogen bonds or a crystalline state, which can provide good shape fixing effects. Therefore, compared with other homopolymer elastomers, polyurethane has excellent toughness and tear resistance. At the same time, by adjusting the ratio of soft and hard segments, a variety of desired moduli and deformation capabilities can be obtained.

[0006] The thiol-ene click reaction, due to its high efficiency and insensitivity to water and oxygen, can be used to prepare a variety of polymer molecules. In recent years, thiol-ene reactions have been demonstrated to be highly suitable for polymerization reactions or polymer modification, requiring only small amounts of initiators and catalysts. Furthermore, thiol-ene polymerization can easily form ideal cross-linked networks or well-defined star polymers. Therefore, thiol-ene reactions have broad applications in general polymer preparation and photopolymerization.

[0007] Photocuring technology involves the polymerization of liquid photosensitive resins into solids under light-induced polymerization. It boasts high efficiency, rapid response, cost-effectiveness, energy efficiency, and environmental friendliness. It is widely used in adhesives, photocurable coatings and inks, photoresists, 3D microstructures, and biomedicine. Photocurable monomers are key factors in controlling the overall performance of the cured product. Their reactivity and dilutability directly influence the curing rate, degree of cure, and ultimately the performance of the end product. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention provides a bio-based isosorbide-itaconate derivative. The main molecule is composed of isosorbide and itaconic anhydride bonded via a carbamate bond. The double bond in itaconimide can further undergo thiol-ene reactions to form larger molecules.

[0009] The second object of the present invention is to provide a method for preparing the above-mentioned bio-based isosorbide itaconic acid derivative compound.

[0010] The third object of the present invention is to provide the use of the above-mentioned bio-based isosorbide itaconic acid derivative compound in the synthesis of polymers, including the use in thermally initiated or photoinitiated thiol-ene polymerization.

[0011] To achieve the above object, the solution of the present invention is:

[0012] The bio-based isosorbide itaconic acid derivative compound includes isosorbide and its derivatives and itaconimide connected by a carbamate bond connected by a flexible chain. It is prepared by reacting isosorbide with a hydroxyl structure and two itaconimide-substituted isocyanates. The molecular end group contains two double bonds. The specific molecular structure is shown in the general formula (I):

[0013]

[0014] Wherein, the R group is selected from C1-C 12 Alkyl, C2-C 12 Any group of alkenyl, aryl and aralkyl, wherein one or more -CH2- can be independently replaced by -O-, -CO-, -COO-, -OCO- or a benzene ring;

[0015] m is selected from an integer between 0 and 10; n is selected from an integer between 1 and 11.

[0016] Furthermore, isosorbide and its derivatives include small molecules or high molecular weight diols having an isosorbide structure.

[0017] Furthermore, the small molecule or high molecular weight diol having an isosorbide structure has a structure as shown in formula (II):

[0018]

[0019] Wherein, the R group is selected from C1-C 12 Alkyl, C2-C 12 Any group of alkenyl, aryl and aralkyl, wherein one or more -CH2- can be independently replaced by -O-, -CO-, -COO-, -OCO- or a benzene ring;

[0020] m is an integer selected from 0-10.

[0021] Furthermore, the number average molecular weight of the small molecule or high molecular weight diol having an isosorbide structure is 146-5000 g / mol.

[0022] A method for preparing the above-mentioned bio-based isosorbide itaconic acid derivative compound (wherein the raw materials used are known compounds in the prior art, which can be purchased commercially or easily prepared by known synthetic methods) comprises the following steps:

[0023]

[0024] (a), 1 equivalent of itaconic anhydride and 1 equivalent of aminocarboxylic acids with alkyl chains of different lengths are heated to reflux in toluene (10 ml per gram of raw material) for 3-5 hours. After the reaction, the mixture is kept at 4°C overnight. The precipitated solid is filtered, washed with ether, and dried in vacuo to obtain the intermediate product I-(a). If further purification is required, it can be recrystallized from isopropanol.

