New Methods in the Synthesis of (Meth)Acrylates

*Cengiz Soykan*

## **Abstract**

Generally, the words "reactive polymers" and "functional polymers" mean the same thing and are used interchangeably in most studies and describe cross-linked (insoluble) bead-structured resins containing chemically reactive functional groups. In this way, reactive polymers are widely used as polymeric reagents or polymer supports in biochemical and chemical applications. Functional (meth) acrylates referred here to supply "functional esters" ruins as a general reactive group precursor. In other sense, the leaving (activating) groups of these monomers may easily react with the alcohols and amines carrying the desired reactive groups and therefore, in general, provide a single reaction step for the synthesis of reactive polymers. In this paper, we suggest new routes for a new (meth)acrylate-based monomers and polymers. Also, the synthesis of a serial new (meth)acrylate esters including amide, dioxolane, benzofuran, and chalcone groups is described.

**Keywords:** activated (meth)acrylates, α-chloro-N-aryl acetamides, dioxolane, benzofuran, chalcone, functional polymers

## **1. Introduction**

Today, the term "functional polymers" is used to compare the specific properties such as chemical, physicochemical or biochemical functions of polymeric materials and to classify polymers in this field. For the preparation of different purpose polymers, new monomers are obtained by binding the functional group to the structure of certain monomers. Copolymers of commercial monomers and monomers with functional groups are prepared and their properties are investigated. In addition, chemical polymers are chemically modified and functional groups are bonded to produce chemical-reactive polymers in both the industry and polymer-based chemistry. The application of chemical modification to the polymers is used to prepare polymers which cannot be prepared by direct polymerization of the monomer.

There are two ways to synthesize a polymer with the planned pendant reactive group: (1) functionalization of a non-functional polymer by chemical modification; (2) binding of a reactive side group to the monomer and polymerization of this reactive group monomer by chain addition polymerization methods [1]. Both methods have been successfully applied to obtain vinyl polymers. The synthesis and studies on (meth)acrylate polymers have attracted the attention of various groups in recently [2–13]. Acrylate homopolymers along with their copolymers are used in various fields such as thin films, adsorption, fibers, filament coatings, lithography, lacquers, adhesives, printing inks, and binders [14–34].

There are some disadvantages in linking functional groups on polymers:


## **2. Functional methacrylate ester monomer and polymer synthesis from oxirane compounds**

## **2.1 Synthesis of aryloxy-2,3-epoxy propane (oxirane)**

The oxirane compound is obtained from the epichlorohydrin with an arylalcohol. The synthesis reaction scheme is given in **Figure 1**.

A typical procedure for the reaction of arylalcohol with epichlorohydrin is as follows: arylalcohol (0.5 mol) and epichlorohydrin (1.5 mol) and sodium hydroxide (0.55 mol) are mixed with magnetic stirrer at 50°C for 10 h, and then

**Figure 1.** *Reaction scheme of aryloxy-2,3-epoxy propane.* *New Methods in the Synthesis of (Meth)Acrylates DOI: http://dx.doi.org/10.5772/intechopen.89767*

the reaction mixture is stirred at room temperature for 15 h. The organic layer is washed several times with diethylether and dried over magnesium sulfate. After removing diethylether, the excess of epichlorohydrin is distilled at 50°C and 60 mmHg. The remaining reaction mixture is distilled at 110°C and 12 mmHg (oxirane product yield: 87%). The structure of the compound aryloxy-2,3-epoxy propane is identified by the FT-IR techniques. FT-IR (cm<sup>−</sup><sup>1</sup> ): 3100–2800 (C▬H); 1590 (C〓C); 1250 (epoxy C▬O); 950–770 (epoxy C▬H).

## **2.2 Synthesis of aryloxy-2-hydroxypropyl methacrylate monomer**

Oxirane compound is distilled off again at 110°C and 12 mmHg by vacuum distillation. In a reaction flask, 0.26 mol of oxirane, 0.54 mole of methacrylic acid, 0.30 mol of pyridine, and 100 ppm of hydroquinone are mixed in 200 ml of toluene solvent at 85°C for 24 h with a magnetic stirrer. After the reaction is complete, 30% sodium hydroxide solution is added until the mixture is taken up in ethereal separation funnel and basic. The basic aqueous phase obtained at the end of the extraction is extracted three times with diethylether in another separating funnel. The collected ethereal phases are taken to the separating funnel and extracted until neutral with water. The etheric phases are taken into a collection container and a sufficient amount of anhydrous magnesium sulfate is thrown into it and left to dry for 24 h. At the end of the filtration process, the mixture separated from magnesium sulfate is distilled off the toluene at 45°C and 50 mmHg. To the remaining mixture, 50 ppm of hydroquinone was added and vacuum distillation is carried out with monomer at 150°C and 1 mmHg (monomer yield: 65%). The synthesis reaction scheme is given in **Figure 2**.

The structure of the monomer is confirmed by the FT-IR and <sup>1</sup> H- and 13C-NMR spectroscopic techniques. FT-IR (cm<sup>−</sup><sup>1</sup> ): 3600–3200 (▬OH); 3100–2800 (C▬H); 1720 (>C〓O); 1630 (CH2〓C); 1580 (aromatic, C〓C); 1250 (C▬O). 1 H-NMR (CDCl3, TMS): 8.0–6.8 (aromatics ▬H); 6.2–5.44 (CH2〓C); 4.25 (O▬H); 1.8 (CH3). 13C-NMR (CDCl3, TMS): 157.2–113.8 (aromatics ▬C); 134.0–124.4 (CH2〓C); 165.6 (>C〓O); 67.8 (CH▬OH); 17.2 (CH3).

## **2.3 Free radical polymerization of aryloxy-2-hydroxypropyl methacrylate monomer**

Appropriate amounts of aryloxy-2-hydroxypropyl methacrylate monomer and chloroform and 2,2′-azobisisobutyronitrile (AIBN) as an initiator (2% of the monomer mass) are disposed in a polymerization tube and liquidated with nitrogen for 10 min. The sealed and waxed polymerization reaction tube is placed at 60 ± 1°C for 24 h in oil bath. The reaction product is poured dropwise into an abundant of diethylether. The obtained polymer is purified by re-precipitation with diethylether from a chloroform solution and the latest operation dried under vacuum oven (conversion 90%). The synthesis reaction scheme is given in **Figure 3**.

**Figure 2.** *Reaction scheme of aryloxy-2-hydroxypropyl methacrylate monomer.*

#### **Figure 3.**

*Reaction scheme of poly aryloxy-2-hydroxypropyl methacrylate.*

The formation of the homopolymer of aryloxy-2-hydroxypropyl methacrylate is confirmed by the FT-IR and 1 H-NMR spectroscopic techniques. The main description for the polymerization of the monomer is that the characteristic double bond (vinyl structure double bond) peak signal of the monomer in the FT-IR spectrum is fully depleted and does not peak in this region in the FT-IR spectrum of the polymer. This is because the addition polymerization proceeds through the opening of the pi bond in the vinyl group. This has been effectively observed in the synthesis and characterizations herein. Two signals altered in the FT-IR spectrum of the monomer: the stretching vibration band of the vinyl group C〓C at 1630 cm<sup>−</sup><sup>1</sup> and the absorption signal at 920 cm<sup>−</sup><sup>1</sup> assigned to the C▬H bending of geminal〓CH2.

