Isosorbide-derived polycarbonate monomer compounds, their preparation methods and applications

Abstract

The present invention provides an isosorbide-derived polycarbonate monomer compound, its preparation method and application. The main structure is composed of biobased isosorbide dicarbonate and four or six peripheral cyclic carbonate structures connected. Two molecular structures can be cationic photoinitiated polymerization or copolymerized with common cyclohexene oxide-based cationically polymerizable monomers. And due to high functionalization, the volume shrinkage of the polymer prepared by photocuring can be adjusted or even volume expansion can be achieved through the proportion of such molecules, solving the problem of volume shrinkage of the photopolymerization product. The preparation process of this molecule is simple, easy to implement and control. Using biobased isosorbide as the raw material and utilizing carbon dioxide in the reaction process is beneficial to achieving the dual-carbon goal. Moreover, the polycarbonate is a degradable polymer, which has the dual effects of saving resources and protecting the environment from preparation to use, and has broad application prospects in the field of photocuring adhesives.

Description

Technical Field

[0001] The present invention belongs to the technical field of new organic chemical materials, and specifically relates to two monomeric compounds derived from isosorbide and polycarbonate, which contain bio-based isosorbide and six or eight carbonate groups in their structures, and their preparation methods, compositions and applications, especially their uses in the fields of UV-LED photocurable low-expansion materials and non-isocyanate polyurethane preparation. Background Art

[0002] With the increasing depletion of petroleum resources, finding sustainable, high-quality and inexpensive substitutes for petroleum is the key to the existence and development of the polymer industry. Bio-based polymer materials, using renewable resources as the main raw materials, not only reduce the consumption of petrochemical products in the plastics industry, but also reduce the environmental pollution during the production of petroleum-based raw materials. It is an important development direction of current polymer materials, with important practical value and broad development space. Since the 21st century, biomass-based materials have been increasingly valued. Sorbitol was listed by the US Department of Energy in 2004 as one of the twelve platform compounds derived from carbohydrates and exists as a sweetener in many berries and fruits. Sorbitol can undergo hydrogenolysis, polymerization, dehydration and other reactions to obtain a series of high-value-added bio-based chemicals and materials. Among them, the secondary dehydration cyclization product isosorbide, as an important new bio-based chemical, can be widely used in the fields of food, cosmetics and medicine. Therefore, isosorbide is considered a biomass renewable raw material.

[0003] In addition to utilizing biomass, how to utilize carbon dioxide is also one of the ways to achieve the "dual carbon" goal. That is to say, if carbon dioxide can be utilized in production, not only will the carbon emissions not increase, but the carbon emissions can also be reduced. Therefore, the fixation of carbon dioxide has been a very popular field in the industry-university-research field in recent years. In the polymer field, polycarbonate is one of the most advantageous technologies: on the one hand, it can consume carbon dioxide; on the other hand, the obtained polycarbonate is also a biodegradable polymer material.

[0004] The photocuring technology is a process in which liquid photosensitive resin polymerizes into a solid under light induction. It has the characteristics of high efficiency, rapidity, energy conservation, economy, environmental friendliness, etc., and is widely used in the fields of adhesives, photocuring coatings and inks, photoresists, 3D microfabrication, biomedicine, etc. Photocuring monomers are the key factors controlling the performance of the entire cured product, and their activity, dilutability, etc. directly affect the photocuring rate, curing degree, and the performance of the end product. Especially in the use of coatings and other applications of free radical curing, photocuring is usually carried out in an air atmosphere. Therefore, oxygen in the air will diffuse into the polymerization system and react with the free radicals generated by the photoinitiator under light irradiation, thus inhibiting the progress of photopolymerization. This is one of the biggest difficulties in the field of photocuring, namely oxygen inhibition of polymerization. It will lead to problems such as poor surface performance of the cured coating or even stickiness. In addition, the monomers for free radical polymerization are mainly acrylate derivatives. After the van der Waals force before polymerization becomes a covalent bond, the volume shrinkage is obvious. The curing shrinkage of trifunctional monomers generally exceeds 15%, which limits the application of free radical polymerization in fields such as adhesives that are sensitive to volume.

