This invention relates to Development of bioplastic by preparing nanocomposites of pine needles, corncob and succinaldehyde as crosslinker and glycol-adipic acid as plasticizer.
BACKGROUND OF THE INVENTION
CN109265943B says that Compositions of biobased polymer blends of polymers and polyhydroxyalkanoate copolymers are described. In certain embodiments, the copolymer is a multiphase copolymer blend having one phase with a glass transition temperature of about-5 ? to about-50 ?. Methods of making the compositions of the invention are also described. Articles, films and laminates made from these compositions are also described.
KR101477049B1 this invention relates to a composition comprising (i) a polymer selected from polyethylene, polypropylene, polystyrene, polyvinyl chloride or mixtures thereof, (ii) cellulose, (iii) amide, (iv) nutrients selected from blue green algae and / v) water. The present invention also relates to a novel biodegradable additive composition for use in the production of a biodegradable plastic product. The composition may be mixed with the initial polymer to obtain a master polymer. This masterbatch composition can be mixed with an initial polymer, which is used to prepare biodegradable polymers.
AU2010251208B2 the invention thus pertains to thermoplastic processable compositions (base compositions) comprising one or more flours, one or more polymers, optionally plasticizers, optionally fillers and optionally additives, characterized in that at least one of the polymers is present in the form of its water-redispersible polymer powder or as aqueous polymer dispersion, whereby the compositions contain less than 12% by weight of polyvinyl alcohol, based on the total amount of polymeric components of the composition.
SUMMARY OF THE INVENTION
In the current scenario, biodegradability of plastics like polythene is a challenge for environment. So this is need of the hour is for development of bioplastic which can be used in making carry bags and can be degraded easily.
So In this work a new nano composite has been developed by using corn-cob ( agri-waste materials), pine needles ( Pine Plant waste in Hill areas of Uttarakhand ) and plasticiser like glycol-adipic acid. This developed new composite materials is having properties of bioplastic. In this all materials used are almost waste materials and minimum use of synthetic chemicals have been involved.
Pine needles and Corn cob are sources of cellulose and Starch mainly. Succinaldehyde has been used as crosslinker and glycol-adipic acid as plasticizer have been used in development of bioplastic film which has shown better strength properties as compared to PVA-Polyethene film, PVA-cellulose Film and PVA-Starch Film or other biodegrdable bags available in the market. These new material film has also shown good thermal stability as compared with traditional bags due to which it can be used in making disposable bags and disposable plates. Such bags may be used for carry material at -0C to 100°C conformably, even film is stable up to 80-120°C. In this study pine needles cellulose, Corn cob starch, Succinaldehyde/Butyraldehyde have been used as a cross likers in the ratio of 2-5%(v/w), in making Nano-composite along with plasticizer (Glycol). In this study less chemical have been used in making of Nano Composite by using modified Sol gel Method (Casting Method) and Thermal (extruder or extrusion) method. Cross linked Agent (2-5%, v/w) are providing higher thermal stability & more strength in Bio Plastic Film. Plasticiser (2-10 %, w/w) is providing smoothness in upper layer and Water replicancy . Bio plastic bag prepared by these nanocomposite film can be used to replace traditional non degradable bags. In this study prepared nanocomposite film is also biodegradable with some photolytic effect. Such composite films were characterized by using Water Absorption, UV- Visible Characterization, SEM, FT-IR and TGA. SEM analysis confirmed formation of Nano-composite in the range of 70-80 nm size. FT-IR proved formation of new bonding in composite and TGA was used for thermal stability determination. Over all such films prepared are bioplastic which are having sufficient strength properties along with thermal stability due to which it can be used in making bio plastic carry bags.
DETAILED DESCRIPTION OF THE INVENTION
The following description is of exemplary embodiments only and is not intended to limit the scope, applicability or configuration of the invention in any way. Rather, the following description provides a convenient illustration for implementing exemplary embodiments of the invention. Various changes to the described embodiments may be made in the function and arrangement of the elements described without departing from the scope of the invention.