[0025] (b) Dissolve I-(a) (1 equivalent) in acetone (5-15 ml per gram of starting material). Cool the solution to approximately -5°C using a low-temperature bath (ice / NaCl cooling bath). Then, add triethylamine (1.1 equivalents) dropwise. Then, add ethyl chloroformate (1.1 equivalents) dissolved in acetone (5-15 ml per gram of starting material) until the solution becomes cloudy and slightly rose-colored. After stirring for an additional 10 minutes, add NaN3 (1 equivalent) and continue stirring for 0.5-2 hours. After the reaction is complete, pour the reaction mixture into H2O and extract with toluene. The combined organic layers are dried over MgSO4 and heated to reflux at 140°C for 100 minutes. After cooling to room temperature, the toluene is removed under reduced pressure to produce an oily substance. The crude product I-(b) is used in subsequent reactions without further purification. It can be stored in a refrigerator under nitrogen; the oil will solidify.

[0026] (c) Isosorbide and its derivatives (1 equivalent) and dibutyltin dilaurate (0.002 equivalent) are added to a dry solvent (5-15 ml per gram of raw material), and then I-(b) (2.1 equivalents) are added. The reaction mixture is stirred overnight at ambient temperature, and most of the organic solvent is removed by distillation under reduced pressure. Then, excess ether is added, and the product is separated by precipitation and filtered. Further purification can be achieved by recrystallization from toluene:isopropanol (80:20). If the product is a viscous liquid, it can be separated by column chromatography. Preferably, the organic solvent is selected from tetrahydrofuran or chloroform.

[0027] Exemplary compounds conforming to the general formula (I) are listed below:

[0028]

[0029] A use of the above-mentioned bio-based isosorbide itaconic acid derivative compound in the preparation of polymers.

[0030] Furthermore, the polymer includes one or more of the above-mentioned bio-based isosorbide itaconate derivative compounds (A monomer component) and one or more small molecule dithiols (B monomer component).

[0031] Furthermore, the polymer includes one or more of the above-mentioned bio-based isosorbide itaconic acid derivative compounds (A monomer component), one or more small molecule dithiols (B monomer component), and a diene chain extender with a non-planar ring structure (C monomer component).

[0032] Furthermore, the polymer includes one or more of the above-mentioned bio-based isosorbide itaconic acid derivative compounds (A monomer component), one or more small molecule dithiols (B monomer component), and a diisocyanate chain extender (D monomer component).

[0033] Furthermore, the polymer includes one or more of the above-mentioned bio-based isosorbide itaconic acid derivative compounds (A monomer component), one or more small molecule dithiols (B monomer component), a diene chain extender with a non-planar ring structure (C monomer component), and a diisocyanate chain extender (D monomer component).

[0034] Furthermore, the double bonds of small molecule dithiols and bio-based isosorbide itaconic acid derivatives undergo alternating copolymerization through a thiol-ene click reaction using a catalyst to produce a polymer containing a carbamate bond.

[0035] Furthermore, the small molecule dithiol is selected from any one or a combination of two or more of 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol or 1,10-decanedithiol.

[0036] Furthermore, the catalyst is selected from organic phosphine molecules. Preferably, the catalyst is selected from one or more of dimethylphenylphosphine and triphenylphosphine.

[0037] Furthermore, the method of introducing a diene chain extender with a non-planar ring structure into the polymer is to obtain the polymer by alternately copolymerizing a small molecule dithiol and a diene with a non-planar ring structure under the initiation of azobisisobutyronitrile, and the two ends of the obtained polymer chain are capped with thiol.

[0038] Furthermore, the diene chain extender with a non-planar ring structure is 1,4-cyclohexanedimethanol divinyl ether.

[0039] Furthermore, the method of introducing a diisocyanate chain extender into the polymer is to obtain the polymer by alternately copolymerizing a small molecule dithiol and a diisocyanate in the presence of a catalyst, and the two ends of the obtained polymer chain are capped with thiol.

[0040] Furthermore, the catalyst is selected from any one or a combination of two or more of bis(dimethylaminoethyl)ether, pentamethyldiethylenetriamine, 2-methylcyclohexylamine, dibutyltin dilaurate, organic bismuth or triazine catalyst (CAS No.: 15875-13-5).

[0041] Furthermore, the diisocyanate in the diisocyanate chain extender is selected from any one or a combination of two or more of isophorone diisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate or dicyclohexylmethane diisocyanate.

[0042] Furthermore, the present invention provides a method for preparing a target polymer through a thiol-ene click reaction. Specifically, in a protective gas, a uniformly mixed reaction system of the above-mentioned bio-based isosorbide itaconic acid derivative compound, a small molecule dithiol, or a dithiol-terminated chain-extended polymer (a diene chain extender or a diisocyanate chain extender with a non-planar ring structure), a catalyst, and an organic solvent is reacted to obtain a polymer with the bio-based isosorbide itaconic acid derivative compound as the basic structure, and the target polymer is obtained after washing and drying.

