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Abbreviation (ISO4): Prog Chem      Editor in chief: Jincai ZHAO

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Progress in Chemistry >

2025 , Vol. 37 >Issue 3: 383 - 396

DOI: https://doi.org/10.7536/PC240521

Review

Synthesis and Polymerizations of Bio-Based （meth）Acrylates

  • Yuchen Yang 1, 3 ,
  • Zhenjie Liu 4 ,
  • Chunhua Lu 1, 3 ,
  • Kai Guo 2, 3 ,
  • Xin Hu , 1, 3 ,
  • Ning Zhu , 2, 3
Expand
  • 1. College of Materials Science and Engineering，Nanjing Tech University，Nanjing 211800，China
  • 2. College of Biotechnology and Pharmaceutical Engineering，Nanjing Tech University，Nanjing 211800，China
  • 3. State Key Laboratory of Materials-Oriented Chemical Engineering，Nanjing 211800，China
  • 4. SINOPEC （Beijing） Research Institute of Chemical Industry Co. ，Ltd. ，Beijing 100013，China
*（Xin Hu）；
（Ning Zhu）

Received date: 2024-05-22

  Revised date: 2024-08-20

  Online published: 2025-02-10

Supported by

National Natural Science Foundation of China(22478188)

National Natural Science Foundation of China(22278205)

National Natural Science Foundation of China(22278223)

R&D Program of SINOPEC(36600000-25-ZC0607-0047)

R&D Program of SINOPEC(30000000-23-ZC0607-0871)

R&D Program of SINOPEC(420106)

R&D Program of State Key Laboratory of Chemical Safety

Fold

Abstract

As an important family of synthetic polymers， poly（meth）acrylates have a wide range of applications in the fields of coatings， adhesives， biomedines， electronic and electrical materials. However， the （meth）acrylates monomers are mainly derived from petrochemical resources.Transformations of biomass into （meth）acrylate monomers and polymers have attracted growing research interest from the viewpoint of sustainability. The bio-based poly（meth）acrylates not only serve as the supplement for the fossil based product but also provide great chance for the development of value-added high performance materials with designed novel structures. This article highlights the recent progress in the synthesis and polymerization of bio-based （meth）acrylates. The lignin， terpene， plant oil， glucose， isosorbide， and furan derivatives as the biomass feedstock are respectively reviewed in consecutive order. The properties and applications of the corresponding bio-based poly（meth）acrylates are summarized. Moreover， the challenges and opportunities of bio-based poly（meth）acrylates are also discussed.

Contents

1 Introduction

2 Preparation of bio-based （meth）acrylates and polymers from lignin

3 Preparation of bio-based （meth）acrylates and polymers from terpene

4 Preparation of bio-based （meth）acrylates and polymers from plant oils

5 Preparation of bio-based （meth）acrylates and polymers from glucose

6 Preparation of bio-based （meth）acrylates and polymers from isosorbide

7 Preparation of bio-based （meth）acrylates and polymers from furan derivatives

8 Conclusion and outlook

Key words： biomass transformation; （meth）acrylates; radical polymerizations; bio-based materials

Cite this article

Yuchen Yang , Zhenjie Liu , Chunhua Lu , Kai Guo , Xin Hu , Ning Zhu . Synthesis and Polymerizations of Bio-Based （meth）Acrylates[J]. Progress in Chemistry, 2025 , 37(3) : 383 -396 . DOI: 10.7536/PC240521

1 Introduction

Since the 20th century, with the continuous advancement of technological progress and global industrialization, synthetic polymer materials have experienced rapid development. For a long time, the raw materials for polymer materials have mainly relied on petrochemical resources, which, while bringing conveniences such as large-scale manufacturing, have also led to increasingly prominent issues related to resources and the environment［1］. Developing sustainable polymer materials from natural biomass has become a significant strategic need in our country and an important development direction in the field of new materials［2-3］. Biomass, characterized by abundant sources, low cost, and renewability, is considered an ideal supplement and alternative material to traditional petrochemical resources［4-6］. Currently, various routes for converting biomass into different monomers have been reported, and corresponding polymer materials are further prepared through polymerization methods such as radical polymerization, ring-opening polymerization, and condensation polymerization. In particular, bio-based routes have achieved new structures that are difficult to synthesize using traditional petrochemical technologies, enhancing the added value of materials and expanding their application fields, drawing joint attention from both academia and industry［7-12］.
(Meth)acrylate polymers, due to their excellent mechanical, optical, and thermal properties, are widely used in coatings［13］, energy storage［14］, biomedicine, and other fields［15-17］. Developing bio-based (meth)acrylate polymers can not only promote the sustainable development of polymer materials but also endow polymers with new structures and functions, which is expected to generate significant economic value［18-20］..This article systematically reviews the recent research progress of bio-based (meth)acrylates and their polymers, classifies them by biomass raw materials, and summarizes the methods for preparing bio-based (meth)acrylate monomers from lignin, terpenes, vegetable oils, and glucose conversion (divided into glucose, isosorbide, and furan derivatives due to length), as summarized in Figure 1. It introduces the preparation, properties, and applications of various bio-based (meth)acrylate polymers and finally discusses and prospects the development opportunities and challenges in related fields.
图1 Synthesis of Bio-Based (Meth)Acrylates and Preparation of Their Polymers

