Heterocyclic Derived Bioplastics with High

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Syntheses of Aromatic/heterocyclic derived bioplastics with high thermal/mechanical performance Mohammad Asif Ali, and Tatsuo Kaneko Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.9b00830 • Publication Date (Web): 10 Apr 2019 Downloaded from http://pubs.acs.org on April 12, 2019

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Industrial & Engineering Chemistry Research

Syntheses of Aromatic/heterocyclic derived bioplastics with high thermal/mechanical performance.

Mohammad Asif Ali1,2, Tatsuo Kaneko1*.

1Graduate

School of Advanced Science and Technology, Energy and Environment

Area, Japan Advanced Institute of Science and Technology, 1-1 Asahidai, Nomi, Ishikawa, 923 1292, Japan 2Soft

Matter Sciences and Engineering Laboratory, ESPCI Paris, PSL University,

CNRS, 10 rue Vauquelin, 75005 Paris, France

ACS Paragon Plus Environment

1

Industrial & Engineering Chemistry Research 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

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KEYWORDS. Aromatic, Heterocyclic, Cinnamic acid, Itaconic acid, Polyamide, Polyester

.

Abstract Bio-based plastics derived from renewable starting materials are indispensable for the establishment of low-carbon green-sustainable society. However, aromatic bio-based plastics are hardly developed although they are expected to show very high thermal/mechanical performances. The cinnamates are one of the aromatic bio-based renewable materials and cinnamates-based photo-functional polyesters were prepared which showed high thermo-mechanical properties. On the other hand, environmentallydegradable heterocyclic polyamides including aliphatic/aromatic components derived


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from itaconic acid showed higher performances than conventional aliphatic polyamides. The heterocyclic polyamides showed UV-triggered solubilization in water which can be expected to apply to a fishing line that is gradually solubilized in sea water under the sunlight. In addition, heterocyclic bio-based PAs derived from cinnamate-photodimer derivatives have a significant impact due to their excellent thermal stability, as well as transparency. Considering the cost/performance of bio-based polymer performances should give higher values and the higher possibility to materialize in industry. In this viewpoint, the aromatic bio-based polymers are excellent candidates. Further exploration of bio-based monomers and the development of cinnamate-derivative production as well as new monomer design present an outstanding prospect to meet the new and advanced horizons of polymer chemistry.


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Introduction In recent years, polymers derived from biomass have been extensively studied, and numerous investigations were conducted including the development of polymers containing cyclic moieties derived from biomass like starch, beetroot, pulp or after fermentation of glucose.1 Bio-based and environmentally-benign polymers originated from renewable starting materials are significant for the establishment of greensustainable society.1 The research on bio-based polymers is based on aliphatic polyesters such as poly(hydroxyalkanoate)s2 which are directly derived from the microorganism polymerization system which has a supreme advantage in terms of short steps for polymer production. A polysaccharide, which can be derived from not only the microorganism but also fungi and plants have established the industrial area of polymer materials3-10. Proteins8 and other poly(amino acid)s9 have also been targeted in biomedical, food, and cosmetic industries.10 However, the biopolymer production system directly from microorganisms or plants have the limitation of molecular design for

controlling

functions

and

thermal/mechanical

performances

because

the

polymerizations are based on the enzymatic reactions inherent to the microorganism,


4

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fungi, and plants. Whereas, white-biotechnological approaches, i.e., a combination of biotechnology and chemical engineering, for bio-based polymer production have innovatively widened the macromolecular design to produce various aliphatic polymers such as polyamide 11,11 poly(glycolic acid),12 poly(lactic acid),13 and their derivatives. However, the bio-based polymers with aliphatic structures did not show enough high performances to apply in engineering plastic fields.14 The extension of the field for biobased polymer has been historically developed under strong relation with the development

of

biodegradable

materials

with

having

low

thermomechanical

properties.14 However, these polymers contributed a small percentage in terms of degradability currently used in the narrow field of materials but can be applied for the daily commodity articles.15 However, some of the partially bio-based polyester having high thermal resistance using non-renewable terephthalic acid have been developed and commercialized by BASF as EcoflexTM

16

and DuPont as BiomaxTM 17. On the other

hand, some of the petroleum-derived materials having high thermal resistances are mainly composed of aromatic groups as represented by Poly(ether ether ketone) (PEEK)18, Liquid-crystal polymers (LCP), aramid19,20, polybenzazoles21,22 and some of


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them have rigid heterocycles23,24. Aromatic biomolecules are undoubtedly the best candidate for renewable starting materials for high-performance bio-based polymers, but aromatic structures in the polymer backbone do not exist in nature except for lignin which

has

been

targeted

as

starting

macromolecules

for

high-performance

polymers.23,24 In this context, lignin is a complex network of an aromatic compound with phenylpropanoid units. However, structural control of lignin is too difficult in the current state of sciences and technologies to materialize in industry. Considering these backgrounds of bio-based polymer design, one of the important methodologies for the development of high-performance bio-based polymers is the usages of small aromatic biomolecules as renewable starting materials.22,23 Here we review the recent researches on the development of high-performance bio-based polymers derived from aromatic renewable starting biomolecules. In this review, monomers derived from plant biomass such as glucose are called “phytomonomers”.25,26 The phenolic phytomonomers are used for the synthesis of biobased polymers.26,27 Following sections have been classified into polyesters26,28 and


6

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polyamides29,30. Some of the bio-based heterocyclic polymers31 introduced in this review have higher performances than all the reported neat polymers. The aforementioned approaches allow the establishment of a new class of high-performance materials beyond bio-based polymers which will contribute to the industrial polymer materials field in the future. Polyesters

Biobased polyester Polyesters are mostly widely commodity plastics used in our daily life such as in food containers, fibers, coating, packaging, rubbers, and composites materials.4,32 As we know the concerns around energy shortage and environmental pollution are highlighted in recent years.32 Therefore alternative biobased polyesters have attracted enormous attention both in academic and industrial fields.4 Polyesters can be prepared by different methods such as through a polycondensation reaction of diacid, hydroxy acids or anhydride and secondary alcohol or via a lactone ring opening polymerization.33,34 Presently, various essential biomass-based polyesters35 are being used in industrial biological material, such as polyhydroxyalkanoate (PHA), polylactic acid (PLA)35, poly(-


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caprolactone) (PCL), poly(glycolic acid) (PGA).4,36 Their copolymers are extensively exploited biodegradable polymeric biomaterials for drug release and tissue engineering. Polyhydroxyalkanoates (PHAs) are the only bioplastics fully produced completely by microorganisms with Tg between -50 to 4 oC, and Tm ranging from 60 to 170 oC.37 Some of the diols such as 2,3-butanediol, 1,6-hexanediol, 1,8-octanediol, and 1,10decanediol are potentially biobased monomers used for the syntheses of polyesters.37,38

