Biodegradable hydrophobic composite materials and process for the preparation thereof

Abstract

The present invention relates to biodegradable hydrophobic composite materials and a process for the preparation of said hydrophobic biodegradable materials from the seaweed polysaccharides through grafting reaction with vinylated monomers e.g. vinyl acetate. The said composites can be used as a substitute for synthetic ropes for varied applications including seaweed cultivation in the open sea. The results of cultivation experiments showed that ropes are suitable for cultivation of seaweeds in the sea environment, and exhibit higher biomass yield as compared to synthetic ropes. The prepared composites are very flexible and can be used for making handles for carry bags and for the preparation of biodegradable designs, bowls, pots, jars, gift items, stud caps and bracelets.

Claims

1. A hydrophobic biodegradable composite prepared from a seaweed derived polysaccharide through a grafting reaction with vinyl acetate comprising: [a] seaweed derived polysaccharide in the range of 30 to 80 wt %; [b] vinyl acetate in the range of 8 to 60 wt %; and [c] plasticizer in the range of 2 to 15 wt %; wherein, the plasticizer is selected from the group consisting of glycerol, ethylene glycol, and sorbitol; and wherein moisture content of said composite is in the range of 5 to 15 wt %.

2. The composite as claimed in claim 1, wherein the seaweed derived polysaccharide is selected from the group consisting of agar, agarose, alginate, and carrageenan.

3. The composite as claimed in claim 1, wherein the seaweed derived polysaccharide is either used alone or as a blend of seaweed derived polysaccharides.

4. The composite as claimed in claim 1, wherein the seaweed derived polysaccharide is agar and/or agarose.

5. The composite as claimed in claim 1, wherein the plasticizer is glycerol.

6. A process for the preparation of the composites as claimed in claim 1, the process comprising: [a] dissolving 1 to 8 wt % of the seaweed derived polysaccharide or a blend of seaweed derived polysaccharides in distilled water by heating at a temperature in the range of 100 to 120 degrees Celsius for 5 to 30 minutes to obtain a homogeneous solution; [b] adding 0.01 to 0.10 wt % potassium persulphate to the homogeneous solution as obtained in step [a] under stirring followed by addition of 2 to 16 wt % vinyl acetate and heating at a temperature in the range of 60 to 85 degrees Celsius in aqueous medium under reflux conditions for 3 to 7 hours under constant stirring to obtain a reaction mixture; [c] adding 0.5 to 5.0 wt % plasticizer into the reaction mixture as obtained in step [b] and transferring the contents into a hollow or tubular device or mould to obtain a moulded composite; [d] treating the moulded composite as obtained in step [c] with an organic solvent at a temperature in the range of 20 to 30 degrees Celsius to remove unreacted homopolymer followed by air drying to obtain the hydrophobic biodegradable composite.

7. The process as claimed in claim 6, wherein the hollow or tubular device or mould is made of glass, plastic, steel, or wood.

8. The process as claimed in claim 6, wherein the organic solvent is selected from the group consisting of isopropyl alcohol, acetone, methanol, ethanol, ethyl acetate, and tetra hydro furan.

Description

BRIEF DESCRIPTION OF ACCOMPANYING DRAWINGS

(1) FIG. 1 illustrates the biodegradable hydrophobic or controlled hydrophobic composites based colored ropes or rods, suitable for making decorative items, coloured handles for carry bags, ornaments accessories, etc.

(2) FIG. 2 illustrates (a) cultivation of Kappaphycus alvarezii on the biodegradable hydrophobic ropes by the raft method, (b) cultivated plant in biodegradable hydrophobic composites based ropes of Examples 15 and 16, and (c) cultivated plant in synthetic ropes. The plant growth was higher in biodegradable ropes compared to synthetic ropes.

(3) FIG. 3 illustrates (a) flexibility property of biodegradable ropes, (b) empty carry bag with handle of ropes of Examples 14-20, and (c) 5 kg weight in carry bag with handles of ropes of Examples 14-20.

(4) FIG. 4 illustrates leather belt with beautiful designs made of biodegradable composites ropes of Examples 14-31.

(5) FIG. 5 illustrates stud caps made of biodegradable composites ropes of Examples 14-31.

(6) FIG. 6 illustrates bowl/basket made of biodegradable composites rope of Examples 14-31.

(7) FIG. 7 illustrates storage of vegetables in bowl/basket made of biodegradable composites ropes of Example 38.