Fig.1 Synthesis and polymerization of bio-based （meth）acrylates

2 Preparation of Bio-Based (Meth)Acrylates and Their Polymers from Lignin

Lignin is the most abundant natural aromatic biomass resource on Earth, and its macromolecules are composed of phenylpropane structural units (guaiacyl (G-type), syringyl (S-type), and p-hydroxyphenyl (H-type)) connected and polymerized through ether bonds and carbon-carbon bonds［21］. Lignin has a three-dimensional network structure, rich in active functional groups such as alcoholic hydroxyl, phenolic hydroxyl, carbonyl, and carboxyl groups, which allow it to undergo various chemical reactions like sulfonation, nitration, graft copolymerization, alkylation, and amination［22-24］. By functionally modifying lignin, high-performance fine polymer products such as hydrogels and adhesives can be prepared, increasing their added value［25-27］.
Eugenol can be extracted from cloves and also obtained through enzymatic hydrolysis of lignin. Due to the presence of both phenolic hydroxyl and allyl groups, it exhibits high reactivity, is easy to functionalize, and can be used to prepare various polymers. Caillol and Lacroix-Desmazes et al.［28］ explored the preparation of eugenol-derived (meth)acrylate monomers and their polymers (as shown in Figure 2). Through hydroxyethylation, the phenolic hydroxyl group was transformed into ethoxy alcohol. Subsequently, in the presence of triethylamine, methacrylic anhydride or acryloyl chloride was added respectively to obtain various monomers such as ethoxyethyl methacrylate eugenol (EEMA), ethoxyisopropyl methacrylate eugenol (EIMA), ethoxydihydro methacrylate eugenol (EDMA), ethoxyethyl acrylate eugenol (EEA), ethoxyisopropyl acrylate eugenol (EIA), and ethoxydihydro acrylate eugenol (EDA). Further functionalization of EEMA yielded epoxy-functionalized ethoxyethyl methacrylate eugenol (epoxy EEMA) and carbonate-functionalized ethoxyethyl methacrylate eugenol (EEMA carbonate). Among them, EEMA, EIMA, EDMA, EDA, and EEA can undergo radical homopolymerization in solution with high monomer conversion rates. However, epoxy EEMA and EEMA carbonate are difficult to homopolymerize and can only serve as modifiers for other polymers. The research group［29］ subsequently continued to study the photo-induced radical polymerization process of EEMA, EIMA, and EDMA under different reaction conditions. It was found that without a photoinitiator, the conversion rate of EMIA reached 59%. Compared to when air was introduced, the conversion rate of EDMA was higher in the absence of air due to the rapid quenching of radicals by oxygen. Under air-exposed conditions, the monomer conversion rates of EIMA and EEMA during radical polymerization could reach 92% and 81%, respectively. In the absence of air, the radical polymerization rate followed the order: EDMA > EEMA > EIMA.
图2 Synthesis of Eugenol-Derived (Meth)Acrylate Derivatives［28］

Fig.2 Synthesis of the （meth）acrylated eugenol derivatives［28］

Wan and Fan et al［30］ synthesized a series of eugenol-based acrylates (as shown in Figure 3) using eugenol, siloxane, and acrylic acid as raw materials under mild and solvent-free conditions. First, the eugenol epoxy monomer reacted with three different siloxanes (1,1,3,3-tetramethyldisiloxane, 3-phenylpentamethyltrisiloxane, and diphenyltetramethyltrisiloxane) to obtain three eugenol siloxane monomers. Subsequently, acrylic acid underwent ring-opening reactions with the epoxy groups of the three eugenol siloxane monomers to produce tetramethyldisiloxane eugenol diacrylate (SIEEA), 3-phenylpentamethyltrisiloxane eugenol diacrylate (SIPEEA), and diphenyltetramethyltrisiloxane eugenol diacrylate (SIDPEEA). The study found that the viscosity and biotoxicity of the eugenol acrylates were much lower than those of commercially available BisGMA. The synthesized acrylates could be effectively cured under ultraviolet light, and the prepared films and 3D printing materials also exhibited excellent thermal properties and hydrophobicity.
图3 Synthesis of SIEEA, SIPEEA, and SIDPEEA ［30］

Fig.3 Synthesis of SIEEA， SIPEEA， and SIDPEEA［30］

Vanillin is obtained either by extraction from vanilla bean or by depolymerization of lignin under alkaline conditions and has high reactivity due to the presence of two functional groups: an aldehyde group and a phenolic hydroxyl group. A series of (meth)acrylate vanillin esters can be obtained by introducing (meth)acrylate groups into vanillin. Sparacin et al［31］ prepared acrylate vanillin ester (VA) and methacrylate vanillin ester (VMA) by reacting vanillin with acryloyl chloride and methacrylic anhydride, respectively. By functionalizing VMA with Jeffamines of different structures and compounding it with VA (as shown in Figure 4), a series of 3D printing materials with self-healing and chemically degradable properties were obtained, which can serve as a good complement to existing petrochemical-based 3D printing materials.
图4 Synthesis of VA and VMA ［31］

Fig.4 Synthesis of VA and VMA ［31］

Ostrauskaite et al［32］ prepared crosslinked polymers by photoinitiated free radical polymerization of vanillin derivatives (vanillin dimethacrylate (VDM) and vanillin diacrylate (VD)) using (2,4,6-trimethylbenzoyl) ethyl phenylphosphinate (TPOL) as a photoinitiator. Under solvent-free conditions, the polymer prepared from vanillin diacrylate (VD) and 3 mol% TPOL exhibited a glass transition temperature of up to 87 ℃ and showed excellent mechanical properties, comparable or even superior to those of commercial photoresins PR48 and FormLabs Clear FL6PCL02.
Sun et al［33］ developed a lignin-based acrylate adhesive (as shown in Figure 5). By reacting the hydroxyl groups in alkali lignin (AL) with methacryloyl chloride (MC), carbon-carbon double bonds were introduced into the lignin macromolecules to obtain modified alkali lignin monomers (MAL). Subsequently, MAL underwent radical copolymerization to prepare the lignin-based acrylate adhesive. The introduction of dodecyl methacrylate (LMA) into the chemical structure of lignin acrylate improved the compatibility, toughness, and strength of the lignin-based adhesive, resulting in a shear strength of 5.10 MPa for the lignin adhesive, which is 114% higher than that of traditional acrylate adhesives, while still exhibiting good hydrophobicity and high shear strength after being immersed in water for 12 hours.
图5 Synthesis of Alkali Lignin Acrylate and Its Polymer ［33］