[0043] The concentration of the reactants in the uniformly mixed reaction system is 10-50 wt %; the reaction temperature is 25-100° C., the reaction time is 1-24 hours, and then post-processing is performed to obtain the target polymer.

[0044] The molar ratio of all double bond groups of the bio-based isosorbide itaconic acid derivative compound and the diene chain extender with a non-planar ring structure to the thiol group in the uniform reaction system is 1:1.

[0045] The protective gas is selected from nitrogen or argon.

[0046] The catalyst is selected from at least one of azobisisobutyronitrile, dibenzoyl peroxide, and phenyldimethylphosphine.

[0047] The organic solvent is selected from any one of tetrahydrofuran, N,N-dimethylformamide, chloroform or tetrachloroethane, or a combination of two or more thereof.

[0048] After the reaction is completed, the obtained solid is washed with a washing liquid and then dried in vacuum at 60-100° C. for 12-36 hours.

[0049] The washing liquid is selected from any one of distilled water, methanol, ethanol, propanol or butanol, or a combination of two or more thereof.

[0050] The bio-based isosorbide itaconic acid derivative compound is used as a monomer (i.e., a monomer with a polyurethane structure) in the field of photocuring. The double bond in the itaconimide can participate in the photocuring formulation of various commercial acrylate monomers, oligomers, or prepolymers. It can also undergo a thiol-ene reaction with dithiol or polythiol photocuring monomers, initiated by a photoinitiator. Photoinitiators include various commercially available α-hydroxyketones, α-aminoketones, acylphosphinoyls, thioxanthones, benzophenones, and the like.

[0051] The field of photocuring includes applications in formulations such as photocuring coatings, photocuring inks, photocuring adhesives, and photocuring 3D printing. Bio-based isosorbide itaconic acid derivative compounds can be the main body of photocuring or an additive.

[0052] The light source excited by the photoinitiator for photocuring is selected from at least one of ultraviolet light and visible light.

[0053] Furthermore, the light source for photocuring is selected from at least one of a mercury lamp that can emit ultraviolet light and visible light, an LED light source, and an LDI light source.

[0054] Furthermore, the photocurable photoinitiator includes 0.01-30 parts by weight of a commercial photoinitiator.

[0055] Furthermore, the photocurable composition comprises 0.5-10 parts by weight of a commercial photoinitiator and 100 parts by weight of an ethylenically (C=C) unsaturated compound, wherein the unsaturated compound comprises one or more bio-based isosorbide itaconic acid derivative compounds.

[0056] In fact, the photocurable composition may contain, in addition to commercial photoinitiators and ethylenically (C=C) unsaturated compounds, any components such as inorganic fillers, organic fillers, colorants, other additives and solvents as needed.

[0057] Wherein, the colorant is selected from pigments or dyes.

[0058] Other additives (auxiliaries) include UV absorbers, light stabilizers, flame retardants, leveling agents (BYK 307) or defoamers (BYK 051).

[0059] The specific steps are as follows: (1) preparing the raw materials according to the mass ratio of monomer to resin: photoinitiator: auxiliary agent of 100:0.5-1:0-4.5; (2) stirring to fully dissolve them; (3) irradiating the polymerization system with light sources of different wavelengths or different light intensities; (4) the polymerization conversion rate can be studied by infrared method through the change of its characteristic peak; wherein: the light source in step (3) can be a mercury lamp (high pressure, medium pressure and low pressure), as well as LEDs and LDI light sources with an emission wavelength of 365-425nm.

[0060] Furthermore, the ethylenically unsaturated compound refers to a compound or mixture in which ethylenic bonds are cross-linked by free radical polymerization, wherein the unsaturated compound includes one or more bio-based isosorbide itaconic acid derivative compounds.

[0061] Furthermore, the ethylenically unsaturated compound is selected from monomers, oligomers or prepolymers, or a mixture or copolymer of the three, or an aqueous dispersion of the three, wherein the unsaturated compound includes one or more bio-based isosorbide itaconic acid derivative compounds.

[0062] Suitable free radical polymerizable ethylenic polymerizable monomers include one or more itaconic acid-derived multiple double bond monomers, and also include but are not limited to (meth)acrylates, acrolein, olefins, conjugated dienes, styrene, maleic anhydride, fumaric anhydride, vinyl acetate, vinyl pyrrolidone, vinyl imidazole, (meth)acrylic acid, (meth)acrylic acid derivatives such as (meth)acrylamide, vinyl halides and vinylidene halides, etc.