Isosorbide

based

polyesters,39

mannitol-based

polyesters

or

copolyesters of dimethyl terephthalate, 1,4-butanediol thermally stable up to 370 oC.40,41 There are some bio-based potential monomer which generates the terephthalic acid which further used for polyamide and polyester syntheses. Terephthalic acid(TA) is a monomer it synthesized from the oxidation of petroleum-derived p-xylene which were used for several polyesters such as PET and also comonomer to condensed with various diamines and used for fibers and resins. There is significant interest for the syntheses of TA, which are derived from citrus derivatives limonene, muconic acid, isobutanol and hydroxymethylfurfural (HMF) 4 are shown in Figure 1. The polyesters and polyamides that are prepared by using muconic acid as shown in Figure 1.42 Moreover,


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the small portion of polyester43 and polyamides research has focused which were derived from 1,6-hexanediol, hexamethylenediamine, adipic acid, caprolactam, and caprolactone.4,44 Polyesters derived from HO

Polyamide

Glucose Isobutanol

O

OH

O

O

O

Furan dicarboxylic acid (FDCA)

5-hydroxymethyl-furfural (HMF)

CH3

OH O

O

O

O

Polyester/PEF

Lignin HO

Terephthalic acid

OH

O

O

HO

Muconic acid

Polyester

CH3

Limonene

OH OH

OH HO

Citrus fruit

OH

OH

O

OH

O

Aldaric acid

Glucose

HO

NH2

H 2N

1,6-Hexanediol

Hexamethylenediamine

O

O

O OH

OH HO

NH

O

Adipic acid O

Caprolactum

Polyester

Polyamide

Polyester/polyamide

Caprolactone

Polyamide/polyester Polyester

Figure 1. Synthetic scheme of biomonomer and polymer from terephthalic acid4,32,37.

carbohydrate-based monomers with a cyclic structure provide chain stiffness with a high

Tg, which makes them useful for packaging used for gaseous beverages.45 Terephthalate polyester like PET, poly(butylene terephthalate)33 poly(trimethylene terephthalate) (PTT) are a class of high-performance polymer which have a wide range of applications.44,46 The poly(ethylene terephthalate) (PET) is the fastest growing bio-


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based plastic but, it can be replaced by furan-based poly(ethylene furanoate) (PEF)47. The glass transition temperatures (Tg) of PEF (Tg~ 87 oC) is higher than PET (Tg~ 80 oC)47

as

but lower Tm compared to PET. Several examples of furan-based polyesters such poly(ethylene

furandicarboxylate)

2,5-furandicarboxylate) (PHQF),

poly(isoidide

(PEF),

poly(1,4-phenylene

2,5-furandicarboxylate)

2,5PDAIF,

poly(isosorbide 2,5-furandicarboxylate)32,48 (PDASF) have high glass transition temperature in between (Tg~ 78-180 oC)32,47,48.

Polymerization of phytomonomers A hydroxy acid biomolecules can be used as a phytomonomer for bio-based polyesters. Phenolic acids have ideal structures for phytomonomers of aromatic polyesters. Especially One of the most important phenolic acids is p-coumaric acid (4hydroxycinnamic acid; 4HCA)49 which can be derived petrochemically but is a very important phytochemical as a base precursor for lignin biosynthesis. 4HCA is produced via the enzymatic reaction of phenylalanine with phenylalanine ammonia lyase, and Cyt P450-dependent monooxygenase.25,50 4HCA is also available in several photosynthetic


10

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bacteria as a photosensor of protein component; Rhodobacter capsulatus.,51

Rhodobacter sphaeroides.,52 and so on53,54 containing photoactive yellow proteins whose structure are changed by a trigger of 4HCA photoconversion. Other coumaric acid derivatives (Figure 2), ferulic acid (3-methoxy-4-hydroxycinnamic acid; MHCA), caffeic acid (3,4-dihydroxycinnamic acid; DHCA), sinapic acid (3,5-dimethoxy-4hydroxycinnamic acid; DMHCA) have also been selected as phytomonomers since these molecules are commonly available in various plants which follows through some pathways of lignin biosynthesis.25,50,54 Furthermore, since the enzymatic conversion of amino acids such as L-phenylalanine (Phe) and L-tyrosine (Tyr) to the coumaric acid derivatives is well defined and straightforward, it is feasible to scale-up for massproduction24,55 These phytomonomers are known to be biodegraded by microbial action.56 We also used 3-hydroxycinnamic acid (3HCA) whose biosynthetic pathway was not found, but it contained in lignin57-58 presumably as a result of lignin degradation. The biobased 3-amino-4-hydroxybenzoic acid (3,4 AHBA) is aromatic renewable starting material which is not included under cinnamate family, but its obtained from

Streptomyces griseus has been reported.59


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Phytomonomers H2N HO COOH H2N Phenylalanine

HO

COOH H2N Tyrosine

COOH

3-amino-4-hydroxybenzoic acid (from Str eptomyces gr iseus)

HO HO

HO

COOH

COOH

COOH

p-Coumaric acid (4HCA)

Cinnamic acid

Caffeic acid (DHCA)

O

lignin

HO

HO COOH

COOH

O

HO m-Coumaric acid (3HCA)

Ferulic acid (MHCA)

Sinnapic acid (DMHCA)

Homopolymers

COOH O

O

O

O O n

P4HCA

PMHCA

O n

O O

P3HCA

O

O n

PDHCA

O n

Hyperbranched copolymers O

O O

O m

O n

AB2-type O O

n O

O

O

m

O AB3-type (Cholic acid)

FigureFigure 1 Structures of aromatic phytomonomers and corresponding polymers 2. Structure of aromatic phytomonomers and corresponding polymers.

Poly(p-coumaric

acid),

P4HCA,

was

obtained

through

thermal

acidolysis

polycondensation of acetylated 4HCA under the N2 atmosphere.26 The 4HCA was heated and agitated around 180-220 oC for 24 hours in the presence of acetic anhydride with an alkalescent catalysts such as sodium acetate,60 sodium phosphate derivatives, and hydrotalcite (HT: [Mg6Al2(OH)16](CO3)4H2O).61 When sodium acetate and sodium


12

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phosphate derivatives were used, multimodal peaks were observed in the analytical curve of gel permeation chromatography (GPC) to suggest side/uncontrolled reactions during the polymerization.61 On the other hand, the polymers prepared in the presence of HT catalyst (0.4-0.6 wt%) shows mono-modal molecular weight distribution, indicating that the HT efficiently catalyzed the acidolysis reaction of the carboxylic acid with the acetyloyloxy groups and significantly reduced the side reactions. HT belongs to the layered-double-hydroxides family, and the hydroxyl groups of HT surface are important for their catalytic activities. HT layers were found to promote acidolysis polymerization and the molecular weight increases with increasing a layer structure ordering evaluated by X-ray diffraction.61 Then, we speculate that the rigid-rod chains of polymers can be adsorbed in the ditches at the end of layer structures to avoid the additional side reaction of oxygen or hydroxyls to cinnamoyl double bonds.


13


Not melt (Crystalline)

Nematic

500 μm

P4HCA

PMHCA

Isotropic (elastic)

Isotropic

500 μm

Page 14 of 77

500 μm

500 μm

P3HCA

Schlieren texture ( nematic)

PDHCA

500 μm

P(4HCA-co-DHCA)

Figure 3. Structures of coumarate polymers and their polarized microscopic photos taken above 200 oC.

