SYNTHESIS OF BIOBASED POLYURETHANE MODIFIED WITH POLY(LACTIC-CO-

GLYCOLIC) ACID ENFORCED WITH IMPERATA CYLINDRICA FIBERS AS A

POTENTIAL SUBSTITUTE FOR COMMERCIAL PLASTICS

A Thesis Proposal

Presented to the Faculty of the Department of Physical Sciences

College of Science

Sta. Mesa, Manila

In Partial Fulfillment of the Requirements for the Degree

Bachelor of Science in Chemistry

By

Caguioa, Krysta Marie Ilumin

Decierdo, Rexiel Angelo Maceda

Pamo, Kier Cernias

October 2018

i
 Table of Contents

Title Page ................................................................................................................... i

Table of Contents ..................................................................................................... ii

Abbreviations ……………………………………………………………………………... iv

List of Tables …………………………………………………………………………….... v

List of Formulas………………………………………………………………………….... v

List of Figures ……………………………………………………………………………...vi

I. THE PROBLEM AND ITS SETTINGS

Introduction …………………………………………………………………………….….... 1

Background of the Study ……………………………………………………………….…...1

Statement of the Problem …………………………………………………………….….... 4

Objective of the Study ……………………………………………………………….…….. 5

Significance of the Study ………………………………………………………….………. 5

Scope and Limitation …………………………………………………………….………... 6

Definition of Terms ……………………………………………………………….………... 7

II. REVIEW OF LITERATURE AND STUDIES

Impact of Plastics ………………………………………………………………………..…. 9

Plastic waste inputs from land into the ocean …………………………….……. 9

Production, use, and fate of all plastics ever made …………………………... 12

Polyurethane …………………………………………………………………………….…. 16

Transurethanization ………………………………………………………………. 18

Phosgene-free and Isocyanate-free carbamate synthesis …………... 18

Bis-Alkylcarbamate synthesis ………………………………..…. 19

Bis-Hydroxylalkylcarbamate …………………………………….. 20

AB-Type Synthons synthesis ………………………………..….. 20

ii
 Polymerization of Carbamate to Polyurethanes …………….. 21

Biobased Polyurethane ……………………………………………………….…. 23

Poly (lactic-co-glycolic) acid ……………………………………………………………... 26

α-hydroxy acid monomers …………………………………………………….… 26

Glycolic acid ……………………………………………………………... 26

Lactic acid ……………………………………………………………….. 27

Syntheses of Poly (lactic acid-co-glycolic acid acid) Serial Biodegradable

Polymer...................................................................................................................... 29

Choice for a catalyst ……………………………………………….……. 29

Melt Copolymerization ………………………………………………….. 30

III. METHODOLOGY

Synthesis ………………………………………………………………………………….... 33

Synthesis of Glycolic Acid …………………………………………………….….. 33

Synthesis of Lactic Acid ……………………………………………………......… 34

Poly(lactic-co-glycolic) acid synthesis …………………………………….….…. 35

Synthesis of Poly(urethane) …………………………………………………....... 35

Pulping of Imperata cylindrica ………………………………………………….... 37

Pulping of Imperata cylindrical…………………………………………...….…… 38

Biobased polyurethane modification with Poly(lactic-co-glycolic) acid enforced with

Imperata cylindrica pulp …………………………………………………………...….…… 39

Methods of analysis ………………………………………………………………………... 39

Molecular weight determination ……………………………………………….… 39

Composition and Microstructure ……………………………………………….… 40

Electron Microscopy …………………………………………………….………... 40

Transmission electron microscopy (TEM) …………………………..…..41

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 Scanning electron microscopy (SEM) ……………………………….….. 41

Thermal Analysis ……………………………………………………….…….……. 41

Differential Scanning Calorimetry (DSC) ………………………...……....41

References ……………………………………………………………………………...…….42

Abbreviations:

CAGR- Compound Annual Growth Rate MT- Metric Tons

DMC- Dimethylcarbonate NMR- Nuclear Magnetic Resonance

DSC- Differential Scanning Calorimetry PE- Polyethylene

FDA- Food and Drugs Association PET- Polyethylene terephthalate

FTIR- Fourier Transform Infrared PLA- Poly(lactic) acid

Spectroscopy PLGA- Poly(lacyic-co-glycolic) acid

HDPE- High Density Polyethylene PP- Polypropylene

HIC- High income PP&A Fibers- Polyester, Polyamide and

HMODAz- 10-Hydroxy-9- Acrylic Fibers

methoxyctadecanoyl Azide PPD- Person per day

HODEAz- 12-Hydroxy-9-cis- PS- Polystyrene

octadecenoyl Azide PU- Polyurethane

LDPE- Low Density Polyethylene PUR-Polyurethane

LI- Low income PVC- Polyvinychloride

LMI- Lower middle income SEC- Size Exclusion Chromatography

MHHDC- Methyl-N-11-hydroxy-9-cis- SEM- Scanning Electron Microscopy

heptadecene Carbamate TEM- Transmission Electron Microscopy

MMT- Million Metric Tons Tg – Glass Transition Temperature

Mt- Metric tons UMI- Upper middle income

iv
 List of Tables

Table 1: Waste estimates for 2010 for the top 20 countries ranked by mass of 10

mismanaged plastic waste (in units of millions of metric tons per year)

Table 2: Share of total polymer resin production according to polymer type and 14

industrial use sector calculated from data for Europe, the United States, China,

and India covering the period 2002–2014 compiled by Geyer et al from various

sources.

Table 3: Effects of catalysts on [η] values of L-PLGA 50/50 29

Table 4: Effects of SnCl2 catalyst quantity on the [η] values of L-PLGA 50/50 30

Table 5: Influences of the Melt Copolymerization Time on the [η] value of 31

L-PLGA 50/50

Table 6: Effects of the Melt Polycondensation Temperature on the [η] value 31

of the L-PLGA 50/50

List of Formulas

Eq 1: Mark Houwink Equation 40

Eq. 2: Viscosity Average Molecular Weight. 40

v
 List of Figures

Figure 1. Cogon Grass (Imperata Cylindica)

Figure 2: Global Primary Plastic Production of 2015 transmuted from table 13

S6 of Production, use, and fate of all plastics ever made, Geyer et al,2017

Figure 3: Cumulative plastic waste generation and disposal (in million metric tons) 16

(Image: Production, use, and fate of all plastics ever made, Geyer et al, 2017, p. 3)

Figure 4: A reaction mechanism for Polyurethane synthesis 17

(Image: Organic Chemistry,9th Edition, McMurry et al, 2016, p. 1045)

Figure 5: Summary of production of PU by their degree of dependence on 17

Phosgene and Isocyanate (Image: Isocyanate-Free Routes to

Polyurethanes and Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. B,

Figure 1)

Figure 6: Mechanism of Transurethanization (Isocyanate-Free Routes to 18

Polyurethanes and Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. B,

Scheme 1)

Figure 7: Three main routes to PU via a transurethane polymerization (Image: 19

Isocyanate-Free Routes to Polyurethanes and Poly(hydroxyUrethane)s,

Maisonneuve et al, 2015, p. C, Figure 2)

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Figure 8: Methoxycarbonylation of Hexamethylene Diamine with 19

Dimethylcarbonate (Isocyanate-Free Routes to Polyurethanes

and Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. C, Scheme 3)

Figure 9: Synthesis of HMODAz derived from Methyl Oleate and 21

Corresponding Polyurethane (Synthesis of Biobased Polyurethane from

Oleic and Ricinoleic Acids as the renewable resources via the

AB-Type Self-Condesation Approach, Palaskar et al, Biomacromolecules,

Volume 11, No. 5, 2010, p. 1205, Scheme 1)

Figure 10: Polymerization of Bis-methylcarbamates (Isocyanate-Free Routes 22

to Polyurethanes and Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. F,

Figure 4)

Figure 11: Polymerization of Bis-hydroxycarbamates (Isocyanate-Free Routes 22

to Polyurethanes and Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. F,

Figure 5)

Figure 12: Polymerization of AB-type monomers (Isocyanate-Free Routes 23

to Polyurethanes and Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. G,

Figure 6)

Figure 13: Curtius rearrangement (Image: Organic Chemistry,9th Edition, McMurry 24

et al, 2016, p.803)

Polyols are produced by a strong oxidant such as ozone and then reduced on a

Nickel catalyst. Which in this case is significant to the paper as triolein are derived

vii
from biobased materials such as olive oil.