[0063] Suitable olefinic prepolymers and oligomers include, but are not limited to, (meth)acryloyl-functional (meth)acrylic copolymers, urethane (meth)acrylates, polyester (meth)acrylates, unsaturated polyesters, polyether (meth)acrylates, silicone (meth)acrylates, epoxy (meth)acrylates, and the like, as well as water-soluble or water-dispersible analogs thereof.

[0064] The above-mentioned commercial olefin-containing monomers and various free-radical polymerizable oligomers, prepolymers, or copolymers are well known to those skilled in the art and are not particularly limited.

[0065] Due to the adoption of the above solution, the beneficial effects of the present invention are:

[0066] 1. The present invention introduces isosorbide and itaconic acid into a compound containing a carbamate bond, utilizing the biomass source of isosorbide and itaconic acid, which is non-toxic and pollution-free, has a simple preparation process, and the raw materials are readily available and sustainable. It is easy to realize process production while increasing environmental protection characteristics, and can effectively avoid the use of petroleum-based resources.

[0067] 2. The compound prepared by the present invention contains double bonds of itaconimide at both end groups, which can undergo polymerization reaction with small molecule dithiols or polymer dithiols with chain extenders through thiol-ene click reaction to prepare polymers with polyurethane structures. Isosorbide can provide rigidity of polyurethane, which helps to improve its recovery ability after stretching.

[0068] 3. The itaconic acid derivative prepared in the present invention can further undergo photopolymerization reaction with an acrylic acid ester photocurable monomer having a double bond due to its double bond, and can also undergo thiol-ene photopolymerization reaction with a dithiol or polythiol in the presence of a photoinitiator. The prepared polymer exhibits better mechanical properties due to the presence of a carbamate group.

[0069] 4. The polymerization method for preparing polyurethane from bio-based isosorbide itaconic acid derivative compounds provided by the present invention has the characteristics of simple process, easy availability of raw materials, and strong controllability of material properties, and has very broad application prospects.

[0070] In summary, the present invention uses two bio-based derivatives of isosorbide and itaconic anhydride as raw materials, linked by a carbamate bond, to prepare a compound containing two itaconic acid double bonds. This compound can be used as an olefinic monomer in thiol-ene polymerization reactions and can be thermally or photopolymerized with dithiols or polythiols to produce polyurethane elastomers. It has promising applications in polyurethane elastomers and photocurable materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Figure 1 The figure is a general structural formula diagram of the bio-based isosorbide itaconic acid derivative compound of the present invention. DETAILED DESCRIPTION

[0072] The technical solution of the present invention is further described in detail below in conjunction with several preferred embodiments and the accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0073] Unless otherwise specified, the experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.

[0074] The technical solution of the present invention will be described clearly and completely below. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0075] Example 1: Preparation of I-(1) molecule

[0076]

[0077] First, itaconic anhydride (11.2 g, 0.1 mol) and 2-aminopropionic acid (8.9 g, 0.1 mol) were heated to reflux in toluene (200 mL) for 4 h. After the reaction was completed, the mixture was placed in a refrigerator at 4°C overnight. The precipitated solid was filtered, washed with ether, and dried in vacuo to obtain the product 3-(3-methylene-2,5-dioxypyrrolidin-1-yl)propionic acid with a yield of 75%.

[0078] Next, 3-(3-methylene-2,5-dioxypyrrolidin-1-yl)propanoic acid (9.15 g, 0.05 mol) was dissolved in acetone (100 mL). The solution was cooled to approximately -5°C using an ice / NaCl cooling bath. Subsequently, triethylamine (5.6 g, 0.055 mol) was added dropwise. Ethyl chloroformate (6.0 g, 0.055 mol) dissolved in acetone (50 mL) was then added, and the solution became turbid and slightly rose-colored. After stirring for an additional 10 minutes, NaN3 (3.25 g, 0.05 mol) was added and stirring continued for 1 hour. After the reaction was complete, the reaction mixture was poured into 300 mL of H2O and extracted with 200 mL of toluene. The combined organic layers were dried over MgSO4 and heated to reflux at 140°C for 100 minutes. After cooling to room temperature, the toluene was removed under reduced pressure to yield an oily substance, 1-(2-isocyanateethyl)-3-methylenepyrrolidine-2,5-dione. The crude product was used in subsequent reactions without further purification. It can be stored in a refrigerator under nitrogen; the oil will solidify.