The reaction mixture was precipitated in methanol. The polymer formed was collected and further washed with acetone and dried upto a get pale yellow powder.26,61 A similar procedure has been widely followed for other homopolymer syntheses such as PMHCA, PDHCA, P3HCA. However, it was impossible to prepare PDMHCA by the same method presumably due to steric hindrance of two methoxyl groups contiguous to hydroxyl.25,61 The introduction of the comonomer units in the polymer structure affects the polymer rigidity, and in-turn provides a novel technique to regulate the thermo-mechanical properties.62


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O

O

O O

H 2N OH

CHO

HO

O

(CH3CO)O, Na2HPO4 200 oC

150 oC -H2O

3,4-BAHBA

n

N

N OH

HO

O

OH

HO

m

O

P(3,4-BAHBA-co-4HCA)

Figure 4. Syntheses of bio-based copolyester, poly(3-benzylidene amino-4-hydroxybenzoic acid-co-tras-4-hydroxycinnamic acid), derived from 3-amino-4-hydroxybenzoic acid and 4hydroxycinnamic acid.

GF LC P

530nm

50 m

A

Figure Microscopic of the glass (GF)cross-nicol taken under cross-nicol polarization Figure 45.Microscopic photosphoto of the glass fibers (GF)fibers taken under polarization using a first-order using a first-order retardation plate (λ=530 nm) inserted in to the light path. GF, middle and retardation plate (λ=530 nm) inserted into the light path. Left: GF, Middle and right: GF on which poly(4HCA-coo right: on which DHCA)GF powder was putpoly(4HCA-co-DHCA) and annealed around 200 oC. powder was put and annealed around 200 C. O

O

O O

a

b

R OR'

O O

O

O O

O

R'O

HO

2+2 cycloaddition R

O

O

O

O O

n OH GeO2

nO m

O

O O R

O

OR'

n= 2, 3, 4, 5

O

O

O

Figure 6. a) Typical photoreaction of cinnamoyl groups. b) Molecular design of semiaromatic polyesters containing photo reactive coumarate group in the main backbone.

A series of copolymers of 4HCA with AB-type, multifunctional AB2-type, and AB3-type


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comonomers were synthesized, and ABx-type comonomers induce to form the hyperbranched structures as shown in the bottom of Figure 2. The weight average molecular weight of the P4HCA measured by GPC was around 8 000 g/mol which is not very high, but the copolymerization induced a wide range of molecular weight from 3 000 to 70 000 g/mol. Thermal properties A series of polymers of coumaric acid derivatives showed glass transition temperature,

Tg, melting values, Tm, and 10 % weight loss, Td10, ranging 130-220 oC, 220-260 oC, and 315-390 oC, respectively. These values are much higher than those of the conventional petroleum-based semi-aromatic polyesters such as Poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT) and also some bio-based polyesters from vanillic acid and glycolic acid

63

respectively. S. Miller et al. reported that semi-aromatic bio-

based polyesters of hydrogenated ferulic acid showed the Tg value of 73 oC,64 which was lower than those of above coumarate-derived polyesters. However, furan-based polyester which is produced after using of aliphatic diols, isosorbide have higher thermal properties. The most spotlighted member of FDCA polyesters family is definitely the high-


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performance

poly(ethylene

2,5-furandicarboxylate)

(PEF),

poly(propylene

2,5-

furandicarboxylate) (PPF), and poly(butylene 2,5-furandicarboxylate) (PBF)65 which have similar thermal and mechanical properties as counterpart of poly(ethylene terephthalate)’ (PET).47,48 The reported polyester exhibited a glass transition temperature Tg values 80-120 oC and a thermal degradation temperature over 300 but lower mechanical properties.65,66 It is clear that the high thermal stability of the coumarate-derived polyesters is directly related to the rigidity of aromatic moiety and unsaturated double bond in the polymer backbone. Besides it is noteworthy that the chain-end modification of poly(lactic acid)s by cinnamoyl derivatives increased thermal degradation temperature, according to the recent literature by K. Kan et al.67 Another character of a p-coumarate moiety in the polyester is mesogenic to induce the formation of a thermotropic liquid crystalline (LC) structure. 4HCA homopolymer has a p-coumarate moiety to exhibit nematic LC phase where the polymer chains are randomly located, but their orientation axes were aligned to n-director.68 Crossed-polarizing microscopy was used to demonstrate the LC exhibition by birefringence observation which appeared around 210-215 ºC as shown in Figure 3 (P4HCA: Schlieren texture). An interesting phenomenon was observed that the crystallization from the nematic phase by heating to 280 ºC presumably due to postpolymerization or decarboxylation, accompanying with the transformation of the microscopic texture from the Schlieren to a needle shape.68 The homopolymers P3HCA and PDHCA did not show the LC phase (Figure 3), and then m-coumarate moiety did not work as a mesogen. The mesogenic behavior of 4HCA units was kept in the copolymers. Hyperbranched copolyesters poly(4HCA-co-DHCA)s exhibited a thermotropic LC phase, where the Schlieren texture was observed by crossed polarizing microscopy (Figure 3). The texture was observed more clearly in the copolymers synthesized in the presence of HT than other alkalescent catalysts61. The


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researcher on the LC copolymers containing 4HCA units were extended to the development of polarized emission materials. LC copolymers, poly(3-benzylidene amino-4-hydroxybenzoic acid-co-4-hydroxycinnamic acid), (structure: Figure 4) have a fluorescent side group of Shiff base which was derived from 3-amino-4-hydroxybenzoic acid (34AHBA).69 34AHBA was wholly-aromatic amino acid derived from Streptomyces sp (Figure 5). The LC oriented film of the copolymer showed a polarized emission whose intensity depended on the direction of polarized excitation light to the n-director. As we recently reported, thermotropic liquid crystalline polybenzoxazoeamide and poly(benzoxazole-co-diazole) has been prepared. The polybenzoxazoeamide the longer alkyl chain induces the lower Tg is around to be 197-240 oC higher than conventional polymers such as PA-11 and PLA.69

Mechanical properties The polymer chains in the LC state are easily orientated at the molecular level to impart better mechanical properties. Among these polymers, poly(4HCA-co-DHCA)s showed the best values of mechanical properties.68 The mechanical bending test of the oriented copolymer samples showed the mechanical strengths at the break, Young’s moduli, and strains at the break, ranging between 25-63 MPa, 7.6-16 GPa, and 1.2-1.3, respectively.68,70 The Young,s moduli and tensile strength of poly(4HCA-co-DHCA)s61 were higher than transparent polycarbonates but lower


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N O

N

O O

N H 2N

x

N

COOH

HO

Poly(benzoxazolediazole)

3-amino-4-hydroxybenzoic acid (3,4-AHBA)

O O

O

N H N

O

C

N

N H

n n = 2,3,4,5,6

x

Poly(benzoxazoleamide)