Figure 14: Chemical reaction procedure of polyols from triolein (Fatty 24

acid-derived Diisocyanate and Biobased Polyurethane produced from vegetable

oil: Synthesis, Polymerization and Characterization, Hojabri et al,

Biomacromolecules 2009, 10, 884-891, scheme 1)

Figure 15: Synthesis of Saturated Diisocyanate from Oleic Acid (Fatty 25

acid-derived Diisocyanate and Biobased Polyurethane produced from vegetable

oil: Synthesis, Polymerization and Characterization, Hojabri et al,

Biomacromolecules 2009, 10, 884-891, scheme 2)

Figure 16: Synthesis of HODEAz (8) and MHHDC (10) Derived from Ricinoleic 26

Acid and Corresponding Polyurethane (9) by (a) Acyl Azido and Hydroxyl AB-Type

Self Condensation Approach and (b) Transurethane Reaction Approach

(Source: Synthesis of Biobased Polyurethane from Oleic and Ricinoleic Acids as

the renewable resources via the AB-Type Self-Condesation Approach, Palaskar

et al, Biomacromolecules,Volume 11, No. 5, 2010, p. 1206, Scheme 2)

Figure 17: Saponification of Monochloroacetic acid to yield Glycolic acid 27

Figure 18: Reaction steps in synthesizing lactic acid by chemical synthesis 28

approach (Image: Polylactic Acid: PLA Biopolymer Technology and Applications,

Lee et al, 2012, p, 83)

Figure 19: Reaction steps for biological reaction and isolation of Lactic Acid 28

viii
via Fermentation approach (Image: Polylactic Acid: PLA Biopolymer Technology

and Applications, Lee et al, 2012, p, 84

ix
 CHAPTER I

THE PROBLEM AND ITS SETTINGS

Introduction

1.1. Background of the Study

The discovery of plastics marks one of the marvels of the industrial revolution in

the late 21st century. With the comprehensive study in the field of polymer chemistry. The

production of plastics aids the boost of economies across the globe lifting the then

developing nations into developed one. Plastic is the most practical material in using as a

container and reinforcing agent to co-exist with other materials; from reducing weight to

enforcing strength, plastics are the most viable option in picking a synthetic material. But

the most important feat of plastics and any other polymer is the production itself (Jambeck

et al, 2015). Compared to any other materials such as composites (woods), ceramics, and

especially metals; Plastic could use various raw organic source mainly petroleum and

existing biological materials especially plants which will be the main source over the

course of this study (PEMRG, 2016).

In these days, plastics was considered as a huge problem of our world. The

growing demands of plastics affects our biodiversity where it pollutes water and air. Many

marine lives and animals in the land where affected that causes of different illnesses or

even death. Microplastics are one of the major problem recently discover where it was

present in every ocean on a global scale and marine organisms at every level of the food

web. Researcher proposed an alternative solution which is by using bioplastics which is

made naturally in plants and other organic materials (Lee, Joe, 2015).

1
 During world war II, Polyurethane (PU) was first developed and used as a

substitute for rubber and Prof. Dr. Otto Bayer was the man behind the discovery and

patented process of producing PU’s (M. Bellis, 2017). Polyurethane is derived from the

copolymerization of dihydric alcohols and di-isocyanates. PU’s is possessed of low glass

transition temperature (Tg) which has characteristics of a rubber. These are used for

vascular application wherein dispensability (elastic deformation) in a material is important

to withstand the rigors and pressure variations of arterial circulation. Polyurethanes are

polymeric materials different in many ways from most of the other plastic types. PU’s are

most important polymeric materials which exhibit versatile properties suitable for use in

many fields, such as paints, elastomers, liquid coatings, insulators, elastic fibers, foams,

etc (J. O. Akindoyo, et al, 2016).

Several attempts have been made to produce a plastic that degrades under

different circumstances. The first historical account of using polymers was the use of

natural plant gum as adhesive to wood for building houses and boat was when Christopher

Columbus was arrived on Haiti and saw people playing with elastic balls (Harpers 2002).

Charles Goodyear patented the method in vulcanizing the rubber using sulfur method.

In 2007, a study funded by the United States Navy was the first attempt to make a

polymer that dissolves in seawater. Scientific American published on its podcast.

The new plastics are made of polyurethane that has been changed with poly(lactic-

co-glycolic) acid, a polymer utilized in surgical sutures. The compound can be altered to

create adaptable, delicate or hard plastic. It tends to sink, not float, and in less than a

month it debases by hydrolysis into natural, nontoxic compounds (Scientific American,

2007)

In the past two decades, poly(lactic-co-glycolic) acid (PLGA) has been among the

most alluring polymeric competitors used to create gadgets for tranquilizing conveyance

and tissue engineering applications. PLGA is biocompatible and biodegradable, displays

2
an extensive variety of disintegration times, has tunable mechanical properties and above

all, is an FDA affirmed polymer (Hirenkumar et al, 2011).

Poly(lactic-co-glycolic) acid (PLGA) is widely for medical application due to its

composition and degradation properties. PLGA is composed of two monomers whereas it

was essential to our body which has no side effects, unlike the petroleum-based that has

non-biodegradable properties. Lactic acid and glycolic acid are the monomers used to

produced PLGA. These two acids will be polymerized using two common methods such

as the direct polymerization method and the ring-opening polymerization method. In Direct

polymerization or polycondensation method, the possibility of producing a high molecular

weight of PLGA is low unlike by using ring-opening polymerization where it has a high

molecular weight (Avgoustakis, 2014).

Lactic acid is an α-hydroxy acid that is a natural by-product of human and animal

metabolism which is industrially synthesized by two approaches: (1) by chemical synthesis

and (2) by fermentation approach. The other one which is glycolic is a natural by-product

of cellular metabolism. It can also be abundantly found in naturally occurring vegetation

(Gupta et al, 2007). Glycolic acid is usually produced industrially by hydrolysis of

monochloroacetic acid with 50% aqueous sodium hydroxide at 90-130 °C. The

experimental yield is 60% with 12-14% sodium chloride on which sodium chloride may be

removed by evaporative concentration, followed by the extraction of acid with acetone.

Imperata Cylindrica also was known as Cogongrass is an invasive, non-native grass which

occurs in several other southeastern countries. It affects pine production and survival,

recreation, habitat, etc. Cogon Grass (Imperata cylindrica) is used as renewable materials

to obtain cellulosic pulps to produce paper and hence preventing the environmental

problems. Also known as japgrass, speargrass, lalang-lalang, alang-alang, and

bladygrass. Imperata cynlindrica is distributed worldwide in the subtropical and tropical

region as aggressive and perennial grass (Dozier et al. 1998). Cogongrass has been

3
found in over 73 countries. Cogon grass is a most noticeable as luxuriant strands

yellowish-green grass growing along roadsides and usually in full sunlight. It can be an

alternative fiber in the pulp and paper-based industries due to the short growth cycle,

abundance, yet unsuitable for grazing animal and lack of commercial application (A. Sari

Mohd Kassim 2016).