Fig.5 Synthesis of alkali lignin acrylate and its polymer［33］

Ma et al［34］ synthesized two aromatic monomers, double-bond modified vanillin (DV) and double-bond modified eugenol (DE) (as shown in Figure 6). The obtained DV and DE were used as substitutes for petroleum-based styrene (ST) and diacetone acrylamide-adipic dihydrazide (DAAM-ADH) copolymers. Through mini-emulsion polymerization technology with butyl acrylate (BA), P(DV-BA-DE) mini-emulsion was prepared. The results showed that the monomer conversion rate, solid content, and gel content of the P(DV-BA-DE) microemulsion were comparable to those of the P(St-BA-DAAM) microemulsion, and it exhibited good stability. After applying the P(DV-BA-DE) microemulsion to leather, the air permeability and tensile strength increased by 2.14% and 11.71%, respectively. Moreover, the bio-based acrylic emulsion, as a leather coating, demonstrated excellent antibacterial performance, with inhibition rates against Escherichia coli (95.15%) and Staphylococcus aureus (99.99%), surpassing those of the P(St-BA-DAAM) emulsion.
图6 Schematic Diagram of Microemulsion Polymerization of DV, BA, and DE［34］

Fig.6 Miniemulsion copolymerization of DV， BA and BE［34］

3 Preparation of Bio-Based (Meth)Acrylates and Their Polymers from Terpenes as Raw Materials

Terpene-based bio-derived raw materials that can be extracted from citrus and wood waste are currently available for large-scale preparation through partial routes［35］. Due to the presence of alkene functional groups in the structure of terpenes, polymers containing terpene structures can be prepared via radical polymerization［36-38］. However, terpenes are typically difficult to homopolymerize, and even in the presence of comonomers (such as styrene or acrylates), it remains challenging to obtain high molecular weight products［39］.
Howdle et al［40］ selected four of the most commercialized terpenes: (+)-α-pinene, (−)-β-pinene, (R)-(−)-limonene, and R-(−)-carvone to prepare terpene-based (meth)acrylates (as shown in Figure 7). Two synthetic routes were adopted. The first route involved modifying the terpenes into alcohols through a reaction, followed by esterification with the corresponding acryloyl chloride or methacryloyl chloride; however, this synthetic route required the use of highly toxic acyl chloride compounds. As an improvement, acrylate and methacrylate were used to replace acryloyl chloride and methacryloyl chloride, respectively. Additionally, propylphosphonic anhydride (T3P®) was introduced to promote the esterification coupling between terpenes and (meth)acrylic acid. Among the obtained polymers, the Tg of carvone methacrylate polymer was relatively high (117 ℃). By adding a crosslinking agent and spray-coating it into a film, a high-hardness film with high transparency and good adhesion could be obtained.
图7 Synthesis of Acrylates 1b-4b and Methacrylates 1c-4c Monomers［40］

Fig.7 Synthesis of acrylate 1b-4b and methacrylate 1c-4c monomers［40］

Howdle et al［41］ built upon the aforementioned work and prepared a series of terpene-based block copolymers through reversible addition-fragmentation chain transfer radical (RAFT) polymerization (as shown in Figure 8). Using 2-cyano-2-propyl dodecyl trithiocarbonate (CPDT) as the CTA agent, they successfully synthesized a series of polyterpene-based (meth)acrylates with controlled polymerization. Among them, polyα-pinene methacrylate (α-PMA) and polyβ-pinene methacrylate (β-PMA) exhibited excellent controllability in polymerization, and the resulting terpene-based (meth)acrylates possessed a wide range of Tg, such as 168 ℃ for PαPMA, 121 ℃ for PβPMA, and -3 ℃ for PLIA, making it possible to synthesize diblock or even multiblock copolymers. A PαPMA-b-PBuA-b-PαPMA block copolymer thermoplastic elastomer was prepared via RAFT polymerization. In addition, this method was extended to monomers β-PMA and LIA, leading to partially and fully renewable terpene (meth)acrylate polymers.
图8 Preparation of PαPMA-b-PBuA-b-PαPMAP Triblock Copolymer by RAFT Polymerization［41］

Fig.8 Synthesis of a PαPMA-b-PBuA-b-PαPMA triblock copolymer via RAFT polymerization［41］

The green sustainability of synthetic routes is also a crucial aspect in the development of bio-based compounds. Du Prez et al［42］ used the CHEM21 toolkit to evaluate different routes for synthesizing terpene-based (methyl) acrylates (as shown in Figure 9). The CHEM21 toolkit is an effective tool for assessing the sustainability of synthetic routes at the laboratory scale. The experiment selected four terpene monomers (L-menthol, citronellol, geraniol, and 3,7-dimethyl-1-octanol) and adopted five routes to synthesize terpene-based (methyl) acrylates. Among these, Method A is the most widely used (methyl) acryloyl chloride esterification reaction currently. Methods B and C involve transesterification reactions with (methyl) acrylates under acid-base or enzymatic catalysis conditions. Methods D and E are esterification reactions carried out in Dean Stark apparatus and reflux setups, respectively. Although Method A has a high conversion rate, it generates substantial amounts of chloride salts during the reaction process. Method E combines desiccants (such as MgSO4) with catalysts, achieving high conversion rates in a shorter time when synthesizing L-(methyl) menthyl acrylate, (methyl) citronellyl acrylate, and 3,7-dimethyl-1-octyl (methyl) acrylate. For (methyl) geranyl acrylate, due to the tendency of geraniol to rearrange under acidic or basic conditions, completing the reaction via enzymatic catalysis (Method C) holds more potential.
图9 Synthesis of Terpenoid Acrylates［42］