[0079] Finally, isosorbide (7.3 g, 0.05 mol) and dibutyltin dilaurate (0.1 mmol) were added to dry tetrahydrofuran (70 mL), followed by 1-(2-isocyanateethyl)-3-methylenepyrrolidine-2,5-dione (19.8 g, 0.11 mol). The reaction mixture was stirred at ambient temperature overnight. Most of the tetrahydrofuran was removed by distillation under reduced pressure, and then 100 mL of anhydrous ether was added to isolate the product by precipitation. The product was filtered and further purified by recrystallization from toluene:isopropanol (80:20). The yield was 83%, and the purity was 99% as determined by HPLC.

[0080] I-(1):MS(C 22 H 26 N4O 10 ): m / e: 506.16; experimental result: 507.17 (M+H + ).

[0081] Example 2: Preparation of I-(2)

[0082]

[0083] First, a mixture of isosorbide (100 g, 0.68 mol) and ethylene carbonate (132 g, 1.50 mol) was placed in a 500 mL two-necked round-bottom flask. After evacuation and nitrogen filling three times, the reaction mixture was added in a 70° C. oil bath under nitrogen protection to dissolve the isosorbide in the ethylene carbonate. K2CO3 (9.4 g, 0.068 mmol) was added to the reaction system, and the temperature was raised to 170° C. and the reaction was allowed to react for 48 h. Excess raw materials were distilled off under reduced pressure, and inorganic salts were filtered to obtain a crude product, which could be purified by silica gel column chromatography (mobile phase: methanol / ethyl acetate = 1 / 9) to obtain dihydroxyethyl-substituted isosorbide.

[0084] Secondly, using dihydroxyethyl-substituted isosorbide and 1-(2-isocyanateethyl)-3-methylenepyrrolidine-2,5-dione, the same reaction method as in Example 1 was used to prepare product I-(2), which was further purified by column chromatography (mobile phase: n-hexane / ethyl acetate = 1 / 2).

[0085] I-(2):MS(C 26 H 34 N4O 12 ): m / e: 594.22; experimental result: 595.22 (M+H + ).

[0086] Example 3: Preparation of I-(3)

[0087]

[0088] First, itaconic anhydride (11.2 g, 0.1 mol) and 3-aminobutyric acid (10.3 g, 0.1 mol) were heated to reflux in toluene (200 mL) for 4 h. After the reaction, the mixture was placed in a refrigerator at 4°C overnight. The precipitated solid was filtered, washed with ether, and dried in vacuo to obtain the product 4-(3-methylene-2,5-dioxypyrrolidin-1-yl)butyric acid with a yield of 73%.

[0089] Next, 4-(3-methylene-2,5-dioxypyrrolidin-1-yl)butanoic acid (9.85 g, 0.05 mol) was dissolved in acetone (100 mL). The solution was cooled to approximately -5°C using an ice / NaCl cooling bath. Subsequently, triethylamine (5.6 g, 0.055 mol) was added dropwise. Ethyl chloroformate (6.0 g, 0.055 mol) dissolved in acetone (50 mL) was then added, and the solution became turbid and slightly rose-colored. After stirring for another 10 minutes, NaN3 (3.25 g, 0.05 mol) was added and stirring continued for 1 hour. After the reaction was completed, the reaction mixture was poured into 300 mL of H2O and extracted with 200 mL of toluene. The combined organic layers were dried over MgSO4 and heated to reflux at 140°C for 100 minutes. After cooling to room temperature, the toluene was removed under reduced pressure to yield an oily substance, 1-(3-isocyanatepropyl)-3-methylenepyrrolidine-2,5-dione. The crude product was used in subsequent reactions without further purification. It can be stored in a refrigerator under nitrogen; the oil will solidify.

[0090] Finally, isosorbide (7.3 g, 0.05 mol) and dibutyltin dilaurate (0.1 mmol) were added to dry tetrahydrofuran (70 mL), followed by 1-(3-isocyanatepropyl)-3-methylenepyrrolidine-2,5-dione (21.3 g, 0.11 mol). The reaction mixture was stirred at ambient temperature overnight. Most of the tetrahydrofuran was removed by distillation under reduced pressure, and further purification was achieved by column chromatography (mobile phase: n-hexane / ethyl acetate = 1 / 2). HPLC monitoring showed a purity of 99%.