The information is clearly seen in <sup>1</sup> H-NMR spectroscopy on polymer formation. The formation of polymer is clearly evident from the disappearing of the two singlets at 6.3 and 5.4 ppm of the vinyl protons and the wide peaks at 2.4–1.3 ppm due to the conversion to the aliphatic ▬CH2 group.

## **3. Functional methacrylate ester monomer and polymer synthesis from arylacetylhalide compounds**

#### **3.1 Synthesis of arylacetylhalide**

Arylacetyl chloride is prepared by reacting arylalcohol with chloroacetyl chloride using the K2CO3. A typical procedure for the acylation reaction of arylalcohol with chloroacetyl chloride is as follows: arylalcohol (1 mol) and K2CO3 are dissolved in 20 ml of anhydrous benzene at 0°C, and then 1.1 mol of chloroacetyl-chloride is added dropwise to this solution. The reaction mixture is stirred at room temperature for 15 h. The organic layer is washed several times with diethylether and dried over MgSO4. After removing diethylether, α-chloro-arylacetamide is crystallized from methanol (yield: 80%). The structure of the compound arylacetylhalide is identified by the FT-IR techniques. FT-IR (cm<sup>−</sup><sup>1</sup> ): 3100–2800 (C▬H); 1730 (>C〓O); 1580 (aromatic, C〓C). The synthesis reaction scheme is given in **Figure 4**.

#### **3.2 Synthesis of aryloxycarbonyl methyl methacrylate monomer**

Aryloxycarbonyl methyl methacrylate is synthesized as follows: a mixture of arylacetyl chloride (1 mol), sodium methacrylate (1.1 mol) in 100 ml acetonitrile and triethylbenzylammonium chloride (TEBAC) (0.1 mol) as a phase transfer

$$\begin{array}{ccccc} & & \mathsf{K\_2CO\_3} & & \\ \mathsf{Ar-OH} & + & \mathsf{Cl-C-C-CH\_2Cl} & \xrightarrow{\begin{subarray}{c} \mathsf{K\_2CO\_3} \\ \mathsf{RO-C-CH\_2Cl} \end{subarray}} & \mathsf{Ar-O-C-CH\_2Cl} & + & \mathsf{HCl-C-CH\_2Cl} & + \\ \end{array}$$

**Figure 4.** *Reaction scheme of arylacetylhalide.* *New Methods in the Synthesis of (Meth)Acrylates DOI: http://dx.doi.org/10.5772/intechopen.89767*

#### **Figure 5.**

*Reaction scheme of aryloxycarbonyl methyl methacrylate monomer.*

catalyst better and sodium iodide (NaI) (0.1 mol) as catalyst are receipt in a threeneck round bottom flask equipped with a thermometer, magnetic stirrer, and heated to 85°C in a reflux condenser in the presence of 100 ppm hydroquinone. The reaction is continued for an additional 30 h. The reaction mixture is cooled to 20°C and moved to a separating funnel, washed sequentially with diethylether, 5% NaOH, and distilled water. The organic layer are spooled and dried over anhydrous magnesium sulfate (MgSO4) for 24 h. Magnesium sulfate is filtered and the diethylether is removed from the organic layers with a rotary evaporator. The resulting monomer is purified by recrystallization from ethanol (yield: 85%). The synthesis reaction scheme is given in **Figure 5**.

The structure of the monomer is confirmed by the FT-IR and <sup>1</sup> H- and 13C-NMR spectroscopic techniques. FT-IR (cm<sup>−</sup><sup>1</sup> ): 3100–2800 (C▬H); 1730 (>C〓O); 1630 (CH2〓C); 1580 (aromatic, C〓C); 1250 (C▬O). 1 H-NMR (CDCl3, TMS): 7.9–6.6 (aromatics ▬H); 6.2–5.41 (CH2〓C); 1.8 (CH3). 13C-NMR (CDCl3, TMS): 157.1– 113.4 (aromatics ▬C); 134.4–124.2 (CH2〓C); 165.2 (>C〓O); 18.1 (CH3).

#### **3.3 Free radical polymerization of aryloxycarbonyl methyl methacrylate monomer**

Homopolymer of aryloxycarbonyl methyl methacrylate is synthesized using 2,2′-azobisisobutyronitrile (AIBN) as an initiator (2% of the monomer mass) in 1,4-dioxane solution. The reaction mixture is de-aerated by passing nitrogen gas for 10 min, then the tube is tightly sealed and kept in a thermostatic oil bath at 60 ± 1°C for 24 h. The homopolymer is precipitated in excess methanol, purified by dissolution in 1,4-dioxane and reprecipitation in methanol. The homopolymer is dried in vacuum to constant weight (conversion 90%). The synthesis reaction path is given in **Figure 6**.

The formation of the homopolymer of aryloxycarbonyl methyl methacrylate is confirmed by the <sup>1</sup> H-NMR and FT-IR spectroscopic techniques. The information is clearly seen in 1 H-NMR spectroscopy on polymer formation. The formation of polymer is clearly evident from the disappearing of the two singlets at 6.3 and 5.4 ppm of the vinyl protons and the wide peaks at 2.4–1.3 ppm due to the conversion to the aliphatic-CH2 group. The main description of the polymer is exactly the extinction of some characteristic peaks of the double bond in the FT-IR spectrum, and this has

**Figure 6.** *Reaction scheme of poly aryloxycarbonyl methyl methacrylate.*

been effectively observed in the synthesis and characterizations herein. Two signals altered in the FT-IR spectrum of the monomer: the stretching vibration band of the vinyl group C〓C at 1630 cm<sup>−</sup><sup>1</sup> and the absorption signal at 920 cm<sup>−</sup><sup>1</sup> assigned to the C▬H bending of geminal〓CH2.

## **4. Functional methacrylate ester monomer and polymer synthesis from α-chloro-N-arylacetamide compounds**

## **4.1 Synthesis of α-chloro-N-arylacetamide**

α-chloro-N-arylacetamide is prepared by reacting arylamine with chloroacetylchloride using the K2CO3. A typical procedure is as follows: arylamine (1 mol) and K2CO3 were dissolved in 20 ml of anhydrous benzene at 0°C, and then 1.1 mol of chloroacetylchloride are added dropwise to this solution. The reaction mixture is stirred at room temperature for 15 h. The organic phase is washed several times with diethylether and dried over MgSO4. After removing diethylether, α-chloro-Narylacetamide is crystallized from methanol (yield: 80%). The synthesis reaction scheme is given in **Figure 7**.

The structure of the compound α-chloro-N-arylacetamide is identified by the FT-IR techniques. FT-IR (cm<sup>−</sup><sup>1</sup> ): 3340 (NH); 3100–2800 (C▬H); 1680 (>C〓O); 1580 (aromatic, C〓C).