[0005] One of the solutions is cationic photopolymerization. Because cationic photocuring is insensitive to oxygen, its polymerizable monomers are mainly epoxy compounds, and the polymerization mechanism is mainly ring-opening polymerization. Therefore, the shrinkage of the cured product is also relatively low. Especially for highly functional expandable monomers, after appropriate addition, zero expansion or even volume increase can be achieved (Journal of Macromolecular Science, Part A: Pure and Applied Chemistry (2012) 49, 361–368). Therefore, the cationic photocuring system has developed rapidly in recent years in the fields of optical adhesives, photocuring adhesives, etc. Especially in the field of electronic adhesives that are very sensitive to volume shrinkage, it is a key research topic in the field of industry, academia and research. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the primary object of the present invention is to provide a polycarbonate monomer compound derived from isosorbide. The molecular main body is based on bio-based isosorbide and is connected to the peripheral cyclic carbonate through carbonate bonds.

[0007] The second object of the present invention is to provide a preparation method for the above two polycarbonate monomer compounds derived from isosorbide.

[0008] The third object of the present invention is to provide the use of the above two polycarbonate monomer compounds derived from isosorbide and their compositions in photocuring, especially in the field of volume-sensitive photocuring adhesives.

[0009] To achieve the above object, the solution of the present invention is:

[0010] An isosorbide-derived polycarbonate monomer compound, in which the main structure is composed of a biobased isosorbide dicarbonate and is combined with four or six peripheral cyclic carbonates, specifically an isosorbide-derived hexacarbonate expandable polymerizable monomer compound and an isosorbide-derived octacarbonate expandable polymerizable monomer compound. The molecular structures are shown in (I) and (II):

[0011]

[0012] Among them, the two molecular structures of (I) and (II) can be cationic photoinitiated polymerization, or copolymerized with a general cyclohexene oxide-based cationically polymerizable monomer. And due to high functionalization, the volume shrinkage of the polymer prepared by photocuring before and after curing can be adjusted by the ratio of such molecules or even achieve volume expansion, solving the problem of volume shrinkage of the photopolymer product.

[0013] A preparation method of the above-mentioned isosorbide-derived polycarbonate monomer compound (wherein the raw materials used are known compounds in the prior art and can be commercially purchased or simply prepared by known synthesis methods), which includes the following process:

[0014]

[0015] (a) Synthesis of isosorbide dicarbonyl imidazole (I, II)-a: Isosorbide (1 molar equivalent) is stirred and dissolved in acetone (20 ml per gram of isosorbide) at room temperature. Nitrogen is introduced below the liquid surface using a long needle. Under the protection of a constant gas flow, 1,1'-carbonyldiimidazole (2 molar equivalents) is added in three batches. After 5 minutes, the solution begins to show white turbidity. Stirring is continued at room temperature, and then a large amount of precipitate appears. The obtained white solid is collected by filtration, washed three times with ether, and dried in vacuo to obtain a white solid, which is the product with a yield of about 70%;

[0016] (b) In a heated and dried flask, under nitrogen protection, isosorbide dicarbonyl imidazole (I, II)-a (1.0 equivalent) is added and dissolved in acetonitrile dehydrated by 4A molecular sieve (10 ml per gram of (I, II)-a). Then an alcohol with different amounts of ethylene oxide (2.0 equivalents) is added, and the reaction is carried out under nitrogen protection. After the reaction is detected by TLC and the reaction is completed, the temperature is lowered to room temperature, chloroform with the same volume as acetonitrile is added, and it is extracted with 5% aqueous oxalic acid solution and deionized water. After drying, the solvent is evaporated to obtain a crude product, which is purified by column chromatography to obtain (I)-b with a yield of 70%; or (II)-b with a yield of 45%;

[0017] (c), Add the catalyst (0.05 molar equivalent of epoxy group) to epoxide (I)-b or (II)-b (calculated as 1 equivalent per epoxy group) at room temperature. While stirring, introduce CO2 gas (about 1 - 5 atm). After 24 - 48 h, dilute the mixture with an organic solvent and wash it with water. Extract the aqueous layer twice with the organic solvent. Combine the organic layers, dry them over sodium sulfate, filter, and evaporate in vacuo; Purify the residue through a short silica gel column to obtain the target product (I) or (II) as a colorless oil with a yield of more than 90%.

[0018] Further, in step (a), the stirring time is 20 h.

[0019] Further, in step (b), the structures of the alcohols with different amounts of ethylene oxide are as follows:

[0020]

[0021] Further, in step (b), the reaction temperature is 50 °C and the time is 4 - 8 h.

[0022] Further, in step (c), the stirring temperature is 45 °C.

[0023] Further, in step (c), the catalyst is selected from one or more of tetrabutylammonium bromide or hydroiodide of 1,8 - diazabicyclo[5.4.0]-7 - undecene.