[0091] (I)-3:MS(C 24 H 30 N4O 10 ): m / e: 534.20; experimental result: 535.20 (M+H + ).

[0092] Example 4: Preparation of I-(4)

[0093]

[0094] Using dihydroxyethyl-substituted isosorbide and 1-(3-isocyanatepropyl)-3-methylenepyrrolidine-2,5-dione, the product I-(4) was prepared using the same reaction method as in Example 1, and further purified by column chromatography (mobile phase: n-hexane / ethyl acetate = 1 / 2).

[0095] I-(4):MS(C 28 H 38 N4O 12 ): m / e: 622.25; experimental result: 623.25 (M+H+ ).

[0096] Example 5: Preparation of polymers of I-(1) and small molecule dithiols by click reaction

[0097]

[0098] To a solution of I-(1) (5.06 g, 10.0 mmol) in tetrahydrofuran (50 mL) was added 1,6-hexanedithiol (1.50 g, 10.0 mmol), followed by a catalytic amount of dimethylphenylphosphine (27.6 μL, 0.194 mmol), and the reaction mixture was stirred at 50°C for 16 h. After 16 h, the reaction mixture was cooled to ambient temperature and added dropwise to diethyl ether (500 mL) to precipitate the polymer from the solution to obtain a white rubbery solid, which was further washed with diethyl ether (200 mL). The polymer was dried in a vacuum oven at 90°C for 5 h to obtain an off-white solid, which was the target polymer.

[0099] Example 6: Preparation of polymers comprising I-(1) and small molecule dithiols and divinyl ether chain extenders by click reaction

[0100]

[0101] First, under nitrogen protection, 1,6-hexanedithiol (30.0 g, 0.2 mol) and 1,4-cyclohexanedimethanol divinyl ether (19.6 g, 0.1 mol) were added to a reactor containing azobisisobutyronitrile (0.164 g, 1 mmol) and chloroform (500 mL). The mixture was heated under reflux for 2 h. After the reaction was completed, the product did not need to be isolated. 500 mL of chloroform containing I-(1) (50.6 g, 0.1 mmol) was added dropwise to the system through a liquid addition system. The mixture was refluxed for another 2 h under nitrogen protection throughout the process. The polymer was precipitated in a large amount of methanol, washed with methanol, and then vacuum dried to obtain a polyurethane elastomer having isosorbide, thioether bonds, and a non-planar ring structure.

[0102] Example 7: Preparation of a polymer comprising I-(2) and a small molecule dithiol and a diisocyanate chain extender by click reaction

[0103]

[0104] First, under nitrogen protection, 1,6-hexanedithiol (30.0 g, 0.2 mol) and isophorone diisocyanate (22.2 g, 0.1 mol) were added to a reactor containing dibutyltin dilaurate (52 mg, 0.1 wt%) and chloroform (500 mL). The reaction was stirred at room temperature for 1 h. After the reaction was completed, the product did not need to be isolated. A 500 mL chloroform solution containing I-(2) (59.4 g, 0.1 mmol) and azobisisobutyronitrile (0.164 g, 1 mmol) was added dropwise to the system through a liquid addition system. The mixture was heated under reflux for 2 h with stirring, under nitrogen protection throughout the process. The polymer was precipitated in a large amount of methanol, washed with methanol, and then vacuum dried to obtain a polyurethane elastomer having isosorbide, thioether bonds, and thiocarbamate.

[0105] <Experiment>: Photoinitiated free radical and thiol-ene photopolymerization experiments and coating performance testing

[0106] <Experiment 1>

[0107] Monomer I-(1) or I-(2) or I-(3) or I-(4) in the embodiment: 10 parts by mass

[0108] Bifunctional monomer (TPGDA): 43 parts by mass

[0109] Trifunctional monomer (TMPTA): 44 parts by mass

[0110] Photoinitiator (Irgacure 184): 2 parts by mass

[0111] Leveling agent (BYK 307): 0.5 parts by mass

[0112] Defoamer (BYK 051): 0.5 parts by mass

[0113] The mixture prepared in the above example was applied to cardboard to form a coating approximately 30-35 μm thick. A 365 nm LED light source (3 cm wide and 80 cm long, manufactured by Guangzhou Heguang Tongsheng Co., Ltd.) was used as the excitation light source. The cardboard was placed on a variable-speed conveyor. The photopolymerization curing was considered complete if repeated fingernail pressure and scratching did not produce marks.