#### **4.2 Synthesis of arylamido methyl methacrylate monomer**

Arylamido methyl methacrylate is synthesized as follows: 1.1 mol sodium methacrylate, 1 mol α-chloroacetamide, 0.1 mol NaI and 0.1 mol TEBAC and as catalyst are stirred in 100 ml acetonitrile at 80°C in a reflux condenser for 30 h in the presence of 100 ppm hydroquinone. After the solution is cooled to 20°C and neutralized with a 5% NaOH solution. The organic phase is washed a few times with water, and the water phase is washed with diethylether a several times. The diethyl ether phase and the acetonitrile phase are spooled and dried over anhydrous magnesium sulfate for 24 h. Diethyl ether and acetonitrile are removed with a rotary evaporator. The organic phases are collected and the residue is distilled at 130°C at 5 mmHg to give a colorless liquid (yield: 80%). The synthesis reaction scheme is given in **Figure 8**.

$$\begin{array}{cccc} \text{Ar-NH}\_2 & \star & \text{Cl} \text{-} \text{C} \text{-} & \text{C} \text{+} \text{O}\_2 \text{Cl} & \begin{array}{c} \text{Ar-CO}\_3, \\ \text{Ar-O} \text{-} \text{C} \text{-} \text{C} \text{+} \text{O}\_2 \text{Cl} & \begin{array}{c} \text{Ar-O} \text{(r} \text{-} \text{S)} \text{(r} \text{-} \text{S)} \end{array} \\ \text{@-} \text{O}\_2 & \begin{array}{c} \text{Ar-O} \text{(r} \text{-} \text{C} \text{-} \text{C} \text{-} \text{S)} \text{(r} \text{-} \text{H} \text{O} \\ \text{O} \end{array} \\ \end{array} \end{array} & \begin{array}{c} \text{Ar-OH} \text{(r} \text{-} \text{C} \text{-} \text{C} \text{H}\_2 \text{O} \text{(r} \text{-} \text{H} \text{O} \text{)} \\ \text{@-} \text{C} \text{(r} \text{-} \text{C} \text{-} \text{C} \text{-} \text{C} \text{(r} \text{-} \text{C)} \text{(r} \text{-} \text{C)} \text{(r} \text{-} \text{C)} \text{(r} \text{-} \text{C)} \text{(r} \text{-} \text{C)} \end{array} \end{array}$$

**Figure 7.** *Reaction scheme of α-chloro-N-arylacetamide.*

$$\begin{array}{ccccc} \text{O} & \text{C} \text{H}\_{2}\text{O} & \text{C} \\ \text{O} & \text{C} \text{O} & \text{C} \\ \text{O} & \text{C} & \text{O} \end{array} \quad \begin{array}{ccccc} \text{O} & \text{C} \text{H}\_{3}\text{O} & \text{C} \text{H}\_{2}\text{O} \\ \text{O} & \text{C} \text{O} & \text{C} \text{O} \\ \text{O} & \text{C} \text{O} & \text{C} \text{O} \\ \text{O} & \text{C} & \text{C} \end{array} \quad \begin{array}{ccccc} \text{T} & \text{T} \text{H}\_{2}\text{O} & \text{C} \\ \text{O} & \text{C} \text{O} & \text{C} \text{O} \\ \text{O} & \text{C} \text{O} & \text{C} \text{O} \\ \text{O} & \text{C} & \text{C} \end{array}$$

**Figure 8.** *Reaction scheme of arylamido methyl methacrylate monomer.*

*New Methods in the Synthesis of (Meth)Acrylates DOI: http://dx.doi.org/10.5772/intechopen.89767*

**Figure 9.**

*Reaction scheme of poly arylamido methyl methacrylate.*

The structure of the monomer is confirmed by the FT-IR and <sup>1</sup> H- and 13C-NMR spectroscopic techniques. FT-IR (cm<sup>−</sup><sup>1</sup> ): 3325 (NH); 3100–2800 (C▬H); 1680 (>C〓O); 1630 (CH2〓C); 1580 (aromatic, C〓C); 1230 (C▬O▬C). 1 H-NMR (CDCl3, TMS): 9.1 (N▬H); 8.0–6.7 (aromatics ▬H); 6.3–5.43 (CH2〓C); 1.8 (CH3). 13C-NMR (CDCl3, TMS): 157.1–113.4 (aromatics ▬C); 134.4–124.2 (CH2〓C); 168.1 (>C〓O); 18.1 (CH3).

#### **4.3 Free radical polymerization of arylamido methyl methacrylate monomer**

Arylamido methyl methacrylate monomer is freed from inhibitor by washing with a dilute KOH solution followed by distilled water and then drying over MgSO4. Appropriate amounts of arylamido methyl methacrylate monomer, 2,2′-azobisisobutyronitrile (AIBN) (2% of the monomer mass) and 1,4-dioxane are placed in a polymerization reaction tube and purged with nitrogen for 15 min. The closed mouth polymerization reaction tube is kept at 60 ± 1°C for 30 h in oil bath. The reaction product is poured dropwise into an abundant of n-hexane. The obtained polymer is purified by re-precipitation with n-hexane from a 1,4-dioxane solution and the latest operation dried under vacuum oven (conversion 90%). The synthesis reaction scheme is given in **Figure 9**.

The structure of poly arylamido methyl methacrylate is confirmed by the FT-IR and <sup>1</sup> H-NMR spectroscopic techniques. The main description for the polymerization of the monomer is that the characteristic double bond (vinyl structure double bond) peak signal of the monomer in the FT-IR spectrum is fully depleted and does not peak in this region in the FT-IR spectrum of the polymer. This is because the addition polymerization proceeds through the opening of the pi bond in the vinyl group. This has been effectively observed in the synthesis and characterizations herein. Two signals altered in the FT-IR spectrum of the monomer: the stretching vibration band of the vinyl group C〓C at 1630 cm<sup>−</sup><sup>1</sup> and the absorption signal at 920 cm<sup>−</sup><sup>1</sup> assigned to the C▬H bending of geminal〓CH2.

The information is clearly seen in <sup>1</sup> H-NMR spectroscopy on polymer formation. The formation of polymer is clearly evident from the disappearing of the two singlets at 6.3 and 5.4 ppm of the vinyl protons and the wide peaks at 2.8–1.4 ppm due to the conversion to the aliphatic ▬CH2 group.

## **5. Functional methacrylate ester monomer and polymer synthesis from aryl-1,3-dioxolane compounds**

#### **5.1 Synthesis of (aryl-1,3-dioxolane-4-yl) methanol**

(Aryl-1,3-dioxalan-4-yl)methanol is prepared by reacting arylaldehyde with glycerin using the *p*-toluenesulfonic acid as catalyst. A typical procedure is as follows: Arylaldehyde (0.1 mol), glycerin (0.1 mol), *p*-toluenesulfonic acid (*p*-TOS)

**Figure 10.** *Reaction scheme of (aryl-1,3-dioxolane-4-yl) methanol.*

(0.5 g, as catalyst) and toluene (30 mL) are placed in a 100 mL three-necked reaction balloon fitted with a thermometer, condenser and a stirrer. The reaction mixture is refluxed at 115°C for 2 h with strong mixing. The reaction mixture is extracted a few times with diethyl ether and then 5% KOH solution, diethyl ether and toluene, respectively. The diethyl ether and toluene solvents are evaporated with rotary evaporator. The raw product is washed with water (40 mL × 3) and dried over anhydrous magnesium sulfate at overnight. The synthesis reaction scheme is given in **Figure 10**.