Figure 7. Synthetic routes for poly(benzoxazolediazole) or poly(benzoxazoleamide) derivatives from 3-amino-4-hydroxybenzoic acid. strain at break (Figure 6). make the application field wider, the higher mechanical strength at break were required. The hybridization with reinforcement fillers were one of the general methods to improve mechanical properties. Renewable Kenaf fibers was used for preparing the hybrids of the poly(4HCA-co-DHCA)s, but the mechanical properties were not very remarkably improved. On the other hand, the fillers of glass fibers (GF)61 were enhancing effects on the mechanical strength of the copolymer resins. The pictures in Figure 5 are microscopic photos of the GF, taken under crossnicol polarization using a first-order retardation plate (λ=530 nm) inserted into the light path. The left picture showed no light transmission except 530 nm wavelength through the GF itself to demonstrate non-orientation. On the other hand, the poly(4HCA-coDHCA)61 powder was put on GF and annealed around 200 oC in the LC state. The


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copolymer LC melt flowed and automatically oriented with a coating on the GF surface


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to show birefringence in the middle and right pictures. From these figures, indicates that


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the polymer birefringence was negative.71 The figure indicates that both the


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birefringence (blue color) in the GF lying from the upper left to the lower right, and the


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additive birefringence (orange color) in the fibers lying from the upper right to the lower left. However, the negative birefringence suggests that the rigid polymer backbone including with the phenylene-vinylene groups in their main chains of the polymer which enhances the orientation along the GF axes. The polymer chains were oriented if the GF was incorporated into the resin in the LC state. As a result, the mechanical strength measured by the three-point bending test showed a good correlation with the GF composition, to attain ca. 140 MPa mechanical strength at break, which is high enough to use as an engineering resin. The biobased using aromatic amino acid 3,4 AHBA with aliphatic diamines (n=5) gave poly(benzoxazole-amide)69 which shows tensile strength and Young’s moduli as 85 MPa and 3.1 GPa (Figure 7). On the other hand, well know

Shape A

Shape B

Shape C

Shape D

1 Figure 8. A typicalc complex photoinduced shape‐memory effect at λ=280-450 nm with o heating at 60 C. m engineering resins such as epoxy resins (e.g. diglycidyl ether of bisphenol A) shows a lower Young’s modulus (1.2 GPa) and tensile strength (35 MPa) as compared with GF


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reinforcement poly(4HCA-co-DHCA)61,68.

Recently, Wang et al. reported that

poly(DHHCA-co-4HPPA) (AB2 type) prepared via thermal polycondensation of 3,4dihydroxyhydrocinnamic acid (DHHCA) and 3-(4-hydroxyphenyl) propanoic acid (4HPPA) is expected to have bio-adhesive properties. The adhesive strength of the copolymers depends on the different ratio of DHHCA /4HPPA which lead to a better adhesive strength as compared with values of 10.3 MPa on carbon, 9.6 MPa on glass, and 6.2 MPa on steel26.

Photoreactions Cinnamic acid derivatives have been very famous for photoreactive chemicals, and P4HCA also shows the photonic [2+2] cycloaddition reaction in the nematic state.70 The photoreactivity of the poly(4HCA-co-DHCA) copolymers shows photo-tunable hydrolysis behavior in an alkaline buffer solution.25 The copolymers formed the photoreactive nanoparticles by controlled reprecipitation method, and the nanoparticles showed reversible size changes from the 860 nm diameter to 420 nm. However, UV irradiation over 280 nm wavelength and rapidly recovered to 620 nm upon subsequent irradiation at 254 nm, based on reversible photonic [2+2] cycloaddition and cleavage (Figure 6a).72


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The size change can be derived from the interchain distance controlled by photoirradiation. The ultraviolet light was irradiated to the surface of P3HCA film which was more easily processed than other homopolymers prepared in this research, to induce the photo bending behavior

73.

Since Tg of P3HCA was around 120 oC, the film

was a kind of hard plastic at room temperature, and the photo bending speed was slow. If the Tg was decreased, the photo bending should be accelerated. The diacid monomer (BMOPS) based on 4HCA including succinyl group was synthesized and BMOPS was polycondensed with various diols (nC) in the presence of GeO2 used as transesterification catalyst, to create the polyester abbreviated as poly-nC, n (no of carbon) (Figure 6b)28. The GeO2 was efficient catalyst to favor transesterification with the number-average, and weight-average molecular weight ranged between Mn = 1.9x104 g/mol and Mw = 4.8x104 g/mol, respectively. The decomposition temperature (10 % weight loss temperature) and Tg of the polyesters were mostly within the range of 319-335 oC and 36-64 oC respectively. The semi-aromatic polyesters film were prepared by a hot press machine at 140 oC with 3 MPa pressure which was further utilized to study the shape memory behaviors. The films were heated to above the glass transition


26

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temperature regain its original position after 15 s. Further, it was investigated under UVlight (280-450 nm) was exposed from upper side with the intensity of 65 mW/cm2 the free edge of film quickly lifted to form a concave shape. The bending speed of the polymer was controlled by the intensity of UV light, in which the diol group affects the bending movement behavior and therefore, it should be derived from [2+2] cycloaddition of cinnamoyl double bond.28 After the external load of UV treatment (280-450 nm) it deforms the shape at 70 oC and then further recovers its original position after UV (λ < 250 nm). Further, the shape recovery cycle of poly2c was performed under light and heat control, with a particular shape of film gingko leaf processed by hot press at 140 oC under pressure of 2MPa for 30 s as shown in Figure 8. The shape of gingko leaf changes to a flying swan at λ= 280-450 nm after cooling down it changes to sleeping swan (screw types) in about 10 sec. In this process, after UV treatment of the film, surface forms the covalently cross-linked structure through photocycloaddition which stabilizes the flying swan forms. The sleeping swan (screw type) shaped polymer was infused into the water at 60 oC, above its glass transition. The shape of the flying swan was recovered. In this process, the shape was additionally recovered into the original


27


Page 28 of 77

shape after UV-light at λ= 250 nm. The shape of sleeping swan after considerable strain by inverse bending of wings and neck was recovered as a flying swan. The multiple kinds of shape memory realized by two external stimuli after heat and photo-irradiation may lead to a verity of potential application in medical and light-driven actuators. Shape memory polymers possess the ability to memorize actual shape and recover their original shape in response to appropriate external stimuli. Shape memory was mostly induced by external stimuli like heat and UV, etc for the use of the biomedical application. External stimuli, especially thermal and UV stimuli confirm through contact or a particular wavelength and were absorbed by the unsaturated bond.28 UV irradiated to facilitate shape-memory effect by [2+2] addition reaction, such irradiation memorizing diverging effect but after mechanical stimuli enhancement of cross-linking density. Z. Wang et al. reported that trans-cinnamic acid based diacid (α-truxillic acid) condensed with diols including ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol (Figure 9).74,75 The polyester shows Tg and Td10 values ranging between 64-81 oC and 340-350 oC respectively. The decreasing trend of the Tg with


28

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increasing diol carbon chain length. The novel building blocks with rigid cyclobutanecontaining polyesters which are comparable to Poly(ethylene terephthalate) (PET).74