[0024] Further, in step (c), the organic solvent is selected from one or more of chloroform or ethyl acetate.

[0025] Application of an isosorbide - derived polycarbonate monomer compound as described above as a multifunctional monomer in cationic photo - initiated polymerization. Among them, the monomer can be used to prepare polymers through cationic photo - initiation such as sulfonium salts and iodonium salts.

[0026] A photopolymerizable composition, which includes one or two isosorbide - derived polycarbonate monomer compounds, and commercially available monomers, resins, or mixtures of the two, different photoinitiators, and a small amount of additives added appropriately as required.

[0027] Among them, the commercially available monomers are selected from epoxy monomers, specifically common raw materials such as bisphenol A epoxy, alicyclic epoxy, or oxetane - type monomers.

[0028] The bisphenol A epoxy is bisphenol A - type E51 epoxy resin; the alicyclic epoxy is 3,4 - epoxycyclohexylmethyl - 3,4 - epoxycyclohexanecarboxylate (EPOX), and the oxetane - type monomer is 3 - methyloxetane (TMPO).

[0029] The resin is selected from commercially available epoxy resins, specifically from Daicel resin 8010 and Daicel resin 2061P.

[0030] The additives include commercially available defoamers (BYK 051), leveling agents (BYK 307), dyes (direct yellow), inorganic fillers (silica), etc.

[0031] Among them, the photoinitiators include, but are not limited to, iodonium salts (diphenyl iodonium hexafluoroantimonate), sulfonium salts (triphenyl sulfonium hexafluoroantimonate), and arene-iron salts (isopropylphenylcyclopentadienyliron hexafluorophosphate), etc. (each salt is a cationic photoinitiator that can generate the corresponding strong acid under photoexcitation). In order to promote the use efficiency of light sources with different wavelengths, different sensitizers can also be added. A sensitizer is a substance that can absorb light and sensitize the decomposition of salt initiators, including, but not limited to, anthracene sensitizers, pyrazoline sensitizers, and coumarin sensitizers, specifically selected from one or more of 9,10-dibutoxyanthracene or 7-dimethylaminocoumarin; the addition amounts of the sensitizer and the initiator are 1-5%, and the ratio between the two is adjusted according to needs.

[0032] The above isosorbide-derived polycarbonate monomer compound or the above photopolymerization composition can be used in various applications of cationically polymerizable coating materials, 3D printing materials, photopolymerization heat-conducting coatings, photocurable adhesives, etc., which are cationically polymerizable monomers initiated by light, especially in applications for reducing volume shrinkage.

[0033] Whether the above various oligomers, prepolymers, or copolymers, photoinitiators or photosensitizers, various additives, etc., are well-known to those skilled in the art and are not particularly limited.

[0034] Due to the adoption of the above solution, the beneficial effects of the present invention are as follows:

[0035] 1. The present invention uses bio-based isosorbide as the main body and connects polycyclic carbonates through carbonate bonds. On the one hand, taking advantage of the characteristic that cyclic carbonates can undergo cationic photopolymerization, it is used as a photocuring monomer to achieve volume control of the formulated products before and after the photocuring process; on the other hand, the core structure of isosorbide dicarbonate endows the prepared polymer with biodegradable characteristics and also has good miscibility and copolymerization ability with conventional commercial monomers and resins. Therefore, a monomer structure containing polycarbonate can achieve the fixation of carbon dioxide during the preparation process. Such a multifunctional monomer is an effective way to achieve the "dual carbon" goal and has broad application prospects.

[0036] 2. The present invention introduces bio-based isosorbide into six- or eight-carbonate monomer compounds. Utilizing the biomass source of isosorbide, it is non-toxic, pollution-free, has a simple preparation process, easily available raw materials, and is easy to realize industrialized production.

[0037] 3. The molecular weights of the cyclic carbonate monomer compounds involved in the present invention exceed 800 and 1000 respectively, and no odor can be smelled before and after photocuring, which is expected to be used in coatings sensitive to odor.

[0038] 4. The photocuring formulation involving the multi-cyclic carbonate monomer compound in the present invention has a wide range of uses in the field of photocuring sensitive to volume shrinkage because the volume of the cyclic carbonate expands after ring-opening during curing. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 It is the molecular structure diagrams of the isosorbide-derived hexacarbonate expandable polymerizable monomer compound and the isosorbide-derived octacarbonate expandable polymerizable monomer compound of the present invention.