The structure of (aryl-1,3-dioxolane-4-yl) methanol is identified by the FT-IR and 1 H- and 13C-NMR spectroscopic techniques. FT-IR (cm−<sup>1</sup> ): 3500–3110 (O▬H); 3100–2800 (C▬H); 1570 (aromatic, C〓C); 1180 (C▬O▬C). 1 H-NMR (CDCl3, TMS): 7.48–7.0 (aromatics ▬H); 6.3–5.52 (CH2〓C); 4.0–3.7 (▬O▬CH); 4.17–4.11 (O▬CH2); 3.16 (▬OH), 3.0 (CH2). 13C-NMR (CDCl3, TMS): 151.1–116.4 (aromatics ▬C); 134.4–124.2 (CH2〓C); 63.1 (CH2); 68.8 (O▬CH2); 77.3 (O▬CH).

#### **5.2 Synthesis of (aryl-1,3-dioxolane-4-yl) methyl acrylate monomer**

(Aryl-1,3-dioxalan-4-yl)methanol (0.1 mol), triethyl amine (NR3) (20 mL, as catalyst) and diethyl ether (40 mL) are filled in a 250 mL four-necked reaction balloon fitted with a thermometer, a condenser, a stirrer and an addition funnel including 15 mL acryloyl chloride. The acryloyl chloride is added drop wise to the solution with a dropping funnel. The temperature of the reaction mixture is hold by a cryostat at −5°C for 18 h. The reaction mixture is extracted a few times with 5% KOH solution and after dried over anhydrous magnesium sulfate for 24 h. The solvents are removed by the vacuum evaporator. The synthesis reaction scheme is given in **Figure 11**.

The structure of (aryl-1,3-dioxolane-4-yl) methyl acrylate is confirmed by the FT-IR and 1 H- and 13C-NMR spectroscopic techniques. FT-IR (cm−<sup>1</sup> ): 3100–2800 (C▬H); 1727 (>C〓O); 1630 (CH2〓C); 1570 (aromatic, C〓C); 1190 (C▬O▬C). 1 H-NMR (CDCl3, TMS): 7.6–7.0 (aromatics ▬H); 6.3–5.52 (CH2〓C); 5.8 (Ar▬CH); 4.2–3.8 (▬O▬CH); 4.2–4.1 (O▬CH2); 3.0 (CH2). 13C-NMR (CDCl3, TMS): 166.2 (>C〓O); 151.1–116.4 (aromatics ▬C); 130.4–122.2 (CH2〓C); 103.2 (Ar▬CH); 63.1 (CH2); 68.8 (O▬CH2); 87.2 (O▬CH).

**Figure 11.** *Reaction scheme of (aryl-1,3-dioxolane-4-yl) methyl acrylate monomer.*

*New Methods in the Synthesis of (Meth)Acrylates DOI: http://dx.doi.org/10.5772/intechopen.89767*

**Figure 12.** *Reaction scheme of poly(aryl-1,3-dioxolane-4-yl) methyl acrylate.*

### **5.3 Free radical polymerization of arylamido methyl methacrylate monomer**

Free radical polymerization reaction of (aryl-1,3-dioxolane-4-yl) methyl acrylate monomer is conducted in a polymerization reaction tube using 2,2′-azobisisobutyronitrile (AIBN) (1% of the monomer mass) as initiator in 10 mL of 1,4-dioxane, at 65°C with 90% conversion in 6 h. The formed polymer is precipitated in ethyl alcohol. The obtained polymer is dried under vacuum at 45°C for 24 h for constant weight. The synthesis reaction scheme is given in **Figure 12**.

The structure of poly(aryl-1,3-dioxolane-4-yl) methyl acrylate is confirmed by the FT-IR and 1 H-NMR spectroscopic techniques. The information is clearly seen in 1 H-NMR spectroscopy on polymer formation. The formation of polymer is clearly evident from the disappearing of the two singlets at 6.3 and 5.42 ppm of the vinyl protons and the wide peaks at 2.9–1.5 ppm due to the conversion to the aliphatic ▬CH2 group. The main description of the polymer is exactly the extinction of some characteristic peaks of the double bond in the FT-IR spectrum, and this has been effectively observed in the synthesis and characterizations herein. Two signals altered in the FT-IR spectrum of the monomer: the stretching vibration band of the vinyl group C〓C at 1630 cm<sup>−</sup><sup>1</sup> and the absorption signal at 920 cm<sup>−</sup><sup>1</sup> assigned to the C▬H bending of geminal〓CH2.

## **6. Functional methacrylate ester monomer and polymer synthesis from benzofuran compounds**

#### **6.1 Synthesis of acetyl benzofuran**

Synthesis of acetyl benzofuran is as follows: Potassium carbonate (K2CO3) (0.1 mol) and 2-hydroxybenzaldehyde (1 mol) are dissolved in 30 ml of absolute acetone. The reaction mixture is taken in a three-neck round bottom reaction balloon equipped with a magnetic stirrer, a thermometer, and cooled to 0°C. After then chloroacetone (1.1 mol) are added dropwise to this solution at 5°C, and stirred at 20°C for 16 h. The organic phase is washed a few times with distilled water and separation layer is filtered through filter paper and dried over anhydrous MgSO4 overnight. Acetyl benzofuran compound is crystallized from ethyl alcohol. Yield: 85%. The synthesis reaction scheme is given in **Figure 13**.

The structure of acetyl benzofuran is identified by the FT-IR techniques. FT-IR (cm<sup>−</sup><sup>1</sup> ): 3100–2800 (C▬H); 1690 (>C〓O); 1570 (aromatic, C〓C).

#### **6.2 Synthesis of bromo-acetyl benzofuran**

Acetyl benzofuran (1 mol) is dissolved in 200 mL acetic acid, and after then bromo is added dropwise to this solution at 25°C for 2 h. After bromination reaction, the mixture is divided into ice-water. The separation layer is filtered through

**Figure 13.**

*Reaction scheme of acetyl benzofuran.*

**Figure 14.**

*Reaction scheme of bromo acetyl benzofuran.*

**Figure 15.** *Reaction scheme of acetyl benzofuryl methyl methacrylate monomer.*

filter paper and dried over anhydrous magnesium sulfate (MgSO4) overnight. Bromo-acetyl benzofuran compound is crystallized from ethyl alcohol. Yield: 85%. The synthesis reaction scheme is given in **Figure 14**.

The structure of bromo acetyl benzofuran is identified by the FT-IR techniques. FT-IR (cm<sup>−</sup><sup>1</sup> ): 3100–2800 (C▬H); 1690 (>C〓O); 1570 (aromatic, C〓C); 780 (CH▬Br).

#### **6.3 Synthesis of acetyl benzofuryl methyl methacrylate monomer**

Sodium methacrylate (1.1 mol), bromo-acetyl benzofuran (1 mol), sodium iodide (0.1 mol) and triethylbenzylammoniumchloride (TEBAC) (0.1 mol) as catalyst are mixed in 100 mL acetonitrile at 70°C in a reflux condenser for 20 h in the beside of 100 ppm hydroquinone as an inhibitor. After then the solution is cooled to 20°C and neutralized with a 5% NaOH solution. The organic phase is washed with diethyl ether a few times. The diethyl ether and acetonitrile layers are spooled and dried over anhydrous magnesium sulfate (MgSO4) overnight. Diethyl ether and acetonitrile are evaporated with a rotary evaporator. The organic layers are collected and the residue is crystallized from ethyl alcohol. Yield: 80%. The synthesis reaction scheme is given in **Figure 15**.