(8) FIG. 8 illustrates storage of bakery items in bowl/basket made of biodegradable composites ropes of Example 38.

(9) FIG. 9 illustrates decorative pot/jar made of biodegradable composites ropes of Examples 14-31.

(10) FIG. 10 illustrates flowers in decorative pot/jar made of biodegradable composites ropes of Example 41.

(11) FIG. 11 illustrates hand belts/bracelet made of biodegradable composites ropes of Examples 14-31.

(12) FIG. 12 illustrates the drying of cloths on biodegradable composites ropes of Examples 15 and 16.

DETAILED DESCRIPTION OF THE INVENTION

(13) The seaweed derived phycocolloids used for the purposes of the present invention are selected from agar bacteriological (product code: 0140132), agarose (product code: 014011) and alginate (product code: 1947295) which were commercially procured from M/s Sisco Research Laboratories (SRL) Pvt. Ltd. Mumbai-400 093, Maharashtra, India, and semi refined carrageenan (product code: Aqua gel 250) which was commercially procured from M/s Aquagri Processing Pvt. Ltd., New Delhi, India.

(14) The present invention relates to biodegradable composite materials of controlled hydrophobicity exhibiting high mechanical strength and good flexibility. The invention also describes a facile, eco-friendly and one-step process for the preparation of the said materials from the seaweed polysaccharides and their blends through chemical reaction with vinylated monomers like vinyl acetate, acrylamide and acetonitrile. According to a non-limiting exemplary embodiment, the said process comprises: dissolving 1 to 10 wt % of seaweed polysaccharides namely agar, carrageenans, alginate, agarose or their blends in distilled water by microwave heating at 100 degree Celsius for 5 to 15 minutes or by autoclaving at 120 degree Celsius for 30 minutes to obtain a homogeneous solution, adding 0.01 to 0.10 wt % of potassium persulphate (KPS) under stirring to said solution followed by addition of 2 to 16 wt % vinylated monomers, heating the reaction mixture in aqueous medium under reflux conditions at 60 to 85 degree Celsius for 3 to 7 hours with constant stirring, adding 0.5 to 2.0 wt % of plasticizers selected from glycerol, sorbitol, ethylene glycol or other polyols into the reaction mixture and transferring the contents to the desired hollow or tubular devices/moulds made of glass or metal to obtain the desired moulded composites in various shapes, treating the resulting moulded composites with organic solvent at a temperature in the range of 20 to 30 degree Celsius so as to remove the unreacted homopolymer followed by air drying under ambient conditions to yield the desired biodegradable hydrophobic composites suitable for multifarious applications including seaweed cultivation in the open seawater environment.

EXAMPLES

(15) The following examples are given by way of illustration and therefore should not be construed to limit the scope of the present invention.

Example 1

(16) Seaweed phycocolloid (SP) agarose (2 wt %) was dissolved in water by microwave (MW) heating at 100 degree Celsius for 15 minutes. To this, 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 4 wt % acrylamide (AAm). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the heated reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water sensitive biodegradable composites named as Agarose/PAAm-composite (Ia). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

(17) TABLE-US-00001 TABLE 1 Effect of different reaction parameters and other variables in Example 1. Seaweed phycocolloid AAm KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 4 0.02 0.5 This produced water sensitive biodegradable composites (2) named as Agar/PAAm-composite (Ib). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation. Semi- 4 0.02 0.5 This produced water sensitive biodegradable composites refined named as SRC/PAAm-composite (Ic). It was observed carrageenan that the prepared composites were not hydrophobic and (SRC) thus not suitable to be used for applications such as (2) seaweed cultivation. Alginate 4 0.02 0.5 This produced highly water sensitive biodegradable (2) composites named as Alginate/PAAm-composite (Id). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

Example 2

(18) Experiments of Example 1 were repeated taking seaweed phycocolloid agarose (4 wt %) which was dissolved in water by autoclave heating at 120 degree Celsius for 30 minutes. To this, 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 8 wt % acrylamide (AAm). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the heated reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water sensitive biodegradable composites named as Agarose/PAAm-composites (IIa). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