Fig.9 Synthesis of terpenoid acrylates［42］

Olsén and Berglund et al［43］ reported a preparation method for a novel limonene methacrylate (LIMA) monomer. First, acetylene-functionalized LIMA was synthesized through the oxidative opening of limonene rings, followed by the preparation of the corresponding acrylate through reaction with acrylic acid (as shown in Figure 10). Under the presence of an AIBN initiator, a thermosetting resin PLIMA with a Tg of 131°C was obtained via radical polymerization, exhibiting a high total transmittance of 95% at a wavelength of 550 nm. Bio-based succinic anhydride (SA) was used to modify the wood substrate, which was then covalently bonded with the LIMA monomer to obtain a bio-composite material with high mechanical properties and transparency.
图10 Synthesis of Limonene Acrylate (LIMA) Monomer［43］

Fig.10 Synthesis of limonene acrylate （LIMA） monomers［43］

Cuzzucoli Crucitti et al［44］ successfully synthesized three corresponding methacrylate monomers (as shown in Figure 11) using α-pinene, β-pinene, and carvone as raw materials. On this basis, they explored the possibility of synthesizing α-terpinyl methacrylate via the coupling reaction of terpenes with MAA catalyzed by iron trifluoromethanesulfonate but obtained a mixture of products that differed from expectations, namely a mixture of bornyl methacrylate (BoMA) and isobornyl methacrylate (iBoMA). This outcome occurred because α-pinene was protonated under the influence of an acidic catalyst to form the pinene cation. The well-established Wagner-Meerwein rearrangement led to the formation of a relatively stable bornyl cation. Finally, the cation was captured by MAA to yield BoMA or iBoMA, respectively. To obtain the target product α-TMA, it was proposed to use α-terpineol as the starting material and generate the target α-TMA structure through a deprotonation reaction followed by esterification with methacryloyl chloride, achieving a yield of up to 68%.
图11 Synthesis of α-TMA［44］

Fig.11 Synthesis of α-terpineol ［44］

4 Preparation of Bio-Based (Methyl) Acrylates and Their Polymers from Plant Oils as Raw Materials

Vegetable oils are important raw materials for the preparation of bio-based chemicals due to their low cost and abundant reserves［45］. However, the reactivity of groups in the long chains of most vegetable oils is not high, requiring chemical modification of vegetable oils to introduce more reactive groups, thereby obtaining a wide variety of bio-based materials［46］, effectively supplementing and partially replacing petrochemical-based chemicals［47-50］.
Yuan et al［51］ used palm oil, olive oil, peanut oil, rapeseed oil, corn oil, and grape seed oil as raw materials to synthesize acrylates from vegetable oils via a one-step method, simplifying the synthesis route. The experiment involved mixing vegetable oil with acrylic acid, followed by adding a certain amount of boron trifluoride ether solution and reacting at 80 ℃ for 2 hours to obtain vegetable oil-based acrylates. Subsequently, the prepared vegetable oil-based acrylate, polyurethane acrylate (PUA-2665), triacrylate propane trimethanol ester (TMPTA), and photoinitiator (PI-1173) were thoroughly mixed to prepare UV-curable films. DMA was used to study the Tg and crosslinking degree of a series of UV-curable films. The Tg of vegetable oil-based acrylates ranged from 30.3 to 50.0 ℃. As the number of double bonds in the vegetable oil increased, the grafting frequency increased, leading to an increase in crosslinking density, which resulted in higher Tg and storage modulus. Consequently, the tensile strength of the corresponding composites increased from 0.62 MPa to 8.94 MPa, and the Young's modulus increased from 13.93 MPa to 468.07 MPa.
In the molecular structure of castor oil (CO), there are many unsaturated double bonds and hydroxyl groups which can be functionalized and modified. Therefore, castor oil is often used to copolymerize in various resin systems to prepare green bio-based materials. Yang and Yuan et al［52］ synthesized a novel trifunctional bio-based methacrylate using a two-step method. Thiol castor oil (MCO) was prepared from castor oil (CO) and thioglycolic acid through a "thiol-ene" reaction, followed by esterification with glycidyl methacrylate (GMA) to obtain castor oil methacrylate (MCOG). MCOG was then mixed with reactive diluent pentaerythritol triacrylate (PETA), photoinitiator (TPO), and another polyurethane acrylate prepolymer (B-215) to prepare UV-curable films. As the content of B-215 increased, the storage modulus and crosslink density of the cured film rose, and correspondingly, the Tg increased. The highest thermal decomposition temperature of the cured film reached above 460 ℃, and it exhibited excellent resistance to acidic and alkaline solutions.
Mendes-Felipe et al［53］ prepared acrylated epoxidized soybean oil (AESO) and acrylated soybean oil (ASO) using epoxidized soybean oil (ESO) and soybean oil (SO) as raw materials, respectively. Acrylated epoxidized soybean oil is generally obtained through a two-step consecutive reaction. First, the vegetable oil undergoes epoxidation, converting the double bonds in the fatty chains into epoxy functional groups. Subsequently, the epoxy functional groups react with the carboxyl group of acrylic acid to obtain bio-based acrylates. The double bonds present in vegetable oils can also directly react with acrylic acid in a one-step reaction without the need to convert them into epoxy rings. Using boron trifluoride dissolved in ether (BF3OEt2) at 48% as an efficient Lewis acid, it is possible to insert acrylic acid molecules into the double bonds of fatty chains, enabling the one-step preparation of ASO. Through research on 3D printing formulations of the two bio-based acrylates, it was found that the printing accuracy of AESO and ASO could reach ±0.1 mm. This work demonstrates the possibility of using bio-based materials as photocurable inks for 3D printing and the feasibility of obtaining 3D printing inks from raw vegetable resources through a one-step reaction.
Wang et al［54］ prepared bio-based acrylates using cuttlefish oil, palm oil, and rubber seed oil as raw materials. As shown in Figure 12, cuttlefish oil reacted with dimethylformamide to obtain cuttlefish oil amide (SSM) through amidation. SSM was then esterified with methacrylic anhydride to obtain cuttlefish oil-acrylate monomer (SSMA). Subsequently, SSMA underwent an epoxidation reaction with meta-chloroperoxybenzoic acid (m-CPBA) to synthesize cuttlefish oil-acrylate epoxy monomer (ESSMA). Similarly, palm oil-acrylate monomer (PMA), palm oil-acrylate epoxy monomer (EPMA), rubber seed oil-acrylate epoxy monomer (RSMA), and rubber seed oil-acrylate epoxy monomer (ERSMA) were synthesized following the same process. The monomer conversion rate exceeded 99%, allowing direct use after production. Furthermore, ESSMA was also used as a sustainable monomer and copolymerized with vinyl acetate (VAc) via miniemulsion polymerization. The copolymerization conversion rates for different monomer ratios were all above 99%. The introduction of plant oil-based segments significantly improved the thermal stability and water resistance of PVAc latex.
图12 ESSMA Synthesis［54］