The structure of acetyl benzofuryl methyl methacrylate is confirmed by the FT-IR and 1 H- and 13C-NMR spectroscopic techniques. FT-IR (cm−<sup>1</sup> ): 3100–2800 (C▬H); 1735 (>C〓O); 1685 (▬C〓O); 1630 (CH2〓C); 1580 (aromatic, C〓C); 1190 (C▬O▬C). 1 H-NMR (CDCl3, TMS): 7.7–7.2 (aromatics ▬H); 6.3–5.48 (CH2〓C); 4.2– 4.0 (O▬CH2); 1.5 (CH3). 13C-NMR (CDCl3, TMS): 178.2 (▬C〓O); 168.1 (>C〓O); 148.1–116.2 (aromatics ▬C); 130.1–122.0 (CH2〓C); 68.8 (O▬CH2); 19.1 (CH3).

#### **6.4 Free radical polymerization of acetyl benzofuryl methyl methacrylate monomer**

The preparation of homopolymer of Acetyl benzofuryl methyl methacrylate monomer is synthesized by free radical polymerization in 1,4-dioxane solvent

*New Methods in the Synthesis of (Meth)Acrylates DOI: http://dx.doi.org/10.5772/intechopen.89767*

**Figure 16.** *Reaction scheme of poly acetyl benzofuryl methyl methacrylate.*

using 2,2′-azobisisobutyronitrile (AIBN) as a free radical initiator. The homopolymer is purified by repeated reprecipitation from 1,4-dioxane and then filtered and dried until a constant weight is attained. The synthesis reaction path is given in **Figure 16**.

The structure of poly acetyl benzofuryl methyl methacrylate is confirmed by the FT-IR and <sup>1</sup> H-NMR spectroscopic techniques. The information is clearly seen in <sup>1</sup> H-NMR spectroscopy on polymer formation. The formation of polymer is clearly evident from the disappearing of the two singlets at 6.3 and 5.42 ppm of the vinyl protons and the wide peaks at 2.9–1.5 ppm due to the conversion to the aliphatic ▬CH2 group. The main description of the polymer is exactly the extinction of some characteristic peaks of the double bond in the FT-IR spectrum, and this real is effectively identified herein. Two signals altered in the FT-IR spectrum of the monomer: the stretching vibration band of the vinyl group C〓C at 1630 cm<sup>−</sup><sup>1</sup> and the absorption signal at 920 cm<sup>−</sup><sup>1</sup> assigned to the C▬H bending of geminal〓CH2.

## **7. Functional methacrylate ester monomer and polymer synthesis from photocrosslinkable functional group (pendant chalcone unit) compounds**

#### **7.1 Synthesis of hydroxyphenyl-methoxystyryl ketone (hydroxy chalcone)**

Substituted benzaldehyde (1 mol) and substituted acetophenone (1 mol) are dissolved in 50 mL of ethyl alcohol and cooled at 18°C. An aqueous NaOH solution (1 mol in 40 mL of distilled water) is then added dropwise with constant mixing and as keeping the temperature constant at 18°C. After stirring the reaction mixture for 12 h at 20°C, it is neutralized with dilute HCl to isolate the compound. The obtained solid matter is filtered through filter paper, washed with ice cold water, dried and recrystallized from ethyl alcohol. Yield: 75%. The synthesis reaction scheme is given in **Figure 17**.

The structure of hydroxyl chalcone is identified by the FT-IR techniques. FT-IR (cm<sup>−</sup><sup>1</sup> ): 3500–3200 (O▬H); 3100–2800 (C▬H); 1690 (>C〓O); 1605 (▬CH〓CH▬); 1570 (aromatic, C〓C).

**Figure 17.** *Reaction scheme of hydroxyl chalcone.*

**Figure 18.** *Reaction scheme of methacryloyloxyphenyl-methoxystyryl ketone.*

#### **7.2 Synthesis of methacryloyloxyphenyl-methoxystyryl ketone**

In a 250 mL three-necked flask, triethylamine (3 mol) and hydroxyphenylmethoxystyryl ketone (1 mol) are dissolved in 100 mL of methyl ethyl ketone (MEK) and cooled between 0 and −5°C. Methacryloyl chloride (1.1 mol) in 50 mL of methyl ethyl ketone is then added drop by drop with mixing. After then, the reaction mixture is mixed for 3 h at 20°C and the precipitated quaternary ammonium salt is filtered off. Later, 100 ppm of hydroquinone is added to this solution and the MEK is removed by the vacuum evaporator. The raw product is dissolved in diethyl ether, washed one after another with a 5% aqueous potassium hydroxide solution and distilled water, dried over anhydrous magnesium sulfate (MgSO4) and the diethyl ether is removed by the evaporator. The obtained material is recrystallized from methyl alcohol to get the shining yellow flakes of sübstitue methacryloyloxyphenyl-methoxystyryl ketone. Yield: 80%. The synthesis reaction scheme is given in **Figure 18**.

The structure of methacryloyloxyphenyl-methoxystyryl ketone is confirmed by the FT-IR and 1 H- and 13C-NMR spectroscopic techniques. FT-IR (cm−<sup>1</sup> ): 3100–2800 (C▬H); 1740 (>C〓O); 1650 (▬C〓O); 1630 (CH2〓C); 1605 (▬CH〓CH▬); 1570 (aromatic, C〓C); 1190 (C▬O▬C). 1 H-NMR (CDCl3, TMS): 8.1–6.9 (aromatics ▬H); 6.3–5.78 (CH2〓C, and ▬CH〓CH▬); 3.84 (OCH3); 1.8 (CH3). 13C-NMR (CDCl3, TMS): 178.0 (▬C〓O); 166.8 (>C〓O); 148.1–116.2 (aromatics ▬C); 130.1–122.0 (CH2〓C, and ▬CH〓CH▬); 58.1 (OCH3); 19.1 (CH3).

## **7.3 Free radical polymerization of substituted methacryloyloxyphenylmethoxystyryl ketone monomer**

Substituted methacryloyloxyphenyl-methoxystyryl ketone is polymerized as a 3 molar solution in MEK using 2,2′-azobisisobutyronitrile (AIBN) as initiator at 70°C. The predetermined quantities of sübstitue methacryloyloxyphenyl-methoxystyryl ketone, the initiator (1 wt.% of monomer) and solvent are placed in a polymerization tube and the mixture is flushed with a slow stream of nitrogen for 20 min. Then, the tube is closed and placed in the thermostated oil bath at 70°C. After the specified time (12 h), the contents are added to excess methyl alcohol to precipitate the polymer. The crude polymer is purified by redissolving in 1,4-dioxane and reprecipitated by methyl alcohol, filtered, washed with methyl alcohol and dried under vacuum at 45°C for constant weight. Yield: 60%. The reaction scheme is shown below (**Figure 19**).