(19) TABLE-US-00002 TABLE 2 Effect of different reaction parameters and other variables in Example 2. Seaweed phycocolloid AAm KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 8 0.02 0.5 This produced water sensitive biodegradable composites (4) named as Agar/PAAm-composite (IIb). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation. Semi- 8 0.02 0.5 This produced water sensitive biodegradable composites refined named as SRC/PAAm-composite (IIc). It was observed that carrageenan the prepared composites were not hydrophobic and thus not (SRC) suitable to be used for applications such as seaweed (4) cultivation. Alginate 8 0.02 0.5 This produced highly water sensitive biodegradable (4) composites named as Alginate/PAAm-composite (IId). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

Example 3

(20) Experiments of Example 1, were repeated taking seaweed phycocolloid agarose (6 wt %) which was dissolved in water by autoclave heating at 120 degree Celsius for 30 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 16 wt % acrylamide (AAm). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the heated reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water sensitive biodegradable composites named as Agarose/PAAm-composites (IIIa). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

(21) TABLE-US-00003 TABLE 3 Effect of different reaction parameters and other variables in Example 3. Seaweed phycocolloid AAm KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 16 0.02 0.5 This produced water sensitive biodegradable composites (6) named as Agar/PAAm-composite (IIIb). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation. Semi- 16 0.02 0.5 This produced water sensitive biodegradable composites refined named as SRC/PAAm-composite (IIIc). It was observed that carrageenan the prepared composites were not hydrophobic and thus not (SRC) suitable to be used for applications such as seaweed (6) cultivation. Alginate 16 0.02 0.5 This produced highly water sensitive biodegradable (6) composites named as Alginate/PAAm-composite (IIId). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

Example 4

(22) Experiments of Example 1, were repeated taking seaweed phycocolloid agarose (2 wt %) which was dissolved in water by microwave heating at 100 degree Celsius for 15 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by the addition of 4 wt % acrylonitrile (ACN). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the heated reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water sensitive biodegradable composites named as Agarose/PACN-composites (IVa). It was observed that the prepared composite was not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

(23) TABLE-US-00004 TABLE 4 Effect of different reaction parameters and other variables in Example 4. Seaweed phycocolloid ACN KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 4 0.02 0.5 This produced water sensitive biodegradable (2) composites named as Agar/PACN-composite (IVb). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation. Semi- 4 0.02 0.5 This produced water sensitive biodegradable refined composites named as SRC/PACN-composite (IVc). carrageenan It was observed that the prepared composites were (SRC) not hydrophobic and thus not suitable to be used for (2) applications such as seaweed cultivation. Alginate 4 0.02 0.5 This produced highly water sensitive biodegradable (2) composites named as Alginate/PACN-composite (IVd). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

Example 5

(24) Experiments of Example 2, were repeated taking seaweed phycocolloid agarose (4 wt %) which was dissolved in water by autoclave heating at 120 degree Celsius for 30 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 8 wt % acrylonitrile (ACN). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the heated reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water sensitive biodegradable composites named as Agarose/PACN-composites (Va). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

(25) TABLE-US-00005 TABLE 5 Effect of different reaction parameters and other variables in Example 5. Seaweed phycocolloid ACN KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 8 0.02 0.5 This produced water sensitive biodegradable composites (4) named as Agar/PACN-composite (Vb). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation. Semi-refined 8 0.02 0.5 This produced water sensitive biodegradable composites carrageenan named as SRC/PACN-composite (Vc). It was observed that (SRC) the prepared composites were not hydrophobic and thus not (4) suitable to be used for applications such as seaweed cultivation. Alginate 8 0.02 0.5 This produced highly water sensitive biodegradable (4) composites named as Alginate/PACN-composite (Vd). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

Example 6

(26) Experiments of Example 3, were repeated taking seaweed phycocolloid agarose (6 wt %) which was dissolved in water by autoclave heating at 120 degree Celsius for 30 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 16 wt % acrylonitrile (ACN). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the heated reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water sensitive biodegradable composites named as Agarose/PACN-composites (VIa). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

(27) TABLE-US-00006 TABLE 6 Effect of different reaction parameters and other variables in Example 6. Seaweed phycocolloid ACN KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 16 0.02 0.5 This produced water sensitive biodegradable composites (6) named as Agar/PACN-composite (VIb). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation. Semi- 16 0.02 0.5 This produced water sensitive biodegradable composites refined named as SRC/PACN-composite (VIc). It was observed that carrageenan the prepared composites were not hydrophobic and thus not (SRC) suitable to be used for applications such as seaweed (6) cultivation. Alginate 16 0.02 0.5 This produced highly water sensitive biodegradable (6) composites named as Alginate/PACN-composite (VId). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