Fig.12 ESSMA synthesis［54］

Hua et al［55］ prepared a series of methyl methacrylate tea oil monomers (MCO) using camellia oil precursors as raw materials and systematically studied their radical polymerization. Due to the ability to generate stable growing radicals, camellia oil-based methacrylate monomers can achieve high conversion polymerization for the preparation of branched polymethacrylates. The plant oil-based branched polymethyl methacrylate PMCO obtained can be used as an organic coating, with an adhesion strength of up to 2.74 MPa. Meanwhile, a series of base-functionalized plant oil-based polymethacrylates were synthesized. Due to the π-π stacking of the bases and their hydrogen bonding and coordination effects with the substrate, the binding strength of the bases was significantly improved. Hydrogen bonds between complementary bases allow us to further enhance the adhesion of the coating, with the maximum adhesion of the supramolecular coating reaching 9.89 MPa.
Fang et al［56］ used anethole, a plant essential oil extract, as a raw material to synthesize a novel renewable acrylate monomer with a yield of up to 89.9% (as shown in Figure 13). In the presence of sodium dodecyl mercaptan, the methoxy group on the benzene ring of anethole can be converted into a hydroxyl group, making this new acrylate contain both acryl and acryloyl functional groups. This monomer was radically copolymerized with methyl acrylate (MA), and the resulting copolymer was post-cured at high temperatures. At this point, the double bonds on the acrylate groups could react with the acryl groups in anethole to form a crosslinked network. The results showed that the crosslinked polymer had good thermal stability, and the Tg of the copolymer increased with the increase in the content of the plant oil acrylate monomer. Among them, the Tg of poly(MA-co-M2) 2/1 reached 148 ℃, and the light transmittance was over 92% in the range of 450-1100 nm. Additionally, the hardness of other copolymers was tested using a Rockwell hardness tester, and the hardness of the copolymers became superior to common optical materials such as PMA and PMMA as the content of M2 increased.
图13 Synthesis of Anisole-Based Acrylate and Its Radical Copolymerization with MA［56］

Fig.13 Synthesis of anisyl acrylate and copolymerization of anisyl acrylate and methyl acrylate［56］

Glycerol, hydrolytically separated from animal and plant oils, is an important bio-based platform compound. Cyclic glycerol ketals obtained by the condensation of glycerol with ketones possess unique properties and are widely used in synthetic fibers, pharmaceuticals, and the food industry［57］. Cochran et al.［58］ prepared a series of glycerol ketal (meth)acrylates using enzymatic transesterification reactions with glycerol ketals of different structures and (meth)acrylic acid monomers. Subsequently, through RAFT polymerization, they synthesized glycerol ketal (meth)acrylate polymers (as shown in Figure 14). They investigated the influence of different ketal structures (acetone, butanone, cyclopentanone) on the properties of glycerol ketal (meth)acrylate polymers. When the molecular weights were similar, the Tg of the acrylate derivative containing a cyclopentyl ketal side group (GCA) was approximately 10 ℃ higher than that of the derivative with an acetone ketal side group (GSA), possibly because rigid side chains like cyclopentyl restrict polymer movement due to steric hindrance, resulting in a higher glass transition temperature. In glycerol butanone ketal (meth)acrylates (GBM/GBA), the longer flexible side chains increase the free volume of the polymer chains, allowing them to slide more easily against each other, leading to the lowest Tg values.
图14 Preparation and Polymerization of Glycerol Acetal Acrylate［58］

Fig.14 Synthesis and polymerizations of［58］

5 Preparation of Bio-Based (Meth)Acrylates and Their Polymers from Glucose as Raw Material

Levoglucosenone (LGO), obtained through the catalytic pyrolysis of glucose or cellulose, is considered a promising bio-platform chemical in the fine chemical industry. LGO possesses easily modifiable functional groups and a double-bond ring structure[59], where the glycosidic bond, ketone group, and carbon-carbon double bond functional groups can impart a wealth of properties to materials[60].
Saito and Simon et al［61］ obtained the derivative dihydro-5-hydroxyfuran-2-one (2H-HBO) through lipase-mediated oxidation of levoglucosan (LGO) and used 2H-HBO to synthesize a bio-based acrylic monomer (as shown in Figure 15). 2H-HBO, methacrylic anhydride (MAN) in the presence of triethylamine (TEA) and 4-dimethylaminopyridine (DMAP), synthesized 2H-HBO methacrylic compound with a yield of 79%. By investigating the polymerization ability and impact on products of bulk polymerization, solution polymerization, and emulsion polymerization, it was found that solution polymerization could achieve the highest molecular weight but with a broader molecular weight distribution ranging from 1.52 to 4.6, while emulsion polymerization reached a conversion rate of 60.2% with a molecular weight distribution of only 1.06 when the polymerization time reached 300 minutes.
图15 Synthesis of Methacrylate-Functionalized 2H-HBO (m-2H-HBO)［61］