Figure 1. Cogon Grass (Imperata Cylindica)

In this study, researchers sink an idea to produce bio-based polyurethane plastic

which strengthens with Imperata cylindrica fibers, that capable as a substitute to

commercial plastics and where it degraded to the natural environment which also essential

to human being and all living organisms.

1.2 Statement of the Problem

 The ever increasing non-biodegradable plastic pollutants that litters the ocean

and other bodies of water that is being consumed by marine animals such as

turtles and fishes that is potentially a part of human consumption

 Methods of plastic production that produce huge amounts of by products that

contributes to carbon footprints.

4
  The source of natural fiber that can be derived from plants that devastates crops

and disrupts agricultural vegetation

1.3 Objectives of the Study

This study aims to produce a commercial plastic that conforms with the

degradation state necessary to be broken down within a short span of time to reduce the

colossal impact of such plastic to the marine ecology and human conditions as well. As

this study seeks to contribute in revolutionizing green chemistry, the researchers also

seek alternative renewable bio-based materials instead of non-renewable petroleum-

based materials to significantly reduce production cost. By devising a method and

product efficiently the researchers specifically aim to:

 Prove that devastating vegetation parasitic plant Imperata cylindrica can be

beneficial as a source in improving current plastic production in the Philippines.

 The economic availability of a fully bio-based polymer-fiber composite that can

potentially replace the current commercial plastic like polyethylene that is more

durable but more biodegradable than the current commercial bioplastics like

poly(lactic) acid especially in sea water

 Maximize the proportions between PLGA, PU, and the amount of Cogon Fiber

accounting the strength, flexibility, degradability and cost of the output/product.

1.4. Significance of the Study

The study is the effort of the researchers to contribute and be a part in

revolutionizing Green Chemistry. By fully understanding the colossal impact of non-

renewable petroleum-based and how it pollutes the bodies of water, the idea of going

towards a greener and using natural alternatives as a starting material for synthesizing the

products can be well established.

5
 Using natural alternative source as a monomeric starting materials would open

new possibilities in characterizing more and better monomers and sources. This will

further benefit in encouraging future researchers into studying more functionalities of

capabilities of plants. The academe will shift their focus from petroleum industry to

agricultural sector which then open opportunities for chemists, biologists, and

agriculturists.

The usage of well-known pests such as Cogon, which are very commonly found

virtually everywhere especially on potential arable lands can be extracted as it is

devastating to the nutrition of the soil. By converting its fibers as an enforcement and

adding to the polymer matrix, the researcher can produce an output that would compete

with the current standard of plastic making by means of synthesis efficiency, cost, and

degradability.

By exerting commercial effort, this study can be further mitigated into industrial

scale. Instead of using weed killers, an extraction plan and method can be devised to pick

the Cogon grass in agricultural lands to increase the yield and crop output at the same

time using the picked parasitical plants into fiber starting material. This idea can be

transpired in Urban planning as these grass covers empty or vacant lands.

Speaking of industry, the synthesis of bio-based monomers and characterizing

functionalities, can encourage chemists to develop reaction new reaction mechanisms and

methods to further increase yields and efficiency of other synthetic demands.

1.5. Scope and Limitations

This study will use bio-based starting materials specifically oleic acid from olive

oils, ricinoleic acids from castor oils, and fibers from Imperata cylindrica. On which the

Imperata cylindrica used in synthesis is assumed to share universal fraternal environment

with other same species.

6
 The methods of synthesis of organic intermediates are mainly from literature which

are mostly a standard operating procedure assumed to be operated under controlled

conditions.

The degradability of the plastic output is inferred from close common commercial

biodegradable plastic Poly(lactic) acid. The comparability of the degradation of the product

in sea water conditions compared to potable water conditions are assumed within a

common degradable time frame of Poly(lactic) acid as no existing literature can support

to further the claim.

The experimentation of this study will be conducted mostly in the College of

Science Laboratory of Polytechnic University of the Philippines and the available

chemicals will be used. Whatever the grade used will be specified. The unavailable

materials duly provided by the researchers are aimed to be synthetic grade.

1.6. Definition of Terms

Polyurethane (PU)- a synthetic polymer that includes urethane groups in their chains. It

produced through a complex synthesis between isocyanates and polyols, in the presence

of suitable catalysts.

Polymerization- a chemical reaction in which two or more molecules combine to form

larger molecules that contain repeating structural units.

Synthetic polymers- human-made polymers. Solid materials made up with long carbon

chain with strong chemical bonds and commonly petroleum-based polymers with an atom

which that’s not easily broken down by microbes

Composite- Composed of two (or more) individual materials, which are polymers, metals,

and ceramics. Its design goal is to achieve the different combination of properties that are

not displayed by any single materials. It also aims to incorporate the best characteristics

of each of the component materials.

7
Polymers- Organic compounds that are chemically based on carbon, hydrogen, and other

nonmetallic elements, such as oxygen, nitrogen, and silicon. Polymers have large

molecular structures which are often chainlike.

Glass Transition Temperature (Tg)- the temperature at which higher molecular weight

materials (polymers) transforms from glassy state to a vicious and rubbery state.

8
 CHAPTER II

REVIEW OF LITERATURE AND STUDIES

2.1 Impact of Plastics

2.1.1 Plastic waste inputs from land into the ocean

In 2015 Jambeck et al investigated the annual input of plastic to the ocean from

waste generated by coastal populations worldwide. Which makes the Philippines be

included in this study and later draw a conclusion on how will the country affects the

worldwide dem1 Impact of Plastics.

The study presented the framework in which the amount of mismanaged plastic

waste generated annually by populations living within 50 km off coast worldwide. These

plastics are obviously an example of non-biodegradable plastics, which makes the large

fraction of plastic produced industrially globally (Jambeck et al, 2015). These non-

biodegradable plastics are refined either by physical interactions (waves, human

mechanical interactions, etc.), introduced as a marine debris and are a potential part of

the diet the marine ecology which is also then a part of the human and animal diet in the

surface especially seabirds and marine mammals (Ryan et al, 1987). The framework

includes the mass of waste generated with respect to its annual per capita, the percentage

of plastic among the waste and the percentage of the mismanaged plastic.

The researchers also estimate that by 2010, 2.5 billion Metric Tons (MT) of

municipal solid waste was generated by 6.4 billion people living in 192 coastal countries

which constitute 93% of the global population. 11% of these are plastics (275 million MT).

On which of the 192 coastal countries, the Philippines ranked third.

9
 It is also estimated that in a scale of a population living within the 50 km of the

coast, 99.5 million MT of plastic waste in coastal regions were generated. 31.9 million MT

were classified as mismanaged and an estimated 4.8 - 12.7 million entered the ocean in

2010, equivalent to 1.7 – 4.6% of the total plastic waste generated in those countries.

About 1.1 MT – 8.8 million MT range of mismanaged plastic waste is generated by a single

country annually, on which 83% of the total in 2010 came from the top 20 countries (Table

1).

Statistically, if the researchers would assume that there won’t be improvements in

the waste management, the cumulative quantity of plastic waste available to enter the

marine environment from land is predicted to increase radically.