O COOH

O HO

HO

m OH

m= 2,3,4,5,6

h

O O

m

n

OH

Cinnamic acid

O O

-truxillic acid

Figure 9. The syntheses of poly(α-truxillate). Polyamide

Molecular design Since Carothers’s invention of polyamide-6,6 in 193075, outstanding thermal/mechanical performances of polyamides higher than those of polyesters have been recognized to induce a wide variety of polyamide molecular design from aliphatics like NylonTM

76

to

aromatics such as KevlarTM.77 These biomonomers such as succinic acid, 1,12dodecanoic acid, glutaric acid, ricinoleic acid, adipic acid, 11-aminoundecanoic acid, cadaverine, putrescine are shown in Figure 1077 were used for development of polyamides (Table 1).77,78 By using these monomer some of the bio-based polyamides such as polyamide-5, polyamide-5,4, polyamide-5,5, polyamide-5,10, polyamide-4,10,


29


Page 30 of 77

polyamide-6,10, polyamide-10,10, polyamide-10,12 and polyamide-11 etc. were developed as shown in Figure 11.26,77,78 Arkema has design several

Table 1. Selected biobased polyamide with characteristic 78,79

Polyamides (PA) properties.

Td10 oC

Tg oC

Tm oC

Water uptake (%)

Biosourcing(%)

PA 4 PA 44 PA 46 PA 410 PA 5 PA 55 PA 6 PA 66 PA610 PA1010 PA1012 PA11 PA12 PA-IA PA-IAAra PA-IAArb PA-IAArc

380 390 395 392 388 400 398 397 398 400 398 380 399 400 408 406 415

ND ND ND ND ND ND 47 50 48 37 49 29 37 86 156 172 256

ND ND 278 250 240 242 220 260 278 191 181 189 178 ND ND ND ND

12 10 15 14 9 ND 10.5 8.2 4.0 1.8 1.6 1.9 2.0 3.0 2.0 2.6 2.0

100 100 63 50 100 100 0 0 64 100 45 100 0 100 50 50 50

a) Bio based polyamide. (b) The thermal decomposition temperature at which 10% weight-loss temperatures (Td10), glass transition temperature (Tg) and melting temperature (Tm)

were

measured. (c) The PA-IA, derived from itaconic acid with ethylenediamine, PA-IAAra, PA-IAArb and PA-IAArc derived from the itaconic acid with aromatic diamine m-xylylenediamine, pxylylenediamine, and 4,4'-Diaminodiphenyl ether, respectively. ND-Not determined.

biobased polyamides comprising 42-100 % biobased materials which uses Castor oil after being hydrolyzed to generate ricinoleic acid which in turn produces 11-undecanoic


30

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acid used to make PA 11 (Rilsan® 11).79,80 Cadaverine is synthesized after the decarboxylation of L-lysine via lysine decarboxylase. Cadaverine is becoming a cheap

(a) Diamine syntheses O

E. coli

NH2 H 2N

NH2

HO O

putrescine

NH2 L-ornithine NH2

HO

E. coli NH2

H 2N O

Cadevarine

L-lysine

NH2

OH HO

Adipic acid

(b) Diacid syntheses

NH2 H 2N


O

H OH O O HO

OH

Fermentation

HO

HO

OH

Glucose

O

OH O

HO

Succinic acid O OH

O

HO

OH

NH2

Glutamic acid

Glutamine OH

O

O

OH

O OH

HO

OH HO

OH

OH

O

Glucaric acid

Adipic acid

O


31


Page 32 of 77

and important chemical to prepared some of polymer such as polyamide 5,10 whose properties are similar to conventional nylon. 66.77,81,82

Figure 10. Syntheses of the biobased monomer such as diamine/diacid.77,78,81 The growing demand of this diamine which is expected to reach 5.8-5.9 billion US dollar by 2021.82,83 T. Iwata et al. developed D-Glucaric acid (GA) (value added product) are isolated from vegetables and fruits further condensed with aliphatic diamine forms amphiphilic polyamides have a low melting temperature (Tm ~119-141 oC).84 Further, this diacid condensed with aromatic diamines produces poly(m-xylylene-acetyl glucaramide) and poly(p-xylylene-acetyl glucaramide)85. The weight-average molecular weight and (Tm~141 oC) increases as compared with aliphatic chains but still lower 10 % weight loss (Td10) (210 oC) as compared with the conventional nylon 6.86 Polyamide 4 is produced by GABA which is produced by decarboxylation of glutamate using glutamate decarboxylase is a bio-based87 degradable polymer, but their thermal performance was quite low because of short aliphatic chain.88 However, due to the aliphatic structure, their thermal resistances were low89

to require inorganic reinforcement fillers for

engineering use. Incorporation of ring structures such as heterocycles, alicycles, and


32

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aromatics were efficient to increase the performance (Table 1). Aromatic/heterocyclic ring based polyamides90 or polyesters prepared by using such as Terpenes/ Rosin/furan ring makes it attractive to the replacement of flexible conventional aliphatic chain based polyamides or polyesters.

87,82,91

However, degradability92 was the issues of useful

development in terms of degradability; quantitative structure-properties measurements are lacking.88 The Furan based polyamides derived from bio-based monomer have a high potential to make high-performance properties. Some of the researchers have reported about the soil degradability, but it takes a longer time for complete degradation.93,33,44 On the other hand, path-breaking advancement for the syntheses of aromatic diamines through [2+2] photocycloaddition reaction of the 4ACA (4aminocinnamic acid) further used for the syntheses of ultrastrong-transparent bioplastics.The degradability of bio-derived polymers into monomers is important in terms of sustainability but stable backbone with aromatic rings and amide bonds that typical hydration methods such as biodegradation would be ineffective.88 A system comprising hydrolysis and photodegradation was tested to accomplish their chemical recycling chemically.


33


Page 34 of 77

O H2 N

OH

11-aminoundecanoic acid

OH

O HN

Castor oil OH

Ricinoleic acid

PA 11

O

NH2 H2 N

H2 N

OH

PA 410

1,4 diaminobutane

O

PA 510

NH2

1,5-pentanediamine

HO

PA 610

NH2

Sebacic acid

H2 N

O

1,6-diaminohexane NH2

H2 N

PA 1010

1,10-decanediamine

Lauric acid O

NH2

OH

PA 1012

H 2N

HO

Decamethylenediamine

1,12-dodecaneioic acid O

Glucose O

NH2 H2 N

OH


PA 66

HO

Adipic acid O

O NH2

HO

OH

E. coli H2 N

NH2 O

HO

O

L-lysine

Succinic acid O

O

O

Pseudomonas putida (PP)

O

PA 55

NH2

5-aminopentanoic acid

PA 54

HO

NH3

Cadevarine

N H

PA-5

HO

OH

Glutaric acid

Glucose

n

O

OAc

O

OAc

OAc

OAc H N

OH

R

HO OAc

OAc

D-Glucaric acid (GA)

OAc

O

Ac = H

R:

H N

OAc

Polyamide

m

O

Ac = COCH3

According to the literature,30 the reaction of itaconic acid (IA) with amine compound forms NFigure 11. Syntheses of biobased aliphatic polyamides.77,78,85,86,94


34

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substituted pyrrolidone which is a heterocyclic amide ring. If the pyrrolidone is incorporated into the polyamide backbone, the thermal/mechanical performances of polyamides can be improved. IA has been an attractive bio-derived acid which contains two carboxylic acids with  -unsaturated double bonds30,31. At first, IA was synthesized through a citric acid cycle with a low yield. However considerable research efforts have been dedicated to improving the production efficiency, and IA is fermented from carbohydrate by fungi Aspergillus terrus (efficiency: 80-85 g/L)90,91 but recently, the introduction of Aspergillus terreus gene in Aspergillus niger which enhances the production level up to 135 g L-1. The worldwide production of IA is estimated to be more than 80,000 tons each year and sold at a price of around US$ 1.8-2/kg and due to high potential demand of these compounds expected to grow by 5.5-6 % every year until 2023. 91,92 Next, we have the study of polymerization of IA, and their derivative has been extensively studied.30,31 Specifically, the radical polymerization of IA and various copolymers such as polyester and heterocyclic polyamides have been an active area of research.31,94 The vinyl-type polymer of IA including their copolymers with styrene butadiene, acrylonitrile, and methyl acrylate possessed low thermal/mechanical


35


Page 36 of 77

properties95 while its polyesters of IA has high thermal/mechanical properties94. Based on the background of IA monomers, the research-extension to syntheses of polyamides including IA-based heterocyclic pyrrolidone was smoothly considered.31 Furan derivatives polyamides

Nowadays, there is a continually growing demand for furonate-based polymers; it is an attempt to substitute the petroleum-derived terephthalate-based polyamides.47 The furan derivatives polyamides can be prepared by using aliphatic and aromatic diamines after condensed with furan derivatives carboxylic acid 2,5-Furandicarboxylic acid (FDCA) to produces polyamides.48,65 The growing interest of the 2,5-FDCA (furan dicarboxylic acid) by oxidation of 5-HMF (5-hydroxymethylfurfural) obtained after dehydration as shown in Figure 12.96,48,65 In the past, furan derivatives polyamide was not considered exceptional due to its low thermo-mechanical performance because following

the

conventional

polymerization

process.48,97,98

However,

solid-state

polymerization (SSP) is the key point to the development of high molecular weight furan derivatives polyamides which have a high glass transition temperature (Tg) due to rigid-


36

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chain44,99,100. Linear aliphatic polyamides by using FDCA and aliphatic diamine by varying the number of alkyl chains have been studied since 1961.

Polyester

O O O

O O

O O

O

O

O O

O

n

O

poly(ethylene 2,5-furandicarboxylate) (PEF) Tg= 78-80 oC Tm = 210-215 oC

O

n

n

O

poly(1,4-phenylene 2,5-furandicarboxylate) (PHQF) Tg= 78-80 oC Tm= ND

O

O

poly(isoidide 2,5-furandicarboxylate) (PDAIF) Tg= 140 oC O Tm = ND O

H

Glucose

O

OH

HO

O

O

n

O OH

O

5-hydroxymethylfurfural (HMF)

O

O

O

O

2,5-furandicarboxylic acid (FDCA)

O

poly(isosorbide 2,5-furandicarboxylate) (PDASF) Tg= 180 oC Tm = ND

Polyamide H N

H N

H N

n

O O

O

n=2, 3, 4, 5, 6

N H

m

Tg = 302 oC

Tg = 68-107 C

H N

H N

O

Tg = 275 oC

O

O

n

n

O

n

O

Tg = 280 oC

O

H N

H N

O

H N

O

O O

O

H N

O

O

O

o

H N

H N

O

O

n

o

Tg = 68-107 C

O

O

n

Tg = 68-107 oC

Figure 12. Syntheses of bio based polyester and polyamide from furan. 44,48,65,96,98 Many authors investigate that because of aliphatic chains it has a low glass transition temperature. Kaiju. et al. reported that FDCA condensed with its derivatives such as Furan based diamine, aliphatic diamine and by varying aromatic diamine having a Tg


37


Page 38 of 77

value 80-302 oC with an exhibiting decomposition temperature above 400 oC as shown in Figure 12.44 The FDCA based polyamides are circulated in the market as our commodity article such as carpet, textiles and used for the automotive and electronic application.44,48 S. tateyama et al. reported that cinnamic acid derivative (α-truxillic acid) condensed with FDCA showed a higher glass transition temperature, Tg, of the polymer of 273 °C.88 These thermal properties are lower than those of previous biopolymers but are higher than those of bio-based plastics reported other researchers. Both values of

Tg and T10 were sufficient for the application of polymer as an industrial plastic with high thermoresistant performance. The stress-strain curve of the maximum tensile strength and Young’s modulus were σ = 356 MPa and E = 11.4 GPa, respectively. All the materials possessed high molecular weight with high glass transition, but higher than those of aliphatic counterparts. The main attraction for replacement of furan derivatives polyamide with itaconic acid based polyamides is to explore the possibility of soildissolubility and soil degradability upon completion of their usage.88

Terpenes and Rosin


38

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Terpenes are hydrocarbons that contain one or more carbon-carbon double bond and share the same elementary unit of isoprene (2-methyl-1,4-butadiene).101,102 The natural product with the cycloaliphatic or aromatic ring structure and its derivatives is used as a monomer. However, in this report, limonene was used as an active agent and not as a monomer, limonene is one of the comonomers, that has been successfully incorporated into novel polymers as a bio-based monomer or monomer precursor. The (R)-(+)- and (S)-(−)-limonene, as well as (−)-β-pinene via thiol-ene additions for the formation of polyamides (Figure 13).102 Polyamides based on 1,8-diamino-p-menthane, a readily available limonene derivative, has been synthesized via interfacial condensation with various diacid chlorides, which led to low molecular weight polymers.103 Further, polyamides with the sulfur atoms also had a higher melting temperature than those without sulfur.102 Polymers with the longer alkyl chains were observed to have a higher melting temperature. The Tg of all polymers was ≈ −45 °C and the Tm varied from -15°C to 50 °C.102 Rosins are classified into three types’ tall oil, wood rosin and gum rosin. The gum rosin is the most common rosin and is obtained from a pine tree, and it has


39


Page 40 of 77

been considered as feedstocks for polymers. The rosin derivatives can be used as a commoner for polyamide, polyester.103,104 The derivatives of rosin are used as

O O

n N

N H

OH

n= 2,3,4,5

n NH2

H 2N

H

m

HO O O

Rosin based polyamides

Rosin based terpinoid

H N

*

H N S

R

S

7

7 O

O

n

Limonene H N

H N S

R

S

7 O

7 R= CH=CH

O

n

Figure 13. Synthesis of rosin and terpenes-based polyamides.82,101,102 diacid which is further utilized as a commoner for polyamides. The syntheses of rosinbased polyamides (Figure 13) are expected to improve high heat resistance due to the rigidity of the chain. The use of rigid curing agents increased the overall Tg of resultant polymers. Some of the rosin acids101,103 are classified as abientane and pimarane type resin acids.82 The derivatives of abientane used as diacid and also following Diels-Alder