[0114] The results showed that the compounds of this example were all cured efficiently at a speed higher than 30 m / min.

[0115] The coating obtained by light curing was tested for hardness using a hand-cranked pencil hardness tester, and the hardness was measured to be 2H.

[0116] Experiment 2

[0117] Monomer I-(1) or I-(2) or I-(3) or I-(4) in the embodiment: 20 parts by mass

[0118] Bifunctional acrylate monomer (TPGDA): 43 parts by mass

[0119] Trimethylolpropane tris(3-mercaptopropionate) (TMPMP): 34 parts by mass

[0120] Photoinitiator (Irgacure 184): 2 parts by mass

[0121] Leveling agent (BYK 307): 0.5 parts by mass

[0122] Defoamer (BYK 051): 0.5 parts by mass

[0123] After mixing the above raw materials, stir at 50°C for 1 hour to form a transparent system. Apply the prepared solution from the example above to cardboard to form a coating approximately 30-35 μm thick. Use a 365 nm LED light source (3 cm wide and 80 cm long LED surface light source, manufactured by Guangzhou Heguang Tongsheng Co., Ltd.) as the excitation light source. Place the cardboard on a variable-speed conveyor. Photopolymerization curing is considered complete if repeated fingernail pressure and scratching do not produce marks.

[0124] The results showed that the compounds of this example all cured efficiently at speeds exceeding 80 m / min. The significantly faster polymerization rate compared to Experiment 1 suggests that, in addition to the free radical polymerization shown in Experiment 1, there was also a free radical-initiated thiol-ene polymerization reaction, which resulted in very rapid and high conversion rates.

[0125] The above description of the embodiments is intended to facilitate understanding and use of the present invention by those skilled in the art. Those skilled in the art will readily be able to make various modifications to these embodiments and apply the general principles described herein to other embodiments without resorting to creative effort. Therefore, the present invention is not limited to the above-described embodiments. Any improvements or modifications made by those skilled in the art based on the principles of the present invention that do not depart from the scope of the present invention should be considered within the scope of protection of the present invention.

Claims

1. A bio-based isosorbide itaconic acid derivative compound, characterized in that: It comprises isosorbide and its derivatives and itaconimide connected by a carbamate bond, and the specific molecular structure is shown in the general formula (I): Wherein, the R group is selected from C1-C 12 Alkyl; m is selected from an integer between 0 and 10; n is selected from an integer between 1 and 11.

2. The bio-based isosorbide itaconic acid derivative compound according to claim 1, characterized in that: The isosorbide and its derivatives include small molecules or high molecular weight diols with an isosorbide structure; The small molecule or high molecular weight diol having an isosorbide structure has a structure as shown in formula (II): Wherein, the R group is selected from C1-C 12 Alkyl; m is an integer selected from 0-10.

3. A method for preparing a bio-based isosorbide itaconic acid derivative compound according to claim 1, characterized in that: It includes the following steps: (a) Itaconic anhydride and aminocarboxylic acids with different alkyl chain lengths were heated to reflux in a toluene system for 3-5 hours. After the reaction was completed, the mixture was allowed to stand at 4°C overnight. The precipitated solid was filtered, washed with ether, and dried in vacuo. ； (b) Dissolve I-(a) in acetone, cool the solution using an ice / NaCl cooling bath, add triethylamine dropwise, then add ethyl chloroformate dissolved in acetone until the solution becomes turbid and slightly rose-colored, stir for 10 minutes, then add NaN3, continue stirring for 0.5-2 hours, and after the reaction is complete, pour the reaction mixture into H2O and extract with toluene; dry the combined organic layers over MgSO4, heat to reflux at 140°C for 100 minutes, cool to room temperature, and remove toluene under reduced pressure to produce an oily substance; ； (c) adding isosorbide and its derivatives and dibutyltin dilaurate to a dry solvent, and then adding I-(b). The reaction mixture is stirred at ambient temperature overnight, and most of the organic solvent is removed by distillation under reduced pressure. Then, diethyl ether is added, and the product is separated by precipitation and filtered; 。 4. The preparation method according to claim 3, wherein: In step (c), the organic solvent is selected from at least one of tetrahydrofuran and chloroform.

5. Use of the bio-based isosorbide itaconic acid derivative compound according to claim 1 in the preparation of a polymer.