Table 1: Waste estimates for 2010 for the top 20 countries ranked by mass of mismanaged plastic waste (in

units of millions of metric tons per year)

Rank Country Econ. Coastal Waste % % Mismanage % of total Plastic

class pop. gen. plastic misman d plastic mismanage marine

if [millions] rate waste aged waste d plastic debris

[kg/ppd] waste [MMT/year] waste [MMT/year]

1 China UMI 262.9 1.10 11 76 8.82 27.7 1.32 – 3.53

2 Indonesia LMI 187.2 0.52 11 83 3.22 10.1 0.48 – 1.29

3 Philippines LMI 83.4 0.5 15 83 1.88 5.9 0.28 – 0.75

4 Vietnam LMI 55.9 0.79 13 88 1.83 5.8 0.28 – 0.73

5 Sri Lanka LMI 14.6 5.1 7 84 1.59 5.0 0.24 – 0.64

6 Thailand UMI 26.0 1.2 12 75 1.03 3.2 0.15 – 0.41

7 Egypt LMI 21.8 1.37 13 69 0.97 3.0 0.15 – 0.39

8 Malaysia UMI 22.9 1.52 13 57 0.94 2.9 0.14 – 0.37

9 Nigeria LMI 27.5 0.79 13 83 0.85 2.7 0.13 – 0.34

10
Table 1. Continuation…….
10 Bangladesh LI 70.9 0.43 8 89 0.79 2.5 0.12 – 0.31

11 South Africa UMI 12.9 2.0 12 56 0.63 2.0 0.09 – 0.25

12 India LMI 187.5 0.34 3 87 0.60 1.9 0.09 – 0.24

13 Algeria UMI 16.6 1.2 12 60 0.52 1.6 0.08 – 0.21

14 Turkey UMI 34.0 1.77 12 18 0.49 1.5 0.07 – 0.19

15 Pakistan LMI 14.6 0.79 13 88 0.48 1.5 0.07 – 0.19

16 Brazil UMI 74.7 1.03 16 11 0.47 1.5 0.07 – 0.19

17 Burma LI 19.0 0.44 17 89 0.46 1.4 0.07 – 0.18

18 Morocco LMI 17.3 1.46 5 68 0.31 1.0 0.05 – 0.12

19 North Korea LI 17.3 0.6 9 90 0.30 1.0 0.05 – 0.12

20 United HIC 112.9 2.58 13 2 0.28 0.9 0.04 – 0.11

States

If per capita waste generation is to be reduced to the identical 2010 average which

is 1.7 kg/day in the 91 coastal countries that exceeds it and the amount of plastics in

wastes were to be capped at 11% (the 192-country average in 2010), a significant 26%

decrease would be achieved by 2025.

Philippines, a middle-income developing country largely depends on cheap

products and packaging which in turn also largely depends on plastics being cheap and

conveniently mass produced. With this being said, contributions to pollutants also affect

the lifestyle and diet of its citizen. Seafood is one of the main course of the Filipino diet as

situated in an archipelagic country. Consumption of this seafood which has potential toxins

found in micro-plastics by its particulate size, the release of persistent organic pollutants

adsorbed to it and its additives has potential health impact given by the food chain which

includes human (Boouwmeester et al, 2015) in this case, the Filipinos.

11
 With the combination of total waste management and capping of plastic waste

generation, a 77% reduction could be realized and will reduce the annual input of plastic

waste into the ocean by 2.4 to 6.4 million MT by 2025.

The statistic presented by Jambeck et al (2015) above were disclaimed for the

methodologies to be not always consistent as some activities such as illegal dumping and

recycling or other informal waste collections are not accounted for. It did not also address

the international import and export of waste which is prevalent in the developing countries

such as the Philippines in the recent Canada waste disposal scandal (Gavilan, Rappler

newspaper).

2.1.2 Production, use, and fate of all plastics ever made

This study presents the demographics and analysis of all mass-produced plastics

made by cross-referencing and combining global data on production, use, and the fate of

polymer resins, synthetic fibers, and additives. It is also a follow up of the study featured

above in which Jambeck, J.R. is also involved and one of the researchers. This analysis

includes all types of non-biodegradable plastics but focuses on the most prevalent resins

and fibers which includes high-density polyethylene (PE), low-density and linear low-

density PE, polypropylene (PP), polystyrene (PS), polyvinylchloride (PVC), polyethylene

terephthalate (PET), and PUR resins; and polyester, polyamide, and acrylic (PP&A) fibers.

The researchers found out that global production of resins and fibers increased

from 2 Million metric tons (Mt) in 1950 to 380 Mt in 2015, with compound annual growth

rate (CAGR) of 8.4%.

On average, 93% of the non-fiber plastics contain 93% polymer resin and 7% is

the additives. The amount of non-fiber plastics (combination of resin and additives) made

since 1950’s increased 7300 Mt. PP&A accounts to another 1000 Mt. Plasticizers, filers,

12
and flame retardants add up for about three-quarters of all additives. The largest fractions

of plastics produced are PE (36%), PP (21%), and PVC (12%), followed by PET, PUR,

and PS (<10% each). Polyester, which is the derivative of PET, accounts for 70% of all

PP&A fiber production. This demographic of plastics account for 92% of all plastics ever

made.

2015 GLOBAL PRIMARY PLASTICS PRODUCTION

Additives
Others 6% LD, LDPE
4% 16%

PP&A Fibers
14%
HDPE
13%

PUR
7%

PET
PP
8%
17%
PVC
PS
9%
6%

Figure 2: Global Primary Plastic Production of 2015 transmuted from table S6 of Production, use, and fate

of all plastics ever made, Geyer et al,2017

(http://advances.sciencemag.org/content/advances/suppl/2017/07/17/3.7.e1700782.DC1/1700782_SM.pdf)

Approximately 42% of all non-fiber plastics have been used for packaging, which

is composed of PE, PP, and PET. The building and construction sector used 69% of all

PVC for piping and other construction and other logistic supports is the next largest

consuming sector which is using 19% of all non-fiber plastics (table 2).

Table 2: Share of total polymer resin production according to polymer type and industrial use sector

calculated from data for Europe, the United States, China, and India covering the period 2002–2014

13
compiled by Geyer et al from various sources

(http://advances.sciencemag.org/content/advances/suppl/2017/07/17/3.7.e1700782.DC1/1700782_SM.pdf)

Market LDPE, HDPE PP PS PVC PET PUR Other Total

Sector LLDPE

Transportatio 0.1% 0.8% 2.6% 0.0% 0.3% 0.0% 1.6% 1.4% 6.7%

Packaging 13.5% 9.3% 8.2% 2.3% 0.9% 10.1 0.2% 0.1% 44.8%

Building and 1.1% 3.3% 1.2% 2.2% 8.1% 0.0% 2.4% 0.5% 18,8%

Construction

Electrical 0.5% 0.2% 0.9% 0.6% 0.4% 0.0% 0.4% 1.0% 3.8%

/Electronic

Consumer & 2.9% 1.7% 3.8% 1.8% 0.6% 0.0% 1.0% 0.2% 11.9%

Institutional

Products

Industrial 0.2% 0.1% 0.2% 0.0% 0.0% 0.0% 0.3% 0.0% 0.8%

Machinery

Other 1.7% 0.9% 4.2% 0.7% 1.4% 1.4% 2.5% 1.7% 13.2%

Total 20.0% 16.3% 21.0 7.6% 11.8 11.8 8.2% 4.9% 100.0

% % % %

The researchers estimate that 407 Mt of primary plastics (plastics manufactured

from virgin materials) has entered the use phase, and 302 Mt left it. Which, in 2015, 105

Mt were added to the in-use stock. The estimated plastic waste generation in 2010 was

274 Mt, almost equal to the independently derived estimate of 275 Mt by Jambeck et al.

14
Most of the packaging plastics that leave use the same year as they manufactured,

whereas construction plastics leaving use were produced decades earlier, when

production were much lower.

By the end of 2015, 5800 Mt of plastic waste are generated from primary plastics,

and 700 Mt of it were PP&A fibers. The three fates for plastic waste suggested were (1)

for it to be recycled or reprocessed as a secondary material, (2) to be thermally destroyed,

and lastly can be discarded either by proper waste containment or left on landfills and

open dumps.

An estimated 2500 Mt or 30% of all plastics ever produced are currently in use.

About 6300 Mt of cumulative waste of both primary and secondary plastic waste were

generated. Of this, approximately 800 Mt (12%) of plastics were thermally destroyed and

600 Mt (9%) were recycled; of which 10% of it has been recycled more than once. Around

4900 Mt – 60% of all plastics ever produced are dumped in a closed or open landfills;

which accumulates the greater fraction for it to be more practical and produce least cost.