Fig.15 Synthesis of methacrylated 2H-HBO （m-2H-HBO）［61］

Saito and Simon et al. used dihydrolevoglucosenone (Cyrene™) as a raw material to prepare another bio-based methacrylate polymer with high Tg, and high thermal stability［62］. As shown in Figure 16, the carbonyl group on Cyrene™ was first reduced to a hydroxyl group, then reacted with methacrylic anhydride to prepare the methacrylate monomer m-Cyrene. This acrylate can undergo homopolymerization and copolymerization through radical polymerization. Compared with solution polymerization, the polymer obtained by emulsion polymerization has the highest yield (92%) and higher relative molecular weight. The Tg of the polymer obtained by emulsion polymerization is as high as 192 ℃, and the non-toxic nature of the bio-derived monomer was confirmed by cytotoxicity tests. Compared with the structurally similar methacrylate monomer IBMA, this newly synthesized monomer exhibits higher chemical reactivity.
图16 Cyrene™ Synthesism-Cyrene［62］

Fig.16 Synthesis of m-Cyrene from Cyrene™［62］

Allais et al［63］ prepared β-butyrolactone (HBO) from LGO through enzymatic catalysis, followed by hydrogenation to obtain 2H-HBO. Under the action of Candida antarctica lipase B (CAL-B), they reacted with methacrylamide (MAA) respectively to prepare the corresponding bio-based methacrylates HBO-m (as shown in Figure 17) and 2H-HBO-m. Both HBO-m and 2H-HBO-m can undergo free radical homopolymerization and participate in copolymerization reactions with other monomers such as MMA, MAA, and α-methylene-γ-valerolactone (MGVL). The copolymers of 2H-HBO-m with MAA and MGVL exhibit relatively high Tg (100 ℃~190 ℃). Additionally, 2H-HBO reacted with 3,4-dihydro-2H-pyran to obtain THP-2H-HBO, and a new acrylate monomer M-THP-2H-HBO was synthesized, which underwent homopolymerization and copolymerization with methyl methacrylate. The glass transition temperature range of this series of copolymers is 101~147 ℃.
图17 Enzymatic Synthesis of HBO-m［63］

Fig.17 Enzymatic synthesis of HBO-m［63］

The preparation of bio-based acrylic acid using biotransformation methods (such as enzymatic hydrolysis and microbial fermentation) has attracted extensive attention from both academia and industry. Biomass such as glucose and glycerol can be used to produce bio-based intermediates like lactic acid and 3-hydroxypropionic acid through fermentation, and after operations such as fractional distillation, bio-sourced precursors of (methyl) acrylate (such as 3-hydroxypropionic acid and acrylic acid) can be obtained. Subsequently, the corresponding bio-based (methyl) acrylate and polymers can be obtained through esterification and polymerization reactions, and this method has broad industrial prospects.
Zhang and Dauenhauer et al［64］ achieved the conversion of glucose to methyl methacrylate by combining biotechnological fermentation with chemical catalysis (Figure 18). The effect of removing 3-isopropylmalate dehydratase was achieved by deleting the gene encoding its subunit from E. coli, which metabolizes citramalate in the leucine biosynthesis pathway. After genetic editing and optimization of the fermentation medium, the intermediate citramalate was produced from glucose. Subsequently, the intermediate citramalate was decarboxylated to methacrylic acid (MAA) through a thermocatalytic method. Due to secondary decarboxylation reactions forming CO2 at high temperatures and high acidity, the yield of liquid products was low. The Pd/C catalyst increased the selectivity of MAA from 45.6% to 63.2%. Finally, glucose was converted into bio-based methyl methacrylate (MMA) and its polymer through esterification and polymerization reactions.
图18 Combining Mixed Fermentation and Thermal Catalysis to Convert Glucose into Methyl Acrylic Acid (MAA) via Citric Acid ［64］

Fig.18 Hybrid fermentation and thermocatalysis to produce methacrylic acid （MAA） from glucose through citramalic acid［64］

Tan et al［65］ used lactic acid (ester) obtained from biological fermentation as raw material and respectively utilized molecular sieves, sulfates, phosphates, and composite catalysts to prepare a series of high-purity acrylic acid (esters) through the dehydration of lactic acid, providing new ideas for further research on bio-based acrylic acid (esters). Yu et al［66］ reviewed the research progress in the preparation of acrylic acid from lactic acid. The preparation of bio-based acrylic acid was achieved through biological and chemical methods such as catalysis by CoA-transferase and solid acid catalysts, laying an important foundation for the preparation of bio-based acrylate.
3-Hydroxypropionic acid (3-HPA) ［67］ is a bio-based platform material and a potential chemical foundation for the sustainable production of acrylic acid and acrylates. Raw materials for obtaining 3-HPA through biological fermentation include glucose, glycerol, and diols. Acrylic acid can be obtained by dehydrating 3-HPA. Borodina et al. ［68］ developed Saccharomyces cerevisiae as an efficient cell factory for high-level production of 3HP. First, glucose is used to synthesize β-alanine, then a novel β-alanine-pyruvate aminotransferase discovered in Bacillus cereus is utilized to convert it into 3-HPA. Under the catalysis of solid acids, it can be efficiently converted into acrylic acid and transformed into corresponding bio-based acrylates and their polymers.