BIOLOGICAL SOURCE
Pine needles waste was obtained/collected from forest/hill areas of Uttarakhand and Corn cob obtained from Vikasnagar( UK) and UP areas.
Bioplastic preparation process had given in three steps, which are as follows:
1. Extraction of cellulose Nano particle from pine nneedles
2. Process of corn cob waste to get in pulpy form
3. Preparation of composite by using corn cob starch and Cellulose from pines along with succinaldehyde/adipic acid with PVA
Nano Extraction of cellulose particle from Pine needles: In this process form approaches by the following method:
10gm Pine needles (AD) is dipped in sufficient quantity of vinegar or diluted acetic acid (30% ) quantity of vinegar and acetic acid varied from 50ml to 75 ml. it was soaked for 16- 24 hours than its was given some heat treatment with mixing using mechanical starrier at 600C to 900C for 30min to 1 hours till we get pulp form than some alkali (NaOH+Na2CO3) treatment was given (5-20% w/w method ) of sample with mixing mechanical stirrer for about 2 hours with heating 700C to 900C for about 2 hours than its filtered with washing than given treatment of some hypchlorite like NaOCl (2-4 %) was given to get cellulose particles. it is washed and dried.
Process of corncob with PVA to get pulpy form
First of all waste of maize i.e corn cob are taken approx. 10- 20gm then cut in small pieces or crushed with using magnetic starrier for about 10-15min at room temperature 300C. Then it is mixed with some vinegar(10% ) for 1 hr and then stirred with PVA ( 10-20% w/w) to get pulpy form. Cellulose Nano particle are prepared in step first & corn cob pulpy were prepared in second step after those different proportions were taken into a 500ml beaker. And started staring at 500-800 rpm by mechanical starrier then PVA solution (5% solution) was added in the mixture. It is stirred for 20- 40min than it was allowed for 10 min for bonding development after that add glycol/adipic acid is added ( 5-10%) .it is mixed with slowly string . If slurry is very thick than some water is added so that film can be casted in Petri dish. Film is dried air dried or oven dried at 400C-500C.
EXAMPLE 1:
Table.1. Formulation table
S.No Film Name
Pine:corncob
( PVA varied) Pine needles pulp waste Corncob waste material PVA
Glycol
(5-10%)
1. Composite
1:0: 10 g - 1 gm 1 ml
2. Composite film (1:1) 10 g 10 g 1gm 1 ml
3. Composite film (1:2) 10 20 2 gm 1 ml
4. Composite film (1:1) 10gm 10gm 2 gm 2 ml
5. Composite film (1:2) 10 g 20 gm 2.5 gm 2.5 ml
6. Composite film (1:3) 10 gm 30 gm 2 gm 2.5 ml
7. Composite film (2:1) 20 gm 10 gm 1 gm 2 ml
8. Bash paper
10gm - - 0.2 gm 2.5 ml
9. PE+PVA gm 2 gm 2 ml
10. Paper thick bags (5 gm) - - 1 gm 2 ml
Bash paper is a brown colour paper which is made up of waste paper /secondary fiber. it's generally thick of nearly 60 microns
Paper thick bag was procured from local market Prem Nagar brand had thickness of nearly +100-150 microns
Characterization
Coasting film were removed from Petri dish and tested strength or physical properties were tested as per ASTM method.
EXAMPLE 2:
Tensile strength and Breaking Length-
Burst factor (strength) were determining by using tearing strength tester. The value of tearing strength value in given table and values were also compared with film of other materials like PVA alone from the table. It is evidence that strength of pine needles/corn cob Nano composite with PVA in the ratio of 1;1 is about 40 % times better than PVA alone or Cellulose Alone and also better as compared with bash paper, bag or biodegradable plastic.
Breaking length (also called self-support length) is a way of measuring the strength of a material; it is the maximum length of a column of a material that can support its own weight if it is anchored only at the top.
Table.2. Tensile strength and breaking length of different concentrations of Bioplastic material.