The primary plastic production trend is tremendously increasing throughout time.

If trend won’t change and to be extrapolated, humankind will have produced 26,000 Mt of

resins, 6000 Mt of PP&A fibers, and 2000 Mt of additives by the end of 2050. Assuming

the same patterns for its fate, 9000 Mt of plastic waste will have been recycled, 12,000 Mt

incinerated, and 12,000 Mt to be dumped in landfills and open dumps which has a huge

impact on the natural environment by the end of the same said year (Figure 3).

15
Figure 3: Cumulative plastic waste generation and disposal (in million metric tons) (Image: Production, use,

and fate of all plastics ever made, Geyer et al, 2017, p. 3)

The statistic provided has been disclaimed that one of the large source of

uncertainty is the lifetime distributions of the product categories and the plastic incineration

and recycling rates outside of Europe and the United States.

2.2 Polyurethane

Urethane is a carbonyl-containing functional group in which the carbonyl carbon is

attached to both an –OR group and an -NR2 group (McMurry, 2011). Classically,

Polyurethanes are made by polyaddition of a diol (polyol) onto a diisocyanate

16
(polyisocyanate) (Figure 3). But this process produced amines and phosgenes which are

rather highly toxic (Maissonneuve, 2015)

But this process produced amines and phosgenes which are rather highly toxic

(Maissonneuve, 2015)

Figure 4: A reaction mechanism for Polyurethane synthesis (Image: Organic Chemistry,9 th Edition, McMurry

et al, 2016, p. 1045)

So, chemists are going towards a greener and safer way of producing

polyurethanes by using naturally derived isocyanates. Figure 5 visually summarizes the

paths of synthetic production of Polyurethane by their degree of dependence on phosgene

and isocyanates

17
Figure 5: Summary of production of PU by their degree of dependence on Phosgene and Isocyanate (Image:

Isocyanate-Free Routes to Polyurethanes and Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. B, Figure

1)

2.2.1 Transurethanization

Transurethanization or transcarbamolyation is a reaction in which an alcohol is

condensed on a carbamate which leads to a production of urethane. A low molar mass

alcohol side product is generated (Maisonneuve, 2015).

Figure 6: Mechanism of Transurethanization (Isocyanate-Free Routes to Polyurethanes and

Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. B, Scheme 1)

2.2.1.1 Phosgene-free and Isocyanate-free Carbamate synthesis

Three types of carbamate synthons are distinguished in these routes. This

includes: bis-alkylcarbamates, bis-hydroxyalkylcarbamates, and AB-type synthons.

Figure 5 shows the main routes in Polyurethane synthesis via transurethanization.

18
Figure 7: Three main routes to PU via a transurethane polymerization (Image: Isocyanate-Free Routes to

Polyurethanes and Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. C, Figure 2)

2.2.1.1.1 Bis-Alkylcarbamate synthesis

According to Jayakannan and Puthanparambil, reacting diisocyanates with

alcohols such as methanol and phenol would yield Bis-alkylcarbamates. As this section

aims to avoid using isocyanates, dialkylcarbonates can be reacted with diamines. The

predominant dialkylcarbonate currently in use ins Dimethylcarbonate (DMC).

Methoxycarbonylation of diamines with dimethyl carbonate would yield Bis-

methylcarbamates (Figure 8).

Figure 8: Methoxycarbonylation of Hexamethylene Diamine with Dimethylcarbonate (Isocyanate-Free Routes

to Polyurethanes and Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. C, Scheme 3)

19
 We note that most of the syntheses of Bis-Alkylcarbamates are solvent-free and

can be considered an example of green chemistry as most of the intermediates can be

found on biobased derivatives.

2.2.1.1.2 Bis-Hydroxylalkylcarbamates

Bis-Hydroxylalkylcarbamates can be easily synthesized by adding diamine on a

cyclic carbonate such as ethylene carbonate and propylene carbonate as suggested by

Blank, W.J. Rokicki et al performed this by reacting 1,4-butanediamine and 1,6-

hexanediamine with ethylene carbonate in methylene chloride at room temperature which

is then made in bulk by the Yang et al and scale the temperature to 120 °C.

2.2.1.1.3 AB-Type Synthons synthesis

Difunctional monomers are vital to perform the polymerization process. One such

includes the route to get PU is through the synthesis of AB-type monomers that has two

different functionalities: (1) as a carbamate and (2) as an alcohol. Stoichiometry between

both functionalities is always achieved, making the polymerization independent by the

stoichiometry.

This paper includes the synthesis 10-Hydroxy-9-methoxyoctadecanoyl Azide

(HMODAz) (Figure 9), 12-Hydroxy-9-cis-octadecenoyl Azide (HODEAz), and Methyl-N-

20
11-hydroxy-9-cis-heptadecene Carbamate (MHHDC) which are all AB-type monomer.

Figure 9: Synthesis of HMODAz derived from Methyl Oleate and Corresponding Polyurethane (Synthesis of

Biobased Polyurethane from Oleic and Ricinoleic Acids as the renewable resources via the AB-Type Self-

Condesation Approach, Palaskar et al, Biomacromolecules,Volume 11, No. 5, 2010, p. 1205, Scheme 1)

2.2.1.2 Polymerization of Carbamates to Polyurethanes

The review material provided by Maisonneuve et al includes Polycondensation of

Bis-alkylcarbamates (Figure 10) and Bis-hydroxyalkylcarbamates (Figure 11) and Self-

polymerization of AB-type monomer (Figure 12).

21
Figure 10: Polymerization of Bis-methylcarbamates (Isocyanate-Free Routes to Polyurethanes and

Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. F, Figure 4)

Figure 11: Polymerization of Bis-hydroxycarbamates (Isocyanate-Free Routes to Polyurethanes and

Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. F, Figure 5)

Polycondensation of Bis-alkylcarbamates and polyols includes phenol as the

leaving group. Jayakannan et al used various diols (aliphatic, cyclic, or polymeric diols) in

their experiment by heating the monomers up to 150 °C using Ti(OBu)4 as catalyst under

reduced pressure. On which they found out that high reactivity is attributed towards

primary alcohols thus giving a greater molecular weight of polymers.

Polycondensation of Bis-hydroxycarbamates involves ethylene glycol as leaving

group. The characterization of Bis-hydroxycarbamates having both bis-alcohol and bis-

carbamate functional groups makes it a good candidate for self-polymerization. Identical

conditions with polycondensation of Bis-alkylcarbamates has been applied on Bis-

22
hydroxycarbamates with metal catalyst such as Tin (II) Chloride (Yang et al) has been

used.

Figure 12: Polymerization of AB-type monomers (Isocyanate-Free Routes to Polyurethanes and

Poly(hydroxyUrethane)s, Maisonneuve et al, 2015, p. G, Figure 6)

Using metal catalysts like Tin (Hocker et al) in high temperature and reduced

pressure has been suggested by various papers in self-polymerizations of AB-type

monomers. Different side products such as phenol and urea leaves are produced as

polymerization occurs and removed in vacuo.

2.2.2 Biobased Polyurethane

Fatty acids which are defined as triesters of glycerol with three long-chain

carboxylic acids (McMurry p. 908, 2011) can be found on natural sources such as

coconuts, palms, and flowers. In terms of polyurethane production, oleic acid and ricinoleic

acid (castor oil) have been used as a starting material in synthesizing monomers.

There are also other biobased sources in which lignins are used instead of fatty

acids (Cateto et al, 2008). But fatty acids are more versatile and compatible for

polymerization. Hojabri et al reported that considering limited literature that involves the

synthesis of diisocyanates to vegetable oils; efforts have been made to prepare linear

23
saturated terminal aliphatic diisocyanate from fatty acid via Curtius rearrangement. Curtis

rearrangement involves the conversion of a carboxylic acid derivative, in this case, an acid

chloride into a primary amine with loss of one carbon (McMurry p. 806, 2011).