Example 7

(28) Experiments of Example 1, were repeated taking seaweed phycocolloid agarose (2 wt %) which was dissolved in water by microwave heating at 100 degree Celsius for 15 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by the addition of 2 wt % polyvinyl alcohol (PVA). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the heated reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water sensitive biodegradable composites named as Agarose/PVA-composites (VIIa). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

(29) TABLE-US-00007 TABLE 7 Effect of different reaction parameters and other variables in Example 7. Seaweed phycocolloid PVA KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 2 0.02 0.5 This produced water sensitive biodegradable (2) composites named as Agar/PVA-composite (VIIb). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation. Semi-refined 2 0.02 0.5 This produced water sensitive biodegradable carrageenan composites named as SRC/PVA-composite (VIIc). It (SRC) was observed that the prepared composites were not (2) hydrophobic and thus not suitable to be used for applications such as seaweed cultivation. Alginate 2 0.02 0.5 This produced highly water sensitive biodegradable (2) composites named as Alginate/PVA-composite (VIId). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

Example 8

(30) Experiments of Example 2, were repeated taking seaweed phycocolloid agarose (4 wt %) which was dissolved in water by autoclave heating at 120 degree Celsius for 30 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 8 wt % PVA. The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the heated reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water sensitive biodegradable composites named as Agarose/PVA-composites (VIIIa). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

(31) TABLE-US-00008 TABLE 8 Effect of different reaction parameters and other variables in Example 8. Seaweed phycocolloid PVA KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 8 0.02 0.5 This produced water sensitive biodegradable composites (4) named as Agar/PVA-composite (VIIIb). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation. Semi-refined 8 0.02 0.5 This produced water sensitive biodegradable composites carrageenan named as SRC/PVA-composite (VIIIc). It was observed that (SRC) the prepared composites were not hydrophobic and thus not (4) suitable to be used for applications such as seaweed cultivation. Alginate 8 0.02 0.5 This produced highly water sensitive biodegradable (4) composites named as Alginate/PVA-composite (VIIId). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

Example 9

(32) Experiments of Example 3, were repeated taking seaweed phycocolloid agarose (6 wt %) which was dissolved in water by autoclave heating at 120 degree Celsius for 30 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 16 wt % PVA. The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the heated reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water sensitive biodegradable composites named as Agarose/PVA-composites (IXa). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

(33) TABLE-US-00009 TABLE 9 Effect of different reaction parameters and other variables in Example 9. Seaweed phycocolloid PVA KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 16 0.02 0.5 This produced water sensitive biodegradable composites (6) named as Agar/PVA-composite (IXb). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation. Semi-refined 16 0.02 0.5 This produced water sensitive biodegradable composites carrageenan named as SRC/PVA-composite (IXc). It was observed (SRC) that the prepared composites were not hydrophobic and (6) thus not suitable to be used for applications such as seaweed cultivation. Alginate 16 0.02 0.5 This produced highly water sensitive biodegradable (6) composites named as Alginate/PVA-composite (IXd). It was observed that the prepared composites were not hydrophobic and thus not suitable to be used for applications such as seaweed cultivation.

Example 10

(34) Experiments of Example 1, were repeated taking seaweed phycocolloids agarose (2 wt %) which was dissolved in water by microwave heating at 100 degree Celsius for 15 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by the addition of 2 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h under constant stirring and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced improved hydrophobicity of the composites named as Agarose/PVAc-composites (Xa). It was observed that the prepared composites are very brittle and non-flexible in nature thus not suitable to be used for applications such as seaweed cultivation.

(35) TABLE-US-00010 TABLE 10 Effect of different reaction parameters and other variables in Example 10. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 2 0.02 NIL This produced improved hydrophobicity of the (2) composites named as Agar/PVAc-composites (Xb). It was observed that the prepared composites are very brittle and non-flexible in nature thus not suitable to be used for applications such as seaweed cultivation. Semi- 2 0.02 NIL This produced improved hydrophobicity of the refined composites named as SRC/PVAc-composites (Xc). It carrageenan was observed that the prepared composites are very (SRC) brittle and non-flexible in nature thus not suitable to be (2) used for applications such as seaweed cultivation. Alginate 2 0.02 NIL This produced improved hydrophobicity of the (2) composites named as Alginate/PVAc-composites (Xd). It was observed that the prepared composites are very brittle and non-flexible in nature thus not suitable to be used for applications such as seaweed cultivation.