6 Preparation of Bio-Based (Meth)Acrylates and Their Polymers from Isosorbide as Raw Material

Isosorbide is a bio-based compound that can be directly obtained by dehydration from sorbitol, a glucose derivative［69-70］. Due to the presence of two secondary alcohols with different reactivity in its structure and the special double five-membered ring ether structure that can impart high rigidity to polymers［71-72］, it has received widespread attention. These structural features also make isosorbide a preferred monomer for forming high-performance bio-based polymers［73-74］, with potential applications in the automotive industry, electronics, coatings, and biomedical engineering［75］.
Reineke et al.［76］ used isosorbide as a raw material and SC(OTf)3 as a catalyst to synthesize a novel monomer, acetylated isosorbide methacrylate (PAMI), through a two-step reaction. Compared with Lewis acids, SC(OTf)3 exhibits higher stability towards air and water, can be handled under normal pressure, and does not require anhydrous reaction conditions. As shown in Figure 19, the first step involved adding isosorbide with an appropriate amount of acetic anhydride and Sc(OTf)3, reacting at room temperature for 10 minutes, and separating the acetylated isosorbide product using column chromatography. Subsequently, methacrylate was introduced. Using dithiobenzoate as the RAFT chain transfer agent, by adjusting the amount of chain transfer agent, the resulting polymer PAMI maintained a low molecular weight distribution (1.06~1.09) while achieving a conversion rate of over 92%, along with a high Tg (Tg=130 ℃) and good thermal stability. Additionally, the influence of isomeric structures on the thermal properties of the polymer was investigated. Under the same conditions mentioned above, an isomeric sample of PAMI was prepared from endo-MI, with the conversion rate of endo-MI reaching 84%. Thermal gravimetric analysis and differential thermal analysis showed no significant differences in Td or Tg between PAMI and PA-endo-MI.
图19 Synthesis of Acetylated Isosorbide Methacrylate (AMI)［76］

Fig.19 Synthesis of acetylated methacrylate isosorbide （AMI）［76］

La Scala et al［77］ developed a series of photocurable isosorbide (meth)acrylates for additive manufacturing. Isosorbide methacrylate (IAM), isosorbide diacrylate (IA), isosorbide dimethacrylate (IM), and bisphenol A (meth)acrylate (BPAMA) were synthesized respectively (as shown in Figure 20). The synthesized isosorbide-based resins exhibited higher Tg and superior mechanical strength compared to bisphenol A-based resins, and showed lower viscosity (140 cP) at 25 ℃. The study conducted experiments on the curing of IM-containing samples using isobornyl acrylate (IBOA) or N-acryloylmorpholine (ACMO) as diluents. Under the action of a series of different ratios of diluents, the IM-based resin achieved relatively high degrees of cure after thermal curing, and further increased the Tg of the polymer while effectively reducing its brittleness, with the Tg of the IM-based resin reaching up to 231 ℃. The study also found that adding suitable (meth)acrylate polyurethane oligomers could further enhance the thermal and physical properties of the IM-based resin.
图20 (A) Synthesis of Isosorbide Diacrylate (IA) and Isosorbide Dimethacrylate (IM), (B) Isosorbide Methacrylate (IAM), (C) Bisphenol A Diacrylate (BPAA) and Bisphenol A Dimethacrylate (BPAMA)［77］

Fig.20 Synthesis of （a） isosorbide diacrylate （IA） and isosorbide dimethacrylate （IM）， （b） isosorbide acrylate methacrylate （IAM）， and （c）Bisphenol A diacrylate （BPAA） and Bisphenol A dimethacrylate （BPAMA）［77］

Leiza et al［78］ explored the preparation method of isosorbide methacrylate (ISOMA) (as shown in Figure 21). Isosorbide and dimethyl nitrosamine were dissolved in dichloromethane to react, yielding a mixture of isosorbide methacrylate (ISOMAraw). ISOMAraw is a mixture with a molar ratio of isosorbide methacrylate to dimethacrylate isosorbide of 8:2. Using n-hexane/ethyl acetate (6:4 V/V) as the eluent, the mixture can be purified by column chromatography to obtain the ISOMA monomer. Radical solution polymerization was used to obtain PISOMA, with a Tg of approximately 80°C. Introducing ISOMA as an additive into the copolymer PSA of IBOMA and 2-octyl acrylate enhanced the copolymer's adhesion while increasing its removal rate in warm water.
图21 Synthesis of ISOMA［78］

Fig.21 Synthesis of ISOMA［78］

Potier et al［79］ developed a method for synthesizing isosorbide methacrylate (as shown in Figure 22). After adding acrylic acid and dried isosorbide to dried acetonitrile, a catalyst (Sc(OTf)3; ZnCl2; HCl or H2SO4) was added dropwise under nitrogen at 40 ℃. After 16 hours of reaction, isosorbide methacrylate monomer containing two diastereomers (endo and exo) was obtained. Subsequently, the IMA monomer underwent radical polymerization, resulting in insoluble material within less than 5 minutes at 90 ℃, demonstrating the extremely high reactivity of the monomer. When conducting radical reactions of IMA in different solvents, it was found that when the monomer to initiator ratio was 100:1, the monomer conversion rate was above 84%, with molecular weight distributions ranging from 1.5 to 1.7, where the highest number-average molecular weight could reach up to 75,100 g·mol-1. The obtained PIMA exhibited excellent thermosetting properties, with the highest molecular weight PIMA showing a Tg (Tg ≈112 ℃) comparable to industrial polyacrylates. When succinic anhydride was used as a crosslinking agent, a PIMA resin with high thermal stability and maintained high transparency was obtained, with a storage modulus near 4 GPa at room temperature.
图22 Synthesis of Isosorbide Monoacrylate (IMA)［79］

Fig.22 Synthesis of isosorbide monoacrylate （IMA）［79］

Vares and Jannasch et al［80］ prepared a series of isosorbide 5-methacrylates and 2-methacrylic acid isosorbide esters through highly selective biocatalytic/chemoenzymatic methods. The synthesized monomers were equipped with acetate, dodecanoate, cyclohexanecarboxylate, and hydroxyl functional groups, which endowed the monomers with good reactivity. The corresponding polymers were obtained via free radical polymerization. Among them, both regioisomeric polymers with free hydroxyl groups exhibited high Tg (close to 170 ℃). Capping the hydroxyl functional group with an acetate group reduced the Tg to approximately 130 ℃. The thermal properties of methacrylate polymers with C12 alkyl esters having different isomeric structures showed significant differences. This laid an important foundation for the design and preparation of high-performance isosorbide polymethacrylate polymers.