Figure 13: Curtius rearrangement (Image: Organic Chemistry,9th Edition, McMurry et al, 2016, p.803)

Polyols are produced by a strong oxidant such as ozone and then reduced on a Nickel catalyst. Which in this

case is significant to the paper as triolein are derived from biobased materials such as olive oil.

Figure 14: Chemical reaction procedure of polyols from triolein (Fatty acid-derived Diisocyanate and

Biobased Polyurethane produced from vegetable oil: Synthesis, Polymerization and Characterization, Hojabri

et al, Biomacromolecules 2009, 10, 884-891, scheme 1)

24
Diisiocyanate can be synthesized from Oleic acid as shown by Figure 15

Figure 15: Synthesis of Saturated Diisocyanate from Oleic Acid (Fatty acid-derived Diisocyanate and Biobased

Polyurethane produced from vegetable oil: Synthesis, Polymerization and Characterization, Hojabri et al,

Biomacromolecules 2009, 10, 884-891, scheme 2)

With special interest of Ricinoleic Acid which is easily obtained from commercial

Castor oils, this paper has a certain bias for the synthesis of 12-Hydroxy-9-cis-

octadecenoyl Azide (HODEAz) AB-Type Monomer. Given that Ricinoleic Acid is a

hydroxyl containing C18 fatty acid with a cis-configuration double bond in the ninth

position. Compared to methyl oleate starting material for PU synthesis by the self-

condensation approach, ricinoleic acid is better due to the hydroxyl group present in the

ester backbone of the fatty acid, thus making the reaction toward acyl-azide hydroxyl AB-

type monomer straightforward.

25
Figure 16: Synthesis of HODEAz (8) and MHHDC (10) Derived from Ricinoleic Acid and Corresponding

Polyurethane (9) by (a) Acyl Azido and Hydroxyl AB-Type Self Condensation Approach and (b) Transurethane

Reaction Approach (Source: Synthesis of Biobased Polyurethane from Oleic and Ricinoleic Acids as the

renewable resources via the AB-Type Self-Condesation Approach, Palaskar et al,

Biomacromolecules,Volume 11, No. 5, 2010, p. 1206, Scheme 2)

2.3 Poly (lactic-co-glycolic) acid

2.3.1 α-hydroxy acid monomers

2.3.1.1 Glycolic acid

Glycolic acid is a natural by-product of cellular metabolism. It can also be

abundantly found in naturally occurring vegetation.

By literature, Ullmann’s Encyclopedia of Industrial Chemistry suggested that

Glycolic is usually produced industrially by hydrolysis of monochloroacetic acid with 50%

aqueos sodium hydroxide at 90-130 °C (Figure 16). The experimental yield is 60% with

26
12-14% sodium chloride on which sodium chloride may be removed by evaporative

concentration, followed by the extraction of acid with acetone.

𝑂𝐻 −
→

Figure 17: Saponification of Monochloroacetic acid to yield Glycolic acid

2.3.1.2 Lactic Acid

Like Glycolic acid, Lactic acid is an α-hydroxy acid that is a natural by-product of

human and animal metabolism. Industrially it is synthesized by two approach: (1) by

chemical synthesis and (2) by fermentation approach. As this paper eagerly suggested,

the researchers have certain bias towards the latter, as to avoid using hazardous

chemicals and help establish and promote green chemistry.

27
Figure 18: Reaction steps in synthesizing lactic acid by chemical synthesis approach (Image: Polylactic Acid:

PLA Biopolymer Technology and Applications, Lee et al, 2012, p, 83)

Figure 19: Reaction steps for biological reaction and isolation of Lactic Acid via Fermentation approach

(Image: Polylactic Acid: PLA Biopolymer Technology and Applications, Lee et al, 2012, p, 84)

28
 Methyl lactate is easier to obtain as it is not corrosive as compared to lactic acid.

2.3.2 Syntheses of Poly (lactic acid-co-glycolic acid) Serial Biodegradable Polymer

Materials via Direct Melt Polycondensation and their Characterization.

This section focused on the paper provided by Wang et al and their findings.

2.3.2.1 Choice for a catalyst

Table 3: Effects of catalysts on [η] values of L-PLGA 50/50

Run Catalyst Dispersability Dissolubility [η] (dL/g) Mw (Da) Mn (Da) Mw/Mn Yield (%)

1 Sn Very Bad Agglomerate 0.1574 14,000 10,700 1.31 60.3

2 SnO Good Wholly Not 0.1769 N N N 54.5

3 SnO2 Common Easily 0.1061 N N N 46.9

sedimented

4 Sn(Oct)2 Common In the end 0.1549 N N N 61.7

dissolved

5 SnCl2 Very Good Good 0.1993 18,000 13,800 1.30 69.6

6 ZnO Bad Wholly not 0.1059 N N N 41.2

7 ZnCl2 Good Good 0.1480 N N N 50.8

8 Zn(LA)2 Common In the end 0.1020 N N N 42.7

dissolved

9 TSA Very Good Good 0.0963 N N 34.9

29
 Table 3 shows the effects of different catalyst according to Wang et al. Effect is

determined not only by the type of metal introduced but also their dispersability and

dissolubility in the process. Stannum series catalysts are significantly better than Zinc

series catalyst. Overall, the obviously best choice for a catalyst is the SnCl2.

Table 4: Effects of SnCl2 catalyst quantity on the [η] values of L-PLGA 50/50

Run Catalyst Dispersability Dissolubility [η] (dL/g) Yield (%)

quantity

(wt %)

1 0.1 Very good Good 0.1469 50.2

2 0.3 Very good Good 0.1812 64.0

3 0.5 Very good Good 0.1993 69.6

4 0.7 Very good Good 0.1628 57.5

5 0.9 Very good Good 0.1415 49.6

While table 4 suggested the specific catalytic amount for a good yield. By inferring

on the tables above; it is fairly safe to use 0.5% w/w of SnCl2 as catalyst.

2.3.2.2 Melt Copolymerization

By basing the previous researches such as by Lee et al and studies made by

Maharana et al on melt homopolymerization of Lactic acid to produce Poly(lactic) acid,

Lactic acid and Glycolic acid monomers are uniformly mixed at a pre-planned molar ratio,

the mixture was dehydrated with temperature around 140 °C for 6 hours and reduced

pressure of 4000 Pa. Using the optimized catalyst, the polymerization proceeds with

varying temperature at an absolute pressure of 70 Pa, and carried out for 5-20 hours.

Effects of time (Table 5) and temperature (Table 6) can be observed.

30
 Table 5: Influences of the Melt Copolymerization Time on the [η] value of L-PLGA 50/50

Run Time (h) Crude product Color after [η] (dL/g) Yield (%)

purification

1 5 Yellowish and White 0.1736 52.2

transparent

2 8 Yellow and transparent White 0.1783 62.3

3 10 Light brown and White 0.1993 69.6

semitransparent

4 12 Light brown and White 0.1882 66.1

semitransparent

5 15 Light brown and opaque Yellowish 0.1801 62.7

6 20 Brown and obviously Yellow 0.1715 60.5

opaque

Table 6: Effects of the Melt Polycondensation Temperature on the [η] value of the L-PLGA 50/50

Run Temperature Crude Color after [η] (dL/g) Yield (%)

(°C) product purification

1 150 Yellowish White 0.1385 49.6

and

transparent

2 158 Yellow and White 0.1545 51.7

transparent

31
 3 165 Light brown White 0.1993 69.6

and semi

transparent

4 173 Brown and Yellow 0.1634 55.7

opaque

5 180 Dark brown Brown 0.1266 20.4

Following the patterns above, Wang et al derived at the conclusion that the optimal

conditions for the best yield is melt-polycondensation at 165 °C using a 0.5% w/w SnCl2

catalyst reacted for 10 h.