The structure of poly methacryloyloxyphenyl-methoxystyryl ketone is confirmed by the FT-IR and <sup>1</sup> H-NMR spectroscopic techniques. The information is clearly seen in 1 H-NMR spectroscopy on polymer formation. The formation of polymer is clearly evident from the disappearing of the two singlets at 6.3 and 5.78 ppm of the vinyl protons and the wide peaks at 2.7–1.3 ppm due to the conversion to the aliphatic ▬CH2 group. The main description of the polymer is exactly the extinction of some characteristic peaks of the double bond in the FT-IR *New Methods in the Synthesis of (Meth)Acrylates DOI: http://dx.doi.org/10.5772/intechopen.89767*

**Figure 19.**

*Reaction scheme of poly methacryloyloxyphenyl-methoxystyryl ketone.*

spectrum, and this real is effectively identified herein. Two signals altered in the FT-IR spectrum of the monomer: the stretching vibration band of the vinyl group C〓C at 1630 cm<sup>−</sup><sup>1</sup> and the absorption signal at 920 cm<sup>−</sup><sup>1</sup> assigned to the C▬H bending of geminal〓CH2.

## **8. Conclusion**

In this paper, reaction pathway for the synthesis of new methacrylates having pendant amide, dioxolane, benzofuran and chalcone groups are described. Molecular structure information such as reaction scheme, Fourier transform infrared (FT-IR) and nuclear magnetic resonance spectroscopy of all the compounds is given. All of the methacrylates are used as photodegradable packaging materials and photoresists for microlithography. The increasing utility of photosensitive polymers in many applications such as microelectronics, printing and UV-curable lacquers, and inks is provided us with an incentive to obtain novel polymers.

## **Conflict of interest**

The authors declare no conflict of interest.

## **Author details**

Cengiz Soykan Department of Materials Science and Nanotechnology, Faculty of Engineering, University of Uşak, Uşak, Turkey

\*Address all correspondence to: cengizsoykan@usak.edu.tr

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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## **Chapter 7**

## Biodegradable Polymers: Opportunities and Challenges

*Marieli Rosseto, Cesar V.T. Rigueto, Daniela D.C. Krein, Naiana P. Balbé, Lillian A. Massuda and Aline Dettmer*

## **Abstract**

The overuse of polymer materials from fossil sources has generated a large volume of waste that causes environmental impacts due to the degradation time. The technological advance has stimulated the search for alternatives that can contribute to sustainability. In this context, the use of biodegradable polymers, that use raw materials from renewable sources stand out because they have that ability to form films and come from abundant sources. Also, in the expectation of optimizing the environmental benefits in this process, it is possible to value the agroindustrial residues, using them as raw material in the synthesis of the polymer, the physical, chemical and mechanical properties of these polymers are important to evaluate the possible applications. The proposal of this chapter is to present current research on renewable sources, including agricultural and industrial residues, to obtain biodegradable polymers, highlighting their properties and possibilities of application.

**Keywords:** sustainability, waste, biodegradable, renewable, agroindustrial

### **1. Introduction**

The increasing environmental impacts of pollution derived from fossil polymers are drawing attention to the need to produce sustainable materials. And the biodegradable polymers generated from renewable sources are an alternative to this problem [1]. They are made from renewable or synthetic sources that have the capacity to degrade by the action of microorganisms [2, 3].

In the search for biodegradable and renewable materials, the biopolymers that are gaining prominence are those that have greater availability: cellulose, chitosan, starch and proteins (collagen, soy, casein). As these sources are widely used in the food, pharmaceutical, agricultural, and other industries, material research has been developing in the quest to recover them from agroindustrial waste. These could be reinserted into the process as a source for synthesizing biodegradable polymers, as both industries and agriculture generate waste that is sometimes incorrectly disposed of in the environment.

Residues and by-products generated in larger quantities include fruit and vegetable residues (husks, seeds and stems), grain residues (rice, wheat, soy) and protein products (chitosan, gelatin, whey protein) [4]. Approximately 26% of food waste is generated from the beverage industry, followed by the dairy industry (21%), fruit and vegetables (14.8%), cereals processing (12.9%), preservation of meat products (8%), processing of oils of vegetable and animal origin (3.9%), among others (12.7%) [5].

The use of residues is seen as an opportunity for sustainability due to its ease of production and low cost, non-toxicity, biocompatibility, biodegradability, chemical and thermal stabilities [6]. Associated with the concern to replace materials of fossil origin, attention to the reuse of wastes/by-products of agricultural or agroindustrial origin is of extreme importance. In this way, in addition to contributing to the reduction of disposal of waste in landfills or the burning of landfills, the principle of reuse affects the economy in a positive way.

Despite these advantages, the water absorption is very high, due to the number of hydrophilic groups contained in the structure of the materials of renewable origin. To overcome this factor, techniques have been applied to improve the physical and mechanical properties of these materials, ensuring a better application performance. In addition, there is still a large gap between policy and implementation of these new technologies [7].

The following sections discuss the main sources of biodegradable polymers, aiming to know their specificities, so that to facilitate the link between possible sources to obtain them from agricultural or industrial waste, as well as the applicability of the material.

#### **2. Sources for obtaining biodegradable polymers: opportunities**

In the search for biodegradable and renewable materials, the biopolymers that are gaining prominence are those that present greater availability: cellulose, chitosan, starch and proteins.

These sources are widely used in the food, pharmaceutical and agricultural industries, causing the generation of large amounts of waste. This problem has aroused interest in research aimed at obtaining biopolymers from the recovery of the same, relating low cost, availability and sustainability.

#### **2.1 Cellulose**

Cellulose is the agroindustrial waste most reuse. Its main sources of production are mainly of vegetal origin (wood and cotton), however, it is also synthesized by algae, tunicates and some bacteria [8–10].

The cellulose molecule ((C6H10O5)n) has a linear ribbon-like conformation, and its compounds bound together by the so-called β1-4, glycosidic bonds. The number of chain repeats n varying according to the source of the obtainment, wherein in wood, for example, is about 10,000 and 15,000 in cotton. These chains impart rigidity to the cellulose, providing good mechanical properties and thermal stability. However, cellulose dissolution is a difficult process and it is necessary to develop new techniques that allow the use of regenerated cellulose as a component of polymeric materials [11, 12].

The materials produced from regenerated cellulose acquire exceptional physical and chemical characteristics, as well as clear benefits for society, especially when minimizing environmental impacts. During the regeneration of the cellulose solution, physical and chemical treatments can be applied generating functional and biocompatible materials, organic hybrids or porous membranes, making the use of cellulose comprehensive [12].

In this sense, the cellulose modification has been the focus of several studies, aiming to evaluate it as a substitute raw material to obtain synthetic polymers, fibers, films and membranes, hydrogels and aerogels, bioplastics, beads and microspheres as shown in (**Table 1**).


#### **Table 1.**

*Studies to obtain materials with cellulose in its composition.*

Recent studies have turned their efforts to provide reuse and value adding to industrial waste. In order to convert lignocellulosic materials into nanocellulose, [26] used the residues of tobacco stalks after steam blasting followed by bleaching and refining to produce nanofibrillated cellulose (NFC), successfully reaching the objective of the study, and generating a promising alternative for the reuse of this residue organic.