S.No Film Name Tensile strength
(kn/m) Breaking length
(M)
1. PVA 2.80 440
2. Composite film (1:0) 2.90 410
3. Composite film (0:1) 3.10 360
4. Composite film (1:1) 3.40 550
5. Composite film (1:2) 3.35 480
6. Composite film (1:3) 3.40 470
7. Composite film (2:1) 2.10 400
8. Bash paper 2.10 340
9. PVA+ PE 3.40 525
10. Paper thick bags 2.15 336
Ratio is for Pine needles and corn cob composites, varying PVA ( about 10%)
EXAMPLE 3:
TGA Analysis
Some materials characterized by using TGA and TGA graph it’s clear that Thermal stability of Pine needles- corncob composite film is better than PVA, Cellulose Nano particle and bash paper. Its thermal stability up to 900C to 1050C.
Table.3. TGA analysis of different concentrations of bioplastic.
S.No Polymer name Sample stability( Tg)
1. PVA 800C
2. Composite film (1:0) 800C
3. Composite film (0:1) 880C
4. Composite film (1:1) 1050C
5. Composite film (1:2) 1100C
6. Composite film (1:3) 1150C
7. Composite film (2:1) 1170C
8. PVA+ PE 1140C

SEM characterization
Preparation of composite film was also confirmed by SEM analysis. An environmental SEM operating in high-vacuum mode was used for observing the surface morphology of the bioplastic films. The samples were glued on aluminum stubs and sputter coated with a thin layer of cellulose. SEM analysis of bioplastic had shown in FIG.2.
While considerable emphasis has been placed herein on the specific features of the preferred embodiment, it will be appreciated that many additional features can be added and that many changes can be made in the preferred embodiment without departing from the principles of the disclosure. These and other changes in the preferred embodiment of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.
Overall in this study , we get a new bioplastic by using pine needles and corn cob with PVA and glycol/adipic acid plasticiser in different proportions. We can prepare a better bio plastic which is thermal stable upto 105°C and strength properties are also better than wash paper or other biodegradable bags available in market.

We Claim:

1. A method of Development of bioplastic by preparing nanocomposites of pine needles, corncob and succinaldehyde as crosslinker comprising the steps of:
Extracting of cellulose Nano particle from pine needles;
Processing of corn cob waste to get in pulpy form;
Preparing of composite by using corn cob starch and Cellulose from pines along with succinaldehyde/adipic acid with PVA.
2. The method as claimed in claim 1, wherein 10gm Pine needles (AD) is dipped in vinegar or diluted acetic acid (30% ) quantity of vinegar and acetic acid varied from 50ml to 75 ml; which is soaked for 16- 24 hours than its was given some heat treatment with mixing using mechanical starrier at 600C to 900C for 30min to 1 hours till gets pulp form than some alkali (NaOH+Na2CO3) treatment was given (5-20% w/w method ) of sample with mixing mechanical stirrer for about 2 hours with heating 700C to 900C for about 2 hours than its filtered with washing than given treatment of some hypchlorite like NaOCl (2-4 %) was given to get cellulose particles; and which is washed and dried.
3. The method as claimed in claim 1, wherein waste of maize which is corn cob are taken 10- 20gm then cut in small pieces or crushed with using magnetic starrier for about 10-15min at room temperature 3000C; then it is mixed with some vinegar (10%) for 1 hr and then stirred with PVA (10-20% w/w) to get pulpy form.
4. The method as claimed in claim 1, wherein Cellulose Nano particle are prepared in step first & corn cob pulpy were prepared in second step after those different proportions were taken into a 500ml beaker; and started staring at 500-800 rpm by mechanical starrier then PVA solution (5% solution) is added in the mixture; which is stirred for 20- 40min than it was allowed for 10 min for bonding development after that add glycol/adipic acid is added ( 5-10%); and it is mixed with slowly string; If slurry is very thick than some water is added so that film is casted in Petri dish; further Film is dried air dried or oven dried at 400C-500C.