6. The use according to claim 5, characterized in that: The polymer comprises one or more bio-based isosorbide itaconate derivative compounds according to claim 1 and one or more small molecule dithiols.

7. The use according to claim 5, characterized in that: The polymer comprises one or more bio-based isosorbide itaconate derivative compounds according to claim 1, one or more small molecule dithiols, and a diene chain extender with a non-planar ring structure.

8. The use according to claim 5, characterized in that: The polymer comprises one or more bio-based isosorbide itaconic acid derivative compounds according to claim 1, one or more small molecule dithiols, and a diisocyanate chain extender.

9. The use according to claim 5, characterized in that: The polymer comprises one or more bio-based isosorbide itaconic acid derivative compounds according to claim 1, one or more small molecule dithiols, a diene chain extender with a non-planar ring structure, and a diisocyanate chain extender.

10. The use according to any one of claims 6 to 9, characterized in that: The double bond of the small molecule dithiol and the bio-based isosorbide itaconic acid derivative compound undergoes a thiol-ene click reaction via a catalyst; The catalyst is selected from one or more of dimethylphenylphosphine and triphenylphosphine.

11. The use according to any one of claims 6 to 9, characterized in that: The small molecule dithiol is selected from one or more of 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol and 1,10-decanedithiol.

12. The use according to claim 7, characterized in that: The method of introducing a diene chain extender with a non-planar ring structure into the polymer is to obtain the polymer by alternately copolymerizing a small molecule dithiol and a diene with a non-planar ring structure under the initiation of azobisisobutyronitrile, and the two ends of the obtained polymer chain are capped with thiol.

13. The use according to claim 7, characterized in that: The diene chain extender with a non-planar ring structure is 1,4-cyclohexanedimethanol divinyl ether.

14. The use according to claim 8, characterized in that: The method of introducing a diisocyanate chain extender into the polymer is to obtain the polymer by alternately copolymerizing a small molecule dithiol and a diisocyanate in the presence of a catalyst, and the two ends of the obtained polymer chain are capped with thiol.

15. The use according to claim 14, characterized in that: The catalyst is selected from one or more of bis(dimethylaminoethyl)ether, pentamethyldiethylenetriamine, 2-methylcyclohexylamine, dibutyltin dilaurate, organic bismuth or triazine catalyst.

16. The use according to claim 14, characterized in that: The diisocyanate in the diisocyanate chain extender is selected from at least one of isophorone diisocyanate, toluene diisocyanate, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate or dicyclohexylmethane diisocyanate.

17. The use according to any one of claims 6 to 9, characterized in that: In a protective gas, a uniformly mixed reaction system of the bio-based isosorbide itaconic acid derivative compound, a small molecule dithiol, or a diene chain extender with a non-planar ring structure or a diisocyanate chain extender, a catalyst and an organic solvent is reacted to obtain a polymer with the bio-based isosorbide itaconic acid derivative compound as a basic structure, and the target polymer is obtained by washing and drying.

18. The use according to claim 17, characterized in that: The concentration of the reactants in the uniformly mixed reaction system is 10-50 wt %; the reaction temperature is 25-100° C., and the reaction time is 1-24 h.

19. The use according to claim 17, characterized in that: The molar ratio of all double bond groups of the bio-based isosorbide itaconic acid derivative compound and the diene chain extender with a non-planar ring structure to the thiol group in the uniform reaction system is 1:

1.

20. The use according to claim 17, characterized in that: The protective gas is selected from nitrogen or argon.

21. The use according to claim 17, characterized in that: The catalyst is selected from at least one of azobisisobutyronitrile, dibenzoyl peroxide, and phenyldimethylphosphine.

22. The use according to claim 17, characterized in that: The organic solvent is selected from at least one of tetrahydrofuran, N,N-dimethylformamide, chloroform or tetrachloroethane.

23. The use according to claim 17, characterized in that: During the washing, the obtained solid is washed with a washing liquid and then vacuum dried at 60-100° C. for 12-36 hours.

24. The use according to claim 23, characterized in that: The washing liquid is selected from one or more of distilled water, methanol, ethanol, propanol or butanol.

25. Use of the bio-based isosorbide itaconic acid derivative compound according to claim 1 as a monomer in the field of photocuring.

26. The use according to claim 25, characterized in that: The photocuring field includes photocuring coatings, photocuring inks, photocuring adhesives, and photocuring 3D printing.

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