Example 11

(36) Experiments of Example 2, were repeated taking seaweed phycocolloid agarose (4 wt %) which was dissolved in water by autoclave heating at 120 degree Celsius for 30 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 8 wt % VAc. The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XIa). It was observed that the prepared composites were brittle, non-flexible and were not suitable to be used for applications such as seaweed cultivation.

(37) TABLE-US-00011 TABLE 11 Effect of different reaction parameters and other variables in Example 11. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 8 0.02 NIL This produced water non sensitive biodegradable (4) composites named as Agar/PVAc-composite (XIb). It was observed that the prepared composites were brittle, non- flexible and thus not suitable to be used for applications such as seaweed cultivation. Semi-refined 8 0.02 NIL This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XIc). It was (SRC) observed that the prepared composites were brittle, non- (4) flexible and thus not suitable to be used for applications such as seaweed cultivation. Alginate 8 0.02 NIL This produced highly water non sensitive biodegradable (4) composites named as Alginate/PVAc-composite (XId). It was observed that the prepared composites were brittle, non- flexible and thus not suitable to be used for applications such as seaweed cultivation.

Example 12

(38) Experiments of Example 3, were repeated taking seaweed phycocolloid agarose (6 wt %) which was dissolved in water by autoclave heating at 120 degree Celsius for 30 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 16 wt % VAc. The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XIIa). It was observed that the prepared composites were brittle, non-flexible and were not suitable to be used for applications such as seaweed cultivation.

(39) TABLE-US-00012 TABLE 12 Effect of different reaction parameters and other variables in Example 12. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 16 0.02 NIL This produced water non sensitive biodegradable (6) composites named as Agar/PVAc-composite (XIIb). It was observed that the prepared composites were brittle, non- flexible and thus not suitable to be used for applications such as seaweed cultivation. Semi-refined 16 0.02 NIL This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XIIc). It was (SRC) observed that the prepared composites were brittle, non- (6) flexible and thus not suitable to be used for applications such as seaweed cultivation. Alginate 16 0.02 NIL This produced highly sensitive to water biodegradable (6) composites named as Alginate/PVAc-composite (XIId). It was observed that the prepared composites were brittle, non-flexible and thus not suitable to be used for applications such as seaweed cultivation.

Example 13

(40) Vinyl acetate 10 wt % was added in 100 ml distilled water. To this 0.02 wt % potassium persulphate (KPS) was added under stirring. The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. The reaction mixture was then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting polymers were treated with organic solvent at room temperature. These produced polymers named as PVAc (XIII), which dispersed in water, exhibited low strength, and were highly sensitive to organic solvents.

(41) Findings from Examples 1 to 13

(42) Examples 1 to 9 demonstrated that vinylated reagents like AAm, ACN, and PVA produced composites (Ia to IXd), which were water sensitive and thus, were not suitable to be used for water applications such as seaweed cultivation and other similar applications. In addition, Examples 10 to 12 further demonstrated that vinyl acetate used as reagent produced composites (Xa to XIId) with improved hydrophobicity compared to the parent seaweed phycocolloids, which are non-flexible, brittle in nature, and thus not suitable to be used for seaweed cultivation and other potential applications. These findings also revealed that a suitable plasticizer needs to be added to improve the flexibility and smoothness of these composites. Example 13 further demonstrated that vinyl acetate alone used as reagent produced hydrophobic PVAc (XIII) polymers, which are highly sensitive to organic solvents, and hence are not suitable to be used for seaweed cultivation and other applications.

Example 14

(43) Experiments of Example 10, were repeated taking agarose (2 wt %) which was dissolved in water by microwave heating at 100 degree Celsius for 15 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 5 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XIVa), which are of low strength and thus not suitable to be used for applications such as seaweed cultivation. Yield of composites: 2.5-5.0 g, containing agarose 40-80 wt %, PVAc 12-45 wt %, glycerol 2-10 wt % and moisture 5-10 wt % [Optimum yield is 50.5 g, composition: Seaweed phycocolloids=402 wt %, PVAc=452 wt %, glycerol 51 wt % and moisture 101 wt %].