Reference [27] extracted microcrystalline cellulose (MCC) and spherical nanocrystalline cellulose (SNCC) by acid hydrolysis from cotton fabric waste, concluding that the developed process is suitable for industrial scale application, since the generation of cotton waste is high, as well as the cellulose content contained in them (about 94%).

Reference [28] isolated microcrystalline cellulose powder (MCC) from waste paper from three sources (books, newspapers and cardboard), evaluating the effect of the

treatment using various concentrations of sodium hydroxide (NaOH) on the properties of the powders obtained, concluding that the lowest concentration, which was 5% (m/v) NaOH in the medium, was ideal for MCC isolation in these paper wastes.

Aiming to reduce the environmental impacts caused in aquatic life due to the contamination of water by complex substances such as petroleum and vegetable oils, [29] developed a hydrophobic aerogel with high sorption capacity, from cellulose nanofibres obtained from waste from the furniture industry, processed via acidic hydrolysis by steam explosion for oil sorption. The authors tested the sorption capacity of the aerogel produced in homogeneous media (pure oil and vegetable oil) and heterogeneous medium (oil in water), where it had high sorption capacity in both media, 19.55 and 19.21 goil gaerogel<sup>−</sup><sup>1</sup> , for petroleum and oil respectively.

#### **2.2 Chitosan**

The chitosan is a molecule with a carbohydrate structure like cellulose, consisting of two types of repeating units, N-acetyl-D-glucosamine and D-glucosamine, linked by β1-4 glycosidic bonds [30]. They are the most abundant organic compounds after cellulose [31].

It is widely distributed in the animal kingdom (shells of crustaceans and mollusks, the backbone of squid and the cuticle of insects) and vegetable (algae, protozoa and the cell wall of several fungal species) [32].

The degree of acetylation differentiates chitin from chitosan, when the polymer has a degree of acetylation greater than 50%, is called chitin, and when the degree of acetylation is less than 50%, it is called chitosan [33].

Reference [34] discuss the main methods of chitosan extraction, measure alkaline treatment, which is most commonly used at the industrial level, and sodium hydroxide (NaOH), which is commonly used for the deacetylation process. The enzymatic deacetylation that uses chitin deacetylases obtained from different biological sources, such as fungi and insects to effect treatment. And steam explosion, which performs a hydrothermal treatment where the chitin is treated with a blow gun, with saturation vapor at increased pressure and temperature for several minutes, followed by explosive decomposition.

There are several studies that provide application opportunities for a chitosan. For the food area: active films, antioxidants, antimicrobials, chitosan compounds, edible coatings, application in fruits and vegetables and application in seafood products [35]. [36] made a comparison between nano-composite films based on gelatin and starch modified by nanocellulose and chitosan for packaging applications. And [37] developed and evaluated an antioxidant film and pH indicator based on sources of chitosan and food waste. [38] incorporated the extract of mango leaves to the antioxidant film of chitosan for active food packaging.

In addition, it can be used in a number of areas, such as biomedicine, pharmaceuticals, food, agriculture, personal care products and the environmental sector [39]. [40] developed nanoparticles of chitosan coating for the treatment of brain diseases. [41] studied nanogels of chitosan as nanocarriers of polyoxometalates for breast cancer therapies. In the environmental area [41] have developed a lysozymechitosan biocomposite for the effective removal of dyes and heavy metals from aqueous solutions. [42] have made antibacterial and ecologically correct membranes of chitosan and polyvinyl alcohol for air filtration. In the area of agriculture [43] chitosan nanoparticle delivery systems for sustainable agriculture and [44] biocompatible chitosan nanoparticles loaded with agrochemicals for pest management.

However, there is a great waste of chitosan in marine waste from processing industries, there has been a significant increase in recent years, due to modern seafood processing practices that result in the accumulation of a large volume of waste (skin, head, tails, shells, scales, spine). As the rate of biodegradation of this material is low because chitin is not soluble in water, this volume accumulates and consequently causing environmental impacts. [45, 46].

These marine residues are potential materials for extracting chitin and chitosan. This requires the recovery of chitosan present in these wastes. [47] extract and characterize the fish scale chitosan (*Labeo rohita*). While [48] make the extraction from abundant shrimp residues (exoskeleton - shells). Already [49] use as extraction source the blue crab. And [50] performed alkaline hydrolysis to recover the chitin and chitosan from the squid feather and used the residual water of this process to recover the proteins and evaluate the antioxidant action.

The challenge is to obtain materials with properties equivalent to fully synthetic products [45]. Since, in the preparation of films, for example, when only chitosan is used, there are disadvantages as poor mechanical and barrier properties due to the absorption of moisture [51]. The ideal would be to use materials that add these absent characteristics.

### **2.3 Starch**

Starch can be found in many vegetables in the granule formula and its composition is basically from two polysaccharides: amylose (linear) and amylopectin (branched) [52]. It is one among foods that have significant energy source in the human diet. In addition to the use for consumption, the starch can be used for pharmaceutical and functional purposes and is widely used for its desirable physicochemical properties such as grain swelling, viscosity, gel formation capacity and water binding affinity [53].

The modification in the structure of starches is closely linked to the process of retrogradation, which generates a reorganization of the molecules present. Research on this phenomenon generally occurs in aqueous dispersions at different concentrations. Other factors that may be associated in the modification of starch are the disorganization and rupture of the granules, which occur in the presence of high temperatures [54].

When the starch is heated at a characteristic temperature called the gelatinization temperature (60–70°C) in aqueous solution, the swelling step of the grain occurs, where the amylose is solubilized. At temperatures lower than 100°C and without mechanical shear the granules have their integral structure and are characterized as viscoelastic [52].

In order to obtain improvements in starch properties, as well as to solve some problems, starch modification has occurred, that can occur genetically, physically, chemically or even enzymatically [55].

With genetically modified starches there are opportunities for starch production with improved functionality, for example with high levels of amylose and phosphates, with amylopectin short chains without the presence of amylose, and as properties one can mention stability to freezing and thawing [55].

As an example of physical modifications, high pressure homogenization has resulted in a physically modified starch having crystallinity reduction properties in the starch grain that could produce a hydrogel with stronger gel networks [56]. Modification by treatment of humidity and heat that generates interactions and new associations between the amylose and amylopectin structures, besides the ultrasound that can also be used as a physical method for the modification of starches [57].

Among the chemical modifications it is important to mention acid hydrolysis, acetylation, esterification, double modification and oxidation. The purpose of the chemical modification is to replace a new functional group that would add desired properties to the starch [58].

The modification of starch through enzymes mainly involves the use of hydrolyzing enzymes, an important aspect is that the enzyme must be free of components that can cause damage to starch molecules [39].

The starch after conversion into thermoplastic presents itself as an alternative for the replacement of polymers of fossil origin, mainly in relation to the properties and biodegradability of the final product. Further, on starch thermoplastic studies show that the higher proportion of amylose to amylopectin provides more flexibility and makes it even more thermoplastic [59].

Since starch can come from a variety of plant sources, it is therefore comprehensive and has high availability, recent studies highlight the use of this biopolymer through alternative sources such as starch recovery or reuse of waste in various applications, such as residual starch from the milling process, or maize residues to obtain bioethanol [60, 61] and applications as biodegradable films as shown in **Table 2**.