[0040] Figure 2 It is the molecular structures of the commercial monomers TMPO and EPOX and the molecular structure of the photoinitiator PAG-002 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0041] The technical solutions of the present invention will be further described in detail below in conjunction with several preferred embodiments and the accompanying drawings. These embodiments are implemented on the premise of the technical solutions of the invention, and detailed implementation manners and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0042] In the following embodiments, the experimental materials used, unless otherwise specified, can be purchased from conventional biochemical reagent companies.

[0043] The technical solutions of the present invention will be described clearly and completely below. Obviously, the described embodiments are some but not all of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0044] Example 1: Preparation of Intermediate (I,II)-a

[0045]

[0046] First, the synthesis of isosorbide dicarbonyl imidazole (I,II)-a: Isosorbide (14.6 g, 0.1 mol) was stirred and dissolved in dry acetone (300 mL) at room temperature. Nitrogen was introduced below the liquid surface using a long needle, and 1,1'-carbonyldiimidazole (32.4 g, 0.2 mol) was added in batches under the protection of a constant gas flow. After 5 minutes, the solution began to show white turbidity, and it was continuously stirred at room temperature for 20 h, and then a large amount of precipitation occurred. The obtained white solid was collected by filtration, washed three times with ether, and dried in vacuo to obtain 23.4 g of white solid as the product, with a yield of about 70%.

[0047] 1 1H NMR(CDCl3)δppm: 4.03(dd, J1 = 11.1 Hz, J2 = 4.4 Hz, 2H); 4.12(dd, J1 = 10.8 Hz, J2 = 3.6 Hz, 1H); 4.18(d, J = 11.3 Hz, 1H); 4.69(d, J = 4.85 Hz, 1H); 5.08(t, J = 5.3 Hz, 1H); 5.42(m, 1H); 5.47(d, J = 3.1 Hz, 1H); 7.08(s, 1H); 7.10(s, 2H); 7.39(s, 1H); 7.44(s, 1H); 8.10(s, 1H); 8.16(s, 1H).

[0048] Example 2: Preparation of the target product (I)

[0049]

[0050] In a heated and dried flask, isosorbide dicarbonyl imidazole (I,II)-a (16.7 g, 0.05 mol) was added under nitrogen protection and dissolved in acetonitrile (167 mL) dehydrated by 4A molecular sieve. Then 2,2-bis((oxiran-2-ylmethoxy)methyl)butanol (24.6 g, 0.1 mol) was added, and the reaction was carried out at 50 °C for 6 h under nitrogen protection. After the reaction was detected to stop by TLC, the temperature was lowered to room temperature, chloroform with the same volume as acetonitrile was added, and it was extracted with 5% aqueous oxalic acid solution and deionized water respectively. After drying the organic solvent, the obtained crude product was purified by column chromatography, and the yield was 70%.

[0051] (I)-b: MS(C 32 H 50 O 16 ): m / e: 690.31; Experimental result: 691.31 (M + H + ).

[0052] 1,8-Diazabicyclo[5.4.0]-7-undecene hydroiodide (140 mg, 0.5 mmol) was added to the diepoxide (I)-b (6.90 g, 10 mmol) at room temperature. CO2 gas (about 1 atm) was introduced under stirring at 45 °C. After 48 h, the mixture was diluted with 50 mL of chloroform and washed with water. The aqueous layer was extracted twice with chloroform (30 mL × 2), the combined organic layers were dried over sodium sulfate, filtered, and evaporated in vacuo. The residue was purified by a short silica gel column to obtain the target product (I) as a colorless oil (as Figure 1 ), and the yield was 92%.

[0053] (I): MS(C 36 H 50 O24 ):m / e: 866.27; Experimental result: 867.27 (M+H + )。

[0054] Example 2: Preparation of the target product (II)

[0055]

[0056] In a heated and dried flask, isosorbide dicarbonyl imidazole (I,II)-a (16.7 g, 0.05 mol) was added under nitrogen protection and dissolved in acetonitrile (167 mL) dehydrated by molecular sieve. Then, 2,2,2-tris((oxirane-2-ylmethoxy)methyl)ethanol (30.4 g, 0.1 mol) was added. The reaction was carried out at 50 °C for 6 h under nitrogen protection. After detecting the reaction by TLC and the reaction stopped, the mixture was cooled to room temperature. Chloroform with the same volume as acetonitrile was added. The mixture was extracted with 5% aqueous oxalic acid solution and deionized water respectively. After drying the organic solvent, the obtained crude product was evaporated to dryness and purified by column chromatography, with a yield of 45%.