7 Preparation of Bio-Based (Meth)Acrylates and Their Polymers from Furan Derivatives

5-Hydroxymethylfurfural (HMF) and its derivatives obtained through the isomerization and dehydration of glucose are versatile biomass-derived platform compounds[81-83]. Due to the special structure of the furan ring, which can impart excellent thermal stability and rigidity to materials, bio-based polyurethanes and bio-based nylons prepared from HMF derivatives are hot research topics in the field of bio-based materials[84-85]. Furan acrylate compounds have wide applications in drug synthesis, organic functional materials, and new polymer monomers.
Makhubela et al［86］ synthesized methacrylate monomers FAMA and SoMA using bio-based furfural and glycerol as raw materials through a simple transesterification reaction (as shown in Figure 23). LAMA was obtained by dropwise addition of methyl methacrylate and toluenesulfonic acid in lactic acid and hydroquinone. Subsequently, the above monomers underwent RAFT homopolymerization and copolymerization. The Tg of the polymers ranged between 67~150 ℃. The Tg of P(FAMA-co-LAMA) could reach 150 ℃ due to the high thermal stability of the furan ring. By blending PFAMA, PSoMA, and P(FAMA-co-SoMA) with polysulfone (PSf) and cellulose acetate (CTA), novel composites with good degradation properties were obtained, showing degradation rates of 10% or more within 24 hours.
图23 (a) FAMA and SoMA (b) FAMA and LAMA (c) LAMA and SOMA Radical Copolymerization［86］

Fig.23 Copolymerization of （a） FAMA and SoMA， （b） FAMA and LAMA， and （c） LAMA and SOMA［86］

Heiskanen et al［87］ synthesized furan diglycidyl ester similar to Bis-GMA structure based on furan dicarboxylic acid. Subsequently, the furan diglycidyl ester was subjected to chain extension reaction with methacrylic acid to obtain the corresponding furan dimethacrylate (FD) and difuran dimethacrylate (BfD). Due to the presence of free hydroxyl groups, the prepared dimethacrylates exhibited relatively high viscosity. To reduce the viscosity of the polymerization system, FD, BfD, and their mixed monomers were copolymerized with methacrylic acid eugenol (ME), respectively. When the ME content reached 40 wt%, the system viscosity significantly decreased, and the Tg of the copolymers could reach approximately 200 ℃. Notably, the Tg of FD60ME40 was as high as 209 ℃.
Webster and Sibi et al［88］ synthesized a series of bio-based (meth)acrylate diluents using biomass-derived raw materials 5-hydroxymethylfurfural (HMF) and 2,5-diformylfuran. Compared with the commercial diluent HDDA, the samples prepared with furan-based (meth)acrylate diluents have higher Tg. Using furan diol diluent and HDDA to react with urethane acrylate resin respectively for preparing UV-curable coatings, the samples prepared with furan diol diluent exhibit higher thermal stability.
Wang et al［89］ developed a highly sensitive and photosensitive furan acrylate derivative (as shown in Figure 24). Using biomass-based furfural as the raw material, they synthesized bifunctional diethylene glycol difurfuryl acrylate (DEFA) and trimethylolpropane trifurfuryl acrylate (TMFA) monomers for photo-induced polymerization. Furfural reacts with acetic anhydride to obtain furan acrylate, which is then esterified with diethylene glycol and trimethylolpropane to obtain DEFA and TMFA, respectively, followed by polymerization under ultraviolet light. The kinetics of the polymerization reaction showed that, in the absence of a photoinitiator, the double bond conversion rates of DEFA and TMFA reached 88% and 78%, respectively, within 1 minute, indicating that both DEFA and TMFA possess excellent photosensitivity.
图24 Synthesis of TMFA and DEFA［89］

Fig.24 Synthesis of TMFA and DEFA［89］

8 Conclusions and Prospects

This article summarizes the research progress in the preparation of bio-based (meth)acrylate monomers and their polymers through biomass conversion. Using various methods, lignin, terpenes, vegetable oils, glucose, isosorbide, and furan compounds were successfully converted into (meth)acrylate monomers with different structures. Corresponding (meth)acrylate homopolymers, copolymers, and other series of materials were obtained via radical polymerization. The bio-based route can not only prepare chemical structures identical to those produced by petrochemical technology (e.g., methyl methacrylate), serving as an important supplement to petrochemical materials, but also design entirely new structures that are difficult to synthesize using petrochemical technology, endowing polymers with new properties and functions, greatly increasing the added value of materials, and expanding application areas. Looking ahead, the following directions deserve attention in the research on the synthesis of bio-based (meth)acrylates and the preparation of their polymers: (1) Designing novel catalytic systems to improve the synthesis efficiency of bio-based (meth)acrylate monomers, reduce costs, and lay a solid foundation for material preparation; (2) Developing efficient polymerization technologies to enhance the controllability of polymerization reactions, combine flow chemistry with external force fields, and precisely construct target polymer structures; (3) Building a collaborative innovation system integrating industry, academia, and research to promote the industrial transformation of bio-based materials and monomers, creating high-end products supported not only by sustainable concepts but also by excellent performance.

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