## **2.4 Proteins**

Proteins are polymers of natural origin, consisting of peptide bonds, the result of hydrogen bonds, ionic bonds and cross-links between amines that can originate from plant or animal material [67]. Some examples of proteins that are used as substitution of polymers of petroleum origin are: soy protein, casein, collagen and some others not so used, as wheat gluten and ovalbumin, due to the low availability of the material [68].

## *2.4.1 Collagen*

Collagen is a natural protein present in animals and is responsible for ensuring the structure that supports the skin and organs. Beyond the skins, it can be found in bones, cartilage and some other structures. Formed by amino acids, the collagen is structured by a helix triple consisting of proline, hydroxyproline and glycine molecules [69].


**Table 2.** *Studies from recovered starch.*

#### *Biodegradable Polymers: Opportunities and Challenges DOI: http://dx.doi.org/10.5772/intechopen.88146*

The origin of this collagen can be derived from residues from slaughterhouses, as well as from fishing activities [70]. The volume of waste from these activities can generate high environmental impact, since there is very little reuse on them. Thus, their destination is usually for landfills, or mostly, in irregular deposits in nature, contributing to contamination of soil and water resources. The high volume and little reuse can be justified by the leftovers during the processing of the raw material and low commercial value of the by-products generated.

Collagen, in its natural form, has little application. Therefore, one chooses to extract the gelatin present in its composition for use. In order to obtain the gelatin, it is necessary for the collagen to undergo a hydrolysis process (acidic, alkaline or enzymatic), associated with high temperatures, to break the covalent bonds, releasing the gelatin molecules, through denaturation of the helix triple. After cooling the solution, the chains absorb the water, forming gelatin [69].

Gelatin is the result of water-soluble proteins, that after extraction, can be purified and concentrated, eliminating some salts or undesirable substances contained in its structure that may compromise its application. This is another factor that may imply its applicability, generating a water absorption in the material larger than the desired one. Depending on the origin of the residue, salts such as chromium and sodium can be found (residues of leather trimmings, for example). The presence of magnesium and chlorine can be observed due to alkaline or acidic hydrolysis, respectively, that was employed in the gelatin extraction process.

Collagen and gelatin are considered good materials for application in several areas, including medical, pharmaceutical and cosmetic areas [71]. For application in the health area, purification should be more complex, involving filtration steps, generally carried out by ultrafiltration membranes.

For the food area, as referred in films for food coating, gelatin extracted from fish waste (bone and cartilage) can be used without contraindications, however gelatin extracted from tanning waste leather is not allowed for use by legislation, due to chrome remnants that exist in the solution. Gelatin from leather residue can be reused to produce films for soil cover [72]. Studies on the use of this polymer for cover application have been increasing, due to the fact of the optimum biodegradability of the material.

For the leather waste there are also other alternatives, besides the use for extraction of gelatin. Many authors have studied its use as fertilizer, due to its high potential for containing nitrogen content in its composition [73]. For use as fertilizers, the residue can be treated by adding more essential mineral salts to the soil with phosphorus and potassium.

### *2.4.2 Soybean*

Soybean is the main grain marketed in the world and is used in many processes to obtain different consumer goods. Because it is widely applied in the industry, it is also capable of generating a lot of waste. Soybean meal, considered as a by-product of the extraction of oil contained in grain for food production or biofuel, is mainly destined for animal feed [74].

Protein isolate from soybean has been the subject of many studies. Despite its high protein content, its reuse is restricted due to its high stiffness and low water resistance [75]. Materials that use soy protein have great potential for replacement of polymers of fossil origin. It can be used as an adhesive for food coatings, as packaging for use in horticulture, guaranteeing its function as both container and fertilizer [76].

When used as a base for packaging manufacture, the soy protein isolate has good advantages such as biodegradability and good gas barrier property. However, its low tensile strength makes its application difficult [77].

#### *Organic Polymers*

Techniques such as coatings and crosslinking are applied to the polymer matrix, resulting in a material with improved mechanical properties, as well as increasing the shelf life of the film.

The coating, when employed, provides low water permeability, while the crosslinking technique provides better mechanical properties when compared to the coating. In addition, it can be seen that the amount of hydrophilic groups is reduced.

Although it is shown as a more efficient technique, the crosslinking uses agents that can present certain toxicity, limiting its application in the food industry [75]. Thus, it is sought to use biological macromolecular materials, such as starch, chitosan, cellulose, for the formation of films [78].

#### *2.4.3 Casein*

Casein is the protein found in milk, of high nutritional value. It can be found in one of the residues that in recent years have generated many problems for dairy products: whey. Despite this being used in dairy production with its due treatment, was once considered as a by-product in the food industry.

Casein can be used in films for food coatings and pharmaceuticals, its main application despite the few studies on its excellent characteristics such as biodegradability, thermal stability and non-toxicity translate a high value-added material for use in drugs. Despite these advantages, the mechanical strength of the material is still quite limited [79, 80].

### **3. Challenges**

Even with promising trends for applicability, biodegradable polymers obtained from renewable sources present some disadvantages, such as low mechanical properties, rapid degradation rate, high hydrophilic capacity, and in some cases, poor mechanical properties, especially in humid environments, rendering their application unviable [81, 82].

In this context divergent opinions arise about the acceptability of biodegradable polymers in industry. While some believe in their potential to replace petroleum polymers, others presume that their shortcomings, both in technical and economic aspects, hinder their rapid adoption, at least in the near future [83].

The challenge is to obtain materials with properties equivalent to synthetic products [45]. To achieve this objective, different techniques are studied to promote modifications of biodegradable polymers, as shown in **Table 3**.



#### **Table 3.**

*Studies to improve the properties of biopolymers.*

## **4. Conclusions**

This chapter addressed a theoretical review of the opportunities and challenges of biopolymers, considering aspects such as generation and use of waste, sustainability and properties that make their applicability unfeasible.

In addition, it is necessary to continue the studies aimed at improving the poor properties of biopolymers, in order to contribute directly to scientific knowledge, ensuring sustainability, environmental preservation and consequently future generations.

## **Acknowledgements**

This work was supported by the Foundation for Research Support of the State of Rio Grande do Sul (FAPERGS) and University of Passo Fundo (UPF) for space and research support.

## **Author details**

Marieli Rosseto1 , Cesar V.T. Rigueto1 , Daniela D.C. Krein2 , Naiana P. Balbé2 , Lillian A. Massuda<sup>2</sup> and Aline Dettmer2 \*

1 Postgraduate Program in Food Science and Technology (PPGCTA), Faculty of Agronomy and Veterinary Medicine (FAMV), University of Passo Fundo, Passo Fundo, Rio Grande do Sul, Brazil

2 Department of Chemical Engineering, Faculty of Engineering and Architecture (FEAR), University of Passo Fundo (UPF), Passo Fundo, Rio Grande do Sul, Brazil

\*Address all correspondence to: alinedettmer@upf.br

© 2019 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

*Biodegradable Polymers: Opportunities and Challenges DOI: http://dx.doi.org/10.5772/intechopen.88146*

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## Chapter 8