40

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reaction forms monomers for polyester, and polyamides.101,102 The obtained polyamides with heterocyclic backbones enhance the thermal properties and glass transition (Tg) over 120 oC.103

4-HCA derived polyamides

On the other hands, there are bio based polyamides which are reported recently to have higher heat resistance over 150 oC with a transparent film which possesses largely amorphous structures with path-breaking molecular design including cyclobutane ring interlinked with aromatic units. Takaya et al. utilized Escherichia coli (E. coli) cells to synthesize a 4-aminocinnamic acid (4ACA) from glucose.104,105 Further by using 4HCA, divergent syntheses of diamine and truxillic acid derivatives by the protection of amine group following HCl and acetic anhydride/trifluoroacetic anhydride/pentafluoropropionic anhydride.88,89,104

Polymerization

of

diamine

and

diacid

was

utilized

for

polycondensation to yielded a rigid Poly-I, Poly-II, and Poly-III (Figure 14) with a high glass transition of over 240 oC with Td10 (10 % weight loss temperature) over 400 oC


41


Page 42 of 77

with excellent transparency over 90-95 % (the highest among transparent plastics and borosilicate glass). Glucose Fermentation COOCH3

NH2

O H N

H N

O CH2

HOOC

Poly-I

n

n= 2,3,4,5,6

4-aminocinnamic acid (4ACA)

n

COOCH3

NH2 COOCH3

O

O

O H N

O

NHR

O

H3CO

Poly-II

N H

COOCH3

n

OCH3 COOCH3 O

O H N

H N

Poly-III

C

NH2

4,4'-diamino--truxillic acid dimethyl ester

n COOCH3

R= -COCH3 -COCF3 -COCF2CF3 NHCOCF3

Figure 14. Syntheses of bio-derived polyamides from 4-aminocinnamic acid (4ACA).88,105 This high Tg value in the case of Poly-I could be altered after copolymerization with various aliphatic diacids such as succinic acid or adipic acid.89 The bio PAs with an over Mn of 10 000, an Mw of 21 000, and was attributed to the high mechanical strength. The direct amidation of 4,4-diamino-α-truxillic acid dimethyl ester with several diacids


42

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and a 2,5-furan dicarboxylic acid as described as Poly-I and Poly-II with Tg value in between the

150-273 oC with tensile strength Young’s modulus, and transparency

values of 356 ± 33 MPa, 11.4 ± 1.6 GPa, and 93%.89,90 The introduction of fluorine side chains improved the transparency of the Poly-III film and suppressed its yellowness.106 The 10% thermal decomposition temperature (Td10) and Tg of the resulting were approximately same and similar to that of non-fluorinated PA.104 Especially the mechanical strength of the fiber is 407 MPa at maximum higher than those borosilicate glasses, presumably due to the molecular spring function possibly showing tautomerization

in

the

phenylenecyclobutanyl

backbone

despite

noncrystalline

structure.88 There is no biodegradation such as soil/bacterial degradation that would be possible which indicates that the polymers are stable, but chemical or photodegradation is important regarding sustainability because it enables their chemical recycling.88 Itaconic acid based polyamides

Polymerization


43


The bio-based polyamides were synthesized through a two-step process; salt monomer formation and subsequent melt-polycondensation.105 An equimolar mixture of diacid or diamine was dissolved in ethanol and allowed to be stirred at 35-40 oC (Figure 15).30

OR O HO

O

O

O

m

OH

n

O

n Radical polymerization

polycondensation

O

R = H, Alkyl, Aryl

CH2

Radical-addition polymerization

HOOC

Glucose

RO

COOH

CH2

CH

CH2

CN

Itaconic acid Michael addition

COOH

C COOH

Michael addition

O

O

O

NH N

N

n

n

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 44 of 77

n = 2, 3, 4, 5, 6 O

m

O

When the solution was subsequently cooled down to 0 oC, salt monomers were precipitated.30,31

Figure 15. Polymer design based on itaconic acid.30,31 The salt monomer polymerization methods were preferable than direct melting polymerization because of the mixing under proper stoichiometric ratio and non-


44

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vaporizing of monomers by heating. The accurate stoichiometric ratio is effective on avoiding the side-reaction to branch the chains by reaction of one IA with three amino groups, which increased the molecular weight of polymers.31 The reaction temperature for polymerization was designated to be 10 oC higher than the melting temperature of salt monomers detected by TGA-DTA analyses.

-

HOOC COOH

n

+ n

H2 N

NH2

EtOH

OOC COO- +H3N

n

NH3+

m

m O HOOC



COOH

n



m

HO N H

m NH2

+ (2n-1) H2O

N C O

H

m=2, 3, 4, 5, 6

N

H

n

Figure 16. Syntheses of itaconic acid biobased polyamides derived from salts of itaconic acid and aliphatic diamine.30,31 During melting, the primary amine reacted with the double bond of IA via the Michael addition to form imine group, and then the imine, it reacts immediately with nonneighboring carbonyl group to forms five-membered pyrrolidone ring31,30 which were shown in Figure 16. As a result, the polyamide including a pyrrolidone ring in the main


45


chain was formed. The polypyrrolidone have some advantages; rigid cyclic amid induce to the reduction of water absorption ratio to only 4 wt % (polyamide-6 or polyamide-66; 9-11 wt %),31 and the thermal/mechanical properties comparing to conventional aliphatic polyamides as described later. The copolymerization is important to tune the bio-based polyamides properties. There are reported the IA-based co-polypyrrolidones prepared using 1,4-butanediamine, 10-decanediamine, succinic acid30. Aromatic one and aliphatic-aromatic-co-polyamides based on IA were also synthesized.

Aliphatic copolymers O O O N

CH2

x

H N

C

O CH2

C

10

O H N

CH2

x

NH

N

n

x

H N

C

CH2

H

C

N

10

m

x= 2, 3 ,4, 5 etc

O

CH2

O

CH2

N

x H

p

O

Aromatic polymer O

N

A

O

A:

N H

n O

Ring opening reaction

O

Under h by alkaline in enviroment

O

OH

HO

HO

n N H O

H

x

n

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 46 of 77

H O

H

x

Figure 17. Synthesis of bio-based polyamides contain pyrrolidone ring.22,30,31,106


46

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Thermal/mechanical properties i) Aliphatic polyamides Aliphatic polyamide shows Tg and Td10 values ranging between 80-152 oC and 300410 oC respectively.30 While the Td10 values were comparable with those of conventional polyamides 390 oC (PA-66) and 400 oC (PA-6), the Tg values were higher than 57 oC (PA-66) and 53 oC (PA-6).