32
 CHAPTER III

METHODOLOGY

3.1 Materials

The different reagents, apparatus and equipment were the materials will be

use for the synthesis and experimentation part of the research.

3.1.1 Reagents

All chemical reagents and apparatus that will be used in the experiment which

be provided by Polytechnic University of the Philippines laboratory storage are

analytically graded. Synthetically graded Reagents cannot be found in the laboratory will

be provided by the researchers which could be obtained either by synthesis or by buying

in well-known chemical distributors.

3.3 Synthesis of the Materials

Different synthesis will be conducted to obtain a final product of bio-based plastics

which has a great tensile strength and be compared to the regular commercial plastics.

3.3.1 Synthesis of Glycolic Acid

The glycolic acid was synthesized using esterification where 175 mg of Sodium

Hydroxide was dissolving into 350 ml of distilled water, then adding 350 mL of

monochloroacetic acid. The solution was put on the hot plate for 30 minutes where the

temperature is maintaining at 90° C upper limit. In the meantime, crystallization will occur

and using a separatory funnel with acetone it will proceed to phase separation, the

recovery of the crystal will occur, Lastly the said to be glycolic acid crystal was put it

vacuum filter which is also being wash using acetone. After it being wash it will be oven

33
dries with a constant temperature of 58° C which remove acetone and researchers will

obtain a crystallize glycolic acid.

3.1.2 Synthesis of Lactic Acid

Different types of the method proposed to produce lactic acid.

(1) Production of Lactobacillus sp. culture by serial dilution

Lactic acid was used commonly in our body for the process of the

gluconeogenesis were it will be converted to pyruvate which is the source of energy of our

body, To synthesis, lactic acid researchers prepare 5 test tubes with labels of 0, 1, 2, 5,

and 10 m respectively. A 5.5 g of lactobacilli MRS Broth will be dissolved in 100 mL of

distilled water and will be heat constantly until it reaches the homogeneous phase. Test

tubes with 10 mL of MRS Broth were placed inside the autoclave and will be run in a set

temperature of 121°C for 15 minutes. After autoclaving add standard Yakult™ for a

Lactobacillus casei Shirota strain in every test tube corresponds to their label then close

using a sterile cotton plug or vacuum rubber plug. Place in a secured biological cooler.

After 3 days, by physically analyzing the turbidity of the samples. Select the appropriate

sample for the succeeding experiment.

(2) Lactic Acid production in Lactate form.

First, prepare 1 L culture medium, which consists of 100 g glucose, 20 g yeast

extract and 20 g polypeptone. The medium will be sterilize using an autoclave and finally

a microbe species, the Lactobacillus sp. from the preceding experiment will be implant.

The mixture is will be culture at a temperature of 37 °C, with the maintaining pH of 7.0

using 6N ammonia-water. The culture takes 15 hours to complete. The culture is

concentrated using 200 g of ethanol and refluxed for 3 hours at between 90 and 100 °C

in a condenser to obtain ethyl lactate. The inconsumable ammonia were be separate using

34
a gas-washing bottle connected at the end of the condenser, cooling with ice-water. This

ammonia entrapping system is able to collect up to 98% of the ammonia. The remaining

reaction mixture has a maintaining temperature of 80 °C to vaporize the 150 g unreacted

ethanol by distillation. The reaction mixture is further raised to a temperature of 120 °C to

remove the water. After the removal of water, the reaction mixture undergoes a distillation

process at 50 mmHg at a liquid temperature of 70-100 °C, to yield a 130 g of purified ethyl

lactate for the poly-condensation process.

3.1.3 Poly(lactic-co-glycolic) acid synthesis

Poly(lactic-co-glycolic) acid was prepared by using of Melt-copolymerization

method. The melt-copolymerization of PLGA is the mixing or binding of two monomers

mixing together with a presence of initiator while heating constantly. The proportion of

monomers, glycolic and lactic acid is in 75:25 ratios respectively. The reagents will heat

at about 140°C for 6 hours where vacuum pump is on and pressure is 4000 joules or about

to 0.8 psi. After the reaction, add 0.5% of SnCL2 with respect to the weight of the solution

and reheat again with maintaining the temperature of 165°C and pressure of 70 Pa or 0.01

psi. The set up will run in 10 hours until the final product which is a white powdery obtain.

3.1.4 Synthesis of Poly(urethane)

via the AB-Type Self-Condensation Approach

Synthesis of AB-Type monomers for self-condensation

(1) Synthesis of 10-Hydroxy-9-methoxyoctadecanoyl Azide (HMODAz) AB-Type

Monomers

(a)Synthesis of Methyl cis-9,10-Epoxyoctadecanoate.

35
 Methyl oleate (5.0 g, 0.017 mol) and meta-chloroperbenzoic acid (4.3 g, 0.025

mol) were dissolved into dichloromethane (100 mL) and the reaction mixture was stirred

at room temperature for 5 h. The reaction mixture was filtered, and the solution was

washed with aqueous saturated sodium bicarbonate (3 × 50 mL) and then with water (3 ×

50 mL). The organic layer was separated and dried with anhydrous sodium sulfate. The

solvent was removed by rotary evaporator to obtain intermediate.

(b)Synthesis of Methyl 10-Hydroxy-9-methoxyoctadecanoate/Methyl 9-Hydroxy-10-

methoxyoctadecanoate.

Methyl cis-9,10-epoxyoctadecanoate (4.8 g, 0.015 mol), amberlyst 15 (0.05 g),

and excess methanol (100 mL) will be reflux for 12 h. The reaction mixture will be filter

and methanol was removed using a rotary evaporator. The reaction mixture will dissolve

into dichloromethane (100 mL) and wash with water (3 × 50 mL). The dichloromethane

solution will separate and evaporate to obtain intermediate Methyl 10-Hydroxy-9-

methoxyoctadecanoate /Methyl 9-Hydroxy-10-methoxyoctadecanoate as a mixture of

regioisomers.

(c)Synthesis of 10-Hydroxy-9-methoxyoctadecanoic Acid/9-Hydroxy10-

methoxyoctadecanoic Acid.

A mixture of regioisomer intermediates (Methyl 10-Hydroxy-9-

methoxyoctadecanoate/Methyl 9-Hydroxy-10-methoxyoctadecanoate; 4.0 g, 0.012 mol)

will dissolve into 1 N methanolic potassium hydroxide solution (100 mL) and reflux for 12

h. The removal of methanol was from the reaction mixture and the crude product which

will dissolve into 100 mL of water. The water solution was neutralized with hydrochloric

acid and the product was be extract with 3 × 50 mL dichloromethane. The rinse

dichloromethane solution with 3 × 50 mL of water and dried on anhydrous sodium sulfate.

36
The filter of the dichloromethane solution and solvent will be removed to obtain a mixture

of intermediates 10-Hydroxy-9-methoxyoctadecanoic Acid/9-Hydroxy10-

methoxyoctadecanoic Acid.

(d)Synthesis of 10-Hydroxy-9-methoxyoctadecanoyl Azide /9-Hydroxy10

methoxyoctadecanoyl Azide (HMODAz) AB-Type Monomer.