(44) TABLE-US-00013 TABLE 14 Effect of different reaction parameters and other variables in Example 14. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 5 0.02 0.5 This produced water non sensitive biodegradable (2) composites named as Agar/PVAc-composite (XIVb). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation. Semi-refined 5 0.02 0.5 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XIVc). It (SRC) was observed that the prepared composites having (2) improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation. Alginate 5 0.02 0.5 This produced water non sensitive biodegradable (2) composites named as Alginate/PVAc-composite (XIVd). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 15

(45) Experiments of Example 11, were repeated taking agarose (4 wt %) which was dissolved in water by microwave heating at 100 degree Celsius for 15 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 10 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XVa). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for applications such as seaweed cultivation. Yield of composites: 4.8-11.2 g, containing agarose 35-86 wt %, PVAc 10-61 wt %, glycerol 5-12 wt % and moisture 7-10 wt % [Optimum yield is 11.20.5 g, composition: Seaweed phycocolloids=362 wt %, PVAc=502 wt %, glycerol 51 wt % and moisture 81 wt %].

(46) TABLE-US-00014 TABLE 15 Effect of different reaction parameters and other variables in Example 15. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 10 0.02 0.5 This produced water non sensitive biodegradable (4) composites named as Agar/PVAc-composite (XVb). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation. Semi-refined 10 0.02 0.5 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XVc). It (SRC) was observed that the prepared composites having (4) improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation. Alginate 10 0.02 0.5 This produced water non sensitive biodegradable (4) composites named as Alginate/PVAc-composite (XVd). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 16

(47) Experiments of Example 12, were repeated taking agarose (6 wt %) which was dissolved in water by microwave heating at 100 degree Celsius for 15 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 12 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XVIa). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for applications such as seaweed cultivation. Yield of composites: 7.5-14.1 g, containing agarose 42-80 wt %, PVAc 13-40 wt %, glycerol 2-8 wt % and moisture 5-10 wt % [Optimum yield is 14.10.5 g, composition: Seaweed phycocolloids=432 wt %, PVAc=422 wt %, glycerol 71 wt % and moisture 81 wt %].

(48) TABLE-US-00015 TABLE 16 Effect of different reaction parameters and other variables in Example 16. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 12 0.02 0.5 This produced water non sensitive biodegradable (6) composites named as Agar/PVAc-composite (XVIb). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation. Semi-refined 12 0.02 0.5 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XVIc). It (SRC) was observed that the prepared composites having (6) improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation. Alginate 12 0.02 0.5 This produced water non sensitive biodegradable (6) composites named as Alginate/PVAc-composite (XVId). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

(49) Examples 15 and 16 further demonstrated that seaweed phycocolloids namely agarose and agar (4 and 6 wt %) with VAc produced water non sensitive biodegradable composites (XVa,b and XVIa,b). It was observed that the prepared composites (XVa,b and XVIa,b) were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation.

Example 17

(50) Experiments of Example 15, were repeated taking hybrid of agarose and semi-refined carrageenans in 1:1 w/w ratio (4 wt %) which was dissolved in water by microwave heating at 100 degree Celsius for 15 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 8 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/SRC/PVAc-composites (XVIIa). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for applications such as seaweed cultivation. Yields and compositions of the prepared composites are in the range as given in the Example 15.

(51) TABLE-US-00016 TABLE 17 Effect of different reaction parameters and other variables in Example 17. Hybrid Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agarose/Agar 8 0.02 0.5 This produced water non sensitive biodegradable (4) composites named as Agarose/Agar/PVAc-composite (XVIIb). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation. Agarose/Alginate 8 0.02 0.5 This produced water non sensitive biodegradable (4) composites named as Agarose/Alginate/PVAc-composite (XVIIc). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 18

(52) Experiments of Example 16, were repeated taking hybrid of agarose and semi-refined carrageenan (SRC) in 1:1 w/w ratio (6 wt %) which was dissolved in water by microwave heating at 100 degree Celsius for 15 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 13 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/SRC/PVAc-composites (XVIIIa). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation. Yields and compositions of the prepared composites are in the range as given in the Example 16.

(53) TABLE-US-00017 TABLE 18 Effect of different reaction parameters and other variables in Example 18. Hybrid Seaweed phycocolloids VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agarose/Agar 13 0.02 0.5 This produced water non sensitive biodegradable (6) composites named as Agarose/Agar/PVAc-composite (XVIIIb). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation. Agarose/Alginate 13 0.02 0.5 This produced water non sensitive biodegradable (6) composites named as Agarose/Alginate/PVAc- composite (XVIIIc). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 19

(54) Experiments of Example 15, were repeated taking hybrid of agar and semi-refined carrageenan (SRC) in 1:1 w/w ratio (4 wt %) which was dissolved in water by microwave heating at 100 degree Celsius for 15 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 11 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agar/SRC/PVAc-composites (XIXa). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation. Yields and compositions of the prepared composites are in the range as given in the Example 15.