[0057] (II)-b: MS (C 36 H 54 O 20 ):m / e: 806.81; Experimental result: 807.82 (M+H + )。

[0058] 1,8-Diazabicyclo[5.4.0]-7-undecene hydroiodide (140 mg, 0.5 mmol) was added to the diepoxide (II)-b (6.90 g, 10 mmol) at room temperature. CO2 gas (about 1.5 atm) was introduced while stirring at 45 °C. After 48 h, the mixture was diluted with 50 mL of chloroform and washed with water. The aqueous layer was extracted twice with chloroform (30 mL × 2). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and the organic solvent was evaporated in vacuo. The residue was purified by a short silica gel column to obtain the target product (II) as a colorless oil (as Figure 1 ), with a yield of 91%.

[0059] (II): MS (C 42 H 54 O 32 ):m / e: 1070.26; Experimental result: 1071.27 (M+H + )。

[0060] <Experiment 1>

[0061] Photocuring experiment of the monomers prepared in the examples and testing of the coating properties

[0062] Monomer (I) or (II) in the example: 10 parts by mass

[0063] 3 - Hydroxymethyl - 3 - ethyloxetane (TMPO): 43 parts by mass

[0064] 3,4 - Epoxycyclohexylmethyl - 3,4 - epoxycyclohexanecarboxylate (EPOX): 43 parts by mass

[0065] Photoinitiator (PAG - 002, Yangfan New Material Monosulfonium Salt): 3 parts by mass

[0066] Leveling agent (BYK 307): 0.5 parts by mass

[0067] Defoaming agent (BYK 051): 0.5 parts by mass

[0068] The two prepared photocurable solutions were coated on a glass slide to form a coating of about 100 μm, and the coating area was 10 cm² with a width of 2 cm and a length of 5 cm 2 An LED light source with a unit power of 2000 mW / cm² 2 and an emission wavelength of 365 nm produced by Guangzhou HeGuang TongSheng Company (3 cm wide and 80 cm long LED surface light source) was used as the excitation light source. It was placed on the conveyor belt, and the end point of curing was set as the contact without fingerprints. It was found that each formulation could undergo photocuring at a speed of 30 m / s. The coating hardness exceeded 3H

[0069] <Experiment 2>

[0070] Test on the volume shrinkage ratio before and after the copolymerization of monomers (I) and (II) with different proportions in the examples

[0071] The volume shrinkage was measured by measuring the density of the formulation system before and after curing. The solution density was measured by weighing a precisely measured liquid preparation according to the method reported in the national standard. The sample to be cured was prepared by dissolving (I) or (II) in a mixed monomer of TMPO and EPOX, and adding 2 wt% of the cationic photoinitiator PAG - 002 (see Figure 2 the chemical structure in). The formulation was placed in an aluminum mold and photocured with a 365 nm LED light source at a light intensity of 200 mW / cm² 2 . Transparent blocks with a thickness of about 2 mm were obtained and characterized. The density was measured with a densitometer and the shrinkage rate before and after curing was calculated. The specific data of different formulations are shown in Table 1 and Table 2. After adding the polycyclic carbonate, the volume of the photocured polymer expanded significantly, and the more the number of cyclic carbonates, the more significant the expansion effect

[0072] Table 1 Volume shrinkage after cationic photocuring polymerization involving monomer (I)

[0073]

[0074]

[0075] Table 2 Volume shrinkage after cationic photocuring polymerization involving monomer (II)

[0076]

[0077] The above description of the embodiments is to enable those of ordinary skill in the art to understand and use the present invention. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative efforts. Therefore, the present invention is not limited to the above embodiments. Improvements and modifications made by those skilled in the art based on the principles of the present invention without departing from the scope of the present invention should be within the protection scope of the present invention.

Claims

1. An isosorbide-derived polycarbonate monomer compound, characterized in that: It includes isosorbide-derived hexacarbonate intumescent polymeric monomer compounds and isosorbide-derived octacarbonate intumescent polymeric monomer compounds, and their specific molecular structures are shown in (I) and (II) respectively:

2. A method for preparing the isosorbide-derived polycarbonate monomer compound according to claim 1, characterized in that: It includes the following processes: (a) Synthesis of isosorbide dicarbonyl imidazole (I,II)-a: Isosorbide is stirred and dissolved in acetone at room temperature. Nitrogen is introduced below the liquid surface using a long needle. Under the protection of a constant gas flow, 1,1'-carbonyldiimidazole is added in batches. The solution starts to become white and turbid. Stirring is continued at room temperature, and then a precipitate appears. The obtained white solid is collected by filtration, washed with ether, and dried in vacuo to obtain the product; (b) In a heated and dried flask, under nitrogen protection, isosorbide dicarbonyl imidazole (I,II)-a is added and dissolved in acetonitrile dehydrated by 4A molecular sieve. Then alcohols with different numbers of ethylene oxides are added, and the reaction is carried out under nitrogen protection. After detecting the end of the reaction by TLC, the temperature is lowered to room temperature, chloroform with the same volume as acetonitrile is added, and the mixture is extracted with oxalic acid aqueous solution and deionized water. After drying, the solvent is evaporated to obtain a crude product, which is purified by column chromatography to obtain (I)-b; or (II)-b; (c) At room temperature, a catalyst is added to epoxide (I)-b or (II)-b. Carbon dioxide gas is introduced while stirring. After 24 - 48 h, the mixture is diluted with an organic solvent and washed with water. The aqueous layer is extracted with an organic solvent. The combined organic layers are dried over sodium sulfate, filtered, and evaporated in vacuo; The residue is purified to obtain the colorless oily target product (I) or (II).

3. The preparation method according to claim 2, characterized in that: In step (a), the stirring time is 20 h.

4. The preparation method according to claim 2, characterized in that: In step (b), the reaction temperature is 50 °C and the time is 4 - 8 h.

5. The preparation method according to claim 2, characterized in that: In step (c), the stirring temperature is 45 °C.

6. The preparation method according to claim 2, characterized in that: In step (c), the catalyst is selected from one or more of tetrabutylammonium bromide or hydroiodide of 1,8-diazabicyclo[5.4.0]-7-undecene.

7. The preparation method according to claim 2, characterized in that: In step (c), the organic solvent is selected from one or more of chloroform or ethyl acetate.

8. Use of the isosorbide-derived polycarbonate monomer compound according to claim 1 as a multifunctional monomer in cationic photopolymerization.

9. A photopolymerizable composition, characterized in that: It includes one or two isosorbide-derived polycarbonate monomer compounds as claimed in claim 1, and commercial monomers, resins or a mixture of the two, photoinitiators and additives.

10. The photopolymerizable composition according to claim 9, characterized in that: The commercial monomers are selected from epoxy monomers.

11. The photopolymerizable composition according to claim 10, characterized in that: The epoxy monomers are selected from one or more of bisphenol A epoxy, alicyclic epoxy or oxetane monomers.

12. The photopolymerizable composition according to claim 11, characterized in that: The bisphenol A epoxy is bisphenol A type E51 epoxy resin.

13. The photopolymerizable composition according to claim 11, characterized in that: The alicyclic epoxy is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

14. The photopolymerizable composition according to claim 11, characterized in that: The oxetane monomer is 3-methoxyoxetane.

15. The photopolymerizable composition according to claim 9, characterized in that: The resins are selected from commercial epoxy resins.

16. The photopolymerizable composition according to claim 15, characterized in that: The epoxy resins are selected from Daicel resin 8010 and Daicel resin 2061P.

17. The photopolymerizable composition according to claim 9, characterized in that:The additives include commercial defoamers, leveling agents, dyes, and inorganic fillers.

18. The photopolymerizable composition according to claim 17, wherein: The defoamer is BYK 051.

19. The photopolymerizable composition according to claim 17, wherein: The leveling agent is BYK 307.

20. The photopolymerizable composition according to claim 17, wherein: The dye is direct yellow.

21. The photopolymerizable composition according to claim 17, wherein: The inorganic filler is silica.

22. The photopolymerizable composition according to claim 9, wherein: The photoinitiators are selected from one or more of iodonium salts, sulfonium salts, arene iron salts or sensitizers.

23. The photopolymerizable composition according to claim 22, wherein: The iodonium salt is diphenyliodonium hexafluoroantimonate.

24. The photopolymerizable composition according to claim 22, wherein: The sulfonium salt is triphenylsulfonium hexafluoroantimonate.

25. The photopolymerizable composition according to claim 22, wherein: The ferrocenium salt is isopropylphenylcyclopentadienyliron hexafluorophosphate.

26. The photopolymerizable composition according to claim 22, wherein: The sensitizer is selected from one or more of 9,10-dibutoxyanthracene or 7-dimethylaminocoumarin.

27. Use of the isosorbide-derived polycarbonate monomer compound according to claim 1 or the photopolymerizable composition according to claim 8 in cationic polymerization coating materials, 3D printing materials, photopolymerizable heat conductive coatings, and photocurable adhesives.

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