Into a 100 mL round-bottom flask equipped with a magnetic stirring bar and an

addition funnel will charge a mixture of hydroxyl acid intermediates 10-Hydroxy-9-

methoxyoctadecanoic Acid/9-Hydroxy10-methoxyoctadecanoic Acid (2.0 g, 0.006 mol),

triethyl amine (1.8 g, 0.018 mol), and THF/water mixture (7:3 v/v, 30 mL). The reaction

mixture will cool to 0 °C and ethylchloroformate (1.96 g, 0.018 mol) add dropwise over a

period of 10 min. The reaction mixture will stir for 2 h and then add a sodium azide (1.2 g,

0.018 mol) in water (7 mL) dropwise for 10 min and stir at 0 °C for 4 h. THF will remove

using a rotary evaporator and crude product was dissolved into dichloromethane (100

mL). The dichloromethane solution will wash with water (2 × 50 mL), dried over anhydrous

sodium sulfate, and filtered and the solvent was removed to obtain HMODAz as an oil with

a slightly yellow in color

(2) Synthesis of 12-Hydroxy-9-cis-octadecenoyl Azide (HODEAz) AB-Type Monomer.

The procedure for the synthesis of HODEAz is similar to HMODAz synthesis

except for ricinoleic acid that is used.

(3) Synthesis of Methyl-N-11-hydroxy-9-cis-heptadecene Carbamate (MHHDC), AB-Type

Monomer for Transurethane Process.

Into a 100 mL round-bottom flask equipped with a magnetic stirring bar and

refluxed condenser will charge 12-hydroxy-9-cis-octadecenoyl azide (2.0 g, 0.006 mol)

and dry methanol (50 mL). The reaction mixture was refluxed for 4 h, and after that, the

37
excess of methanol will remove on a rotary evaporator. The crude urethane product was

will dissolve into dichloromethane (100 mL), washed with water (2 × 50 mL), dry over

anhydrous sodium sulfate, and filter and the solvent will remove to obtain the carbamate

product.

AB-Type Self-Condensation of HMODAz and HODEAz

Into a 50 mL two necked round-bottom flask equipped with a magnetic stirring bar

and a nitrogen inlet will charge HMODAz (2.0 g, 0.005 mol) and kept in an oil bath at

different temperatures (50, 60, 80, and 110 °C) for various times

Polycondensation of MHHDC via Melt-Transurethane

Into a 50 mL two-necked round-bottom flask equipped with a magnetic stirring

bar, vacuum adapter, and a nitrogen inlet were charged Methyl-N-11-hydroxy-9-cis-

heptadecene carbamate (1.0 g, 0.003 mol) and titanium tetrabutoxide (0.035 g, 1 × 10-4

mol). The reaction mixture will purge with nitrogen, followed by vacuum twice. The reaction

flask was kept in an oil bath at 130 °C for 4 h under a nitrogen purge and then under

vacuum at 130 °C for 2 h.

3.1.5 Pulping of Imperata cylindrical

The abundance of Imperata cylindrical also known Cogongrass in the

Philippines was the problem in agriculture mostly by farmers. The Cogon grass has an

ability to grow in a short period of time and mostly saw all around the Philippines and said

to be “damong ligaw´. Fibers of Imperata cylindrical need to be synthesized because this

will be used for reinforcement for a strengthening of our study which is the bio-based

plastics. To synthesize the fibers, 400 g of cogon grass will be oven-dried and will pulping

using 15% active alkaline in a 7:1 liquid to sample ratio. The sample will be carried in a

digester at a cooking temperature 170°C then isothermally cooked for another 120 min.

38
The cook cogongrass will undergo disintegrate using hydro-pulper for 15 mins followed by

through. Then, the pulp was screened on a fractionator vibratory flat screen with 0.25 mm

slits. The pulp thorough washing with tap water was concentrated by a centrifuge to about

20 min and homogenized using a Hobart mixer for 10 min. Rejected and screened pulp

was dried to constant weight at 105 °C for determination of dry weight and subsequently,

the yield of the pulp.

3.1.6 Biobased polyurethane modification with Poly(lactic-co-glycolic) acid enforced with

Imperata cylindrica pulp

Fractions of total polymer and pulp were set that constitute the total concentration

[a. (50% w/w PU, 25 % w/w PLGA, 25% w/w pulp), b. (33.33% w/w PU, 33.33% w/w

PLGA, 33.33% pulp), c. (50% w/w PU, 50% PLGA), d. (50% PU, 50% Pulp), e. (50% w/w

PLGA, 50% w/w pulp), f. (50% w/w PLGA, 25% PU w/w, 25% w/w pulp), g. (50% w/w

pulp, 25% w/w PLGA, 25% w/w PU). Add a twice the weight equivalent of DMSO.

Solutions will maintain the heat at 90 °C and stir for 24 h to aid dissolution of the polymer

to form a homogeneous solution. The solution is then will transfer in a water bath at -5 °C

to freeze the solution. The solution will wash with cold water to leach out the DMSO, repeat

until no visible solvent is present. The product is then vacuum dried to remove further the

contaminants.

3.2 METHODS OF ANALYSIS

3.2.1 Molecular weight determination

Size exclusion Chromatography (SEC)

Viscometry is to be applied, in this technique the researcher will measure the time

for a dilute solution of the product to flow through a capillary. By measuring the times at

various polymer concentrations and comparing with the time obtained for the neat solvent,

39
a value for the intrinsic viscosity [η] can be obtained. Which can be related to the molecular

weight using the Mark-Houwink-Sakurada relationship

[𝜂] = 𝐾𝑀𝑎 (eq. 1)

Where K and a are constants. The value for a is determined directly by polymer-solvent

interactions which can be found on hydrodynamic values. M is the viscosity average

molecular weight.

∑∞ 1+𝑎
𝑖=0 𝑁𝑖 𝑀𝑖
[𝑀𝑛 = ∑∞
]^(1/𝑎) (eq. 2)
𝑖=0 𝑁𝑖 𝑀𝑖

3.2.2 Composition and Microstructure

H1 and C13NMR, FTIR, and Raman spectroscopy

The product will be tested to see the reactivity ratios and the unreacted monomers.

NMR is a particularly important method of analysis as it not only determines the

compositions and reactivity ratio of the monomers but also determines the monomer

sequences within the chain. This enables us to distinguish whether the polymer product

made is a block or an alternating copolymer.

The researchers also aim to use other analytical techniques such as Fourier

Transform Infrared Spectroscopy (FTIR) and Raman spectroscopy which is conduct inside

the Adamson University, Manila as this will help the researchers to support the structural

analysis for example, when by virtue of cross-linking or the presence of rigid aromatic

units, on which materials neither melts nor dissolve in any solvent suitable for NMR.

3.2.3 Electron Microscopy

Electron Microscopy involves two areas in which TEM involves thin samples and

SEM involves bulk samples.

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3.2.3.1 Transmission electron microscopy (TEM)

The fundamental requirement for TEM is that the specimen is sufficiently thin for

transmission for transmission of electron beam (~100 nm). Making thin specimens be

examined directly or after dispersion upon a support film.

Image contrasts depend upon variations in atomic number (Z-contrast), variations

in thickness (thickness contrast) and Bragg diffraction (diffraction contrast). Z-contrast is

the most widely used contrast imaging for polymers and blends, compositional variations

can lead to meaningful contrast.

3.2.3.2 Scanning electron microscopy (SEM)

In the SEM, a narrow (~10 nm) primary electron beam, particularly with energy 10

keV, is used to scan across the surface of the specimen and the image is built up by

consequent pixels. Although many processes occur within the sample, for imaging

purpose it is convenient to consider two processes; low energy secondary electron

emissions and high energy backscattered electrons. Secondary electron emission and

surface topography are the most commonly used for imaging polymers as it directly

examines the externals surface of the sample or the internal fracture surface. SEM

techniques also produce excellent images of the phase structure of stained blends and

block copolymers which is fundamental in this study.

3.2.4 Thermal analysis

3.2.4.1. Differential Scanning Calorimetry (DSC)

Most widely used technique for the study of polymers, especially systems that

crystallize. DSC can be divided into two categories; heat flow instruments based upon on

differential thermal analysis and those which are true power compensated instruments.

41
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