30,31

The high heat resistance is directly related to the

heterocyclic moiety and hydrogen bonding in the polymer backbone. The obtained tensile strength of aliphatic polyamide fiber was in the range of 65-165 MPa, and Young’s modulus was in the range of 430-2800 MPa, respectively. The N-substituted rigid ring provides extra stability, its fibers can be stretched easily but restrict to get high elongation at break. The elongation at break of aliphatic polyamides ranged 0.018-0.049 which were low due to the rigidity of N-substituted pyrrolidone ring. In the case of copolymers, elongation at break is drastically increased to 0.04-0.07 as compared with homopolymers. This might be entropic effects of the presence of different flexible alkyl chains in the polymer backbones.31,22

ii) Aromatic polyamides


47


Wholly aromatic polyamides such as NomexTM 22 and KevlarTM

Page 48 of 77

31

are representative

members of high-performance polymeric materials. Then IA-based polyamides were synthesized with aromatic diamines to prepare high-performance bio-based polyamides (Figure 17)22 Tg, and Td10 ranged 156-240 oC and 370-400 oC of m-xylylenediamine, pxylylenediamine, and 4,4'-diaminodiphenyl ether based polyamide, respectively.

Tg values were higher than those of aliphatic polyamides, but processability is too low to prepare the specimen for the mechanical test due to their rigidity of aromatic ring as well as non-planarity of pyrrolidone ring. The copolymerization of aromatic polypyrrolidones with aliphatic one were tried to prepare, but the resulting copolymer resins were too brittle.

Degradability The aliphatic polypyrrolidones were not soluble in water but became soluble in alkaline water after stirring at 60 oC about pH 9-10.30,31 FT-IR and 1H-NMR analysis demonstrated the ring opening reaction of pyrrolidones shown at the bottom of Figure 17, which induced to solubilize the polyamides. The water solubilization test was


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monitored in the water under the irradiation of mercury-lamp with a wavelength range between 280-400 nm (Figure 18).

Soil corrosion behavior of polymer resins Before Beforeburied buriedin the soil PLA

n: 2

n: 3

n: 4

n: 5

n: 6

After After one one year yearinside soil

wt% 8484 wt%

wt% 4 4wt%

wt% 0 wt% 2 wt% 00wt% wt% 00wt% wt%

Photosolublization behavior of polymer resins

0h

1h

2h

3h

4h

5h

6h

Figure 18. Environmental corrosion of itaconic acid based polyamides. Hydrolysis of pyrrolidones occurred partially to generate hydrophilic carboxyl side chains. The polypyrrolidone resin disappeared in water about 6-24 hrs. Usually, sunlight includes UV-A and UV-B covering 280-400 nm which comes to earth and makes our


49


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resins corrosive after a long period of exposure and we expect hence the utilization of the phenomenon can reduce fishing lines floating on the ocean to save marine creatures. Additional analysis of polymer resin in soil with pH 7.5-7.9 was examined concerning changes in shape and weight loss, and molecular weights were examined. Polymer resin and biodegradable PLA (positive control) were buried inside the soil with polyethylene nets and dug out after one year.

22,30,31

Most of the polymer resin

disappeared, and others became very small due to the soil corrosion while PLA loss was only 16 wt % (Figure 18). The size reduction should be derived from the environments

including

chemical/physical/biological

activity.30

Thus,

IA-based

polyamide including pyrrolidone rings was expected to show corrosion behavior in the environment, which reduces the accumulation of plastics waste in landfill thereby, promotes an environmental-harmonizing function as compared with the petroleumbased polyamides.31,32

iii) Polypyrrolidone hybrids The synthesized itaconic based polyamides resulted in the limitation of thermal and mechanical properties.30,31 The effect of the addition of montmorillonite (MMTs) as


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nanofiller at 220 °C by following cryogenic hybridization (around 77 K in liquid nitrogen) with polymer resins which have high requirements to tailoring the properties.

107

The

prepared nanohybrids structure favors the ionic/van der Waals interaction between clay and PA, which disrupt dislocation of clay. In order to achieve well-exfoliated morphologies and subsequently to improve properties, it is necessary to use organic/inorganic Nano clay. The clay used as a NaMMT which further treated with benzyl ammonium chloride, alkyl bis(2-hydroxyethyl)methyl ammonium chloride designated as (ArMMT) and (OHMMT).

107

The synthesized PA and its nanohybrids

have different thermal degradation behavior, Td10 of the neat PA was 399 °C but after hybridization with NaMMT enhances up to 409 °C, On the contrary, the cryogenic treated based PA/NaMMT hybrids further increased Td10 to 423 °C. Tg of the neat polyamide appeared at around 73 oC while increasing the content of the NaMMT from 1 wt% to 7 wt% decreased Tg to 60 oC. When other clays of organically-modified MMT were uses such as ArMMT and OHMMT after cryogenic hybridization, the decrease in

Tg was only slight. However, a cryogenic hybridized sample showed a Tg value of 61 oC which was slightly higher than a noncryo-treated sample (57 oC). The reinforcement


51


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effects of clay on PA enhance mechanical strength and hardness. However, the used NaMMT had a ductilization effect because of catalytic activities over the pyrrolidone ring that improve elongation degree. Since Young’s moduli were enhanced, this is not a simple plasticizing effect. The drastic improvement of strain energy density was attributed to the catalytic effect which further confirmed the interaction of the silicates layer with the pyrrolidone moiety. The tensile strength of without/with cryo-treated nanohybrids were: with NaMMT (102 MPa, 129MPa), with OHMMT (170MPa, 203 MPa) and with ArMMT (185 MPa, 217 MPa).

107

The improvement in modulii were with

nanohybrids such as NaMMT (2.7 GPa, 2.5 GPa), with OHMMT (4.8 GPa, 5.1 GPa) and with ArMMT (5.2 GPa, 5.3 GPa).

Conclusion and future outlook

The cinnamates-based photo-functional polyesters such as poly(p-coumaric acid-cocaffeic acid) showed high thermo-mechanical properties and can be used as a commodity to the high-tech application. On the other hand, environmentally degradable heterocyclic polyamides derived from itaconic acid showed higher performances than


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conventional aliphatic polyamides. The heterocyclic polyamides which are solubilized in water under the ultraviolet irradiation will solve problems for serious issues for marine creatures such as a fishing line that is left in the ocean. It is believed to provide a clue and an initiative step for solving plastic waste problems. In this viewpoint, the aromatic bio-based polymers are excellent candidates. Further exploration of bio-based monomers and the development of cinnamate derivative production as well as new monomer design present an outstanding prospect to meet the new and advanced horizons of polymer chemistry. The series of bio-based polymers will contribute great impact in the materials world because of the new development of human prosperity along with a low-carbon sustainable society.

AUTHOR INFORMATION

ORCID, Mohammad Asif Ali: 0000-0002-5717-5659 ORCID, Tatsuo Kaneko: 0000-0001-9794-083X

Corresponding Author Tatsuo Kaneko


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Tel: +81-761-51-1631, FAX: +81-761-51-1635, Email: [email protected].

Notes Any additional relevant notes should be placed here.


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TOC:

COOH

Glucose

COOH HOOC

Aromatics/pro-heterocycles

0hbioplastics 1h High-performance/functional


77

Heterocyclic Derived Bioplastics with High

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