(55) TABLE-US-00018 TABLE 19 Effect of different reaction parameters and other variables in Example 19. Hybrid Seaweed phycocolloids VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar/Alginate 11 0.02 0.5 This produced water non sensitive biodegradable (4) composites named as Agar/Alginate/PVAc-composite (XIXb). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 20

(56) Experiments of Example 16, were repeated taking hybrid of agar and semi-refined carrageenan (SRC) in 1:1 w/w ratio (6 wt %) which was dissolved in water by microwave heating at 100 degree Celsius for 15 minutes. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 9 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agar/SRC/PVAc-composites (XXa). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation. Yields and compositions of the prepared composites are in the range as given in the Example 16.

(57) TABLE-US-00019 TABLE 20 Effect of different reaction parameters and other variables in Example 20. Hybrid Seaweed phycocolloids VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar/Alginate 9 0.02 0.5 This produced water non sensitive biodegradable (6) composites named as Agar/Alginate/PVAc-composite (XXb). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 21

(58) The experiments of Examples 15 and 16 were repeated taking 7 wt % agarose. To this 0.04 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 14 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXI a & a). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for applications such as seaweed cultivation. [Optimum yields (11.40.2 g) and compositions of composites with 4 wt % agarose: containing agarose=362 wt %, PVAc=502 wt %, glycerol 51 wt % and moisture 81 wt %; while optimum yields (14.30.2 g) and compositions of composites with 6 wt % agarose is: agarose=402 wt %, PVAc=492 wt %, glycerol 51 wt % and moisture 61 wt %].

(59) TABLE-US-00020 TABLE 21 Effect of different reaction parameters and other variables in Example 21. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 14 0.04 0.5 This produced water non sensitive biodegradable (7) composites named as Agar/PVAc-composite (XXIb & b). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation. Semi-refined 14 0.04 0.5 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XXIc & (SRC) c). It was observed that the prepared composites (7) having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation. Alginate 14 0.04 0.5 This produced water non sensitive biodegradable (7) composites named as Alginate/PVAc-composite (XXI d & d). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 22

(60) The experiments of Examples 15 and 16 were repeated taking 5 wt % agarose. To this 0.08 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 5 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXIIa & a). It was observed that the prepared composites were hydrophobic biodegradable with lower strength than the composites (XVa and XVIa) prepared in Examples 15 and 16 and thus not suitable to be used for applications such as seaweed cultivation. [Optimum yields (11.00.5 g) and compositions of composites with 4 wt % agarose: containing agarose=352 wt %, PVAc=512 wt %, glycerol 51 wt % and moisture 81 wt %; while optimum yields (13.90.5 g) and compositions of composites with 6 wt % agarose is: agarose=392 wt %, PVAc=502 wt %, glycerol 51 wt % and moisture 61 wt %].

(61) TABLE-US-00021 TABLE 22 Effect of different reaction parameters and other variables in Example 22. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 2-16 0.08 0.5 This produced water non sensitive biodegradable (5) composites named as Agar/PVAc-composite (XXIIb & b). It was observed that the prepared composites were hydrophobic biodegradable with lower strength than the composites (XVb and XVIb) prepared in Examples 15 and 16 and thus not suitable to be used for applications such as seaweed cultivation. Semi-refined 2-16 0.08 0.5 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XXIIc & (SRC) c). It was observed that the prepared composites were (5) hydrophobic biodegradable with lower strength than the composites (XVc and XVIc) prepared in Examples 15 and 16 and thus not suitable to be used for applications such as seaweed cultivation. Alginate 2-16 0.08 0.5 This produced water non sensitive biodegradable (5) composites named as Alginate/PVAc-composite (XXIId & d). It was observed that the prepared composites were hydrophobic biodegradable with lower strength than the composites (XV d and XVI d) prepared in Examples 15 and 16 and thus not suitable to be used for applications such as seaweed cultivation.

Example 23

(62) The experiments of Examples 15 and 16 were repeated taking 4 wt % agarose. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 9 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 1.5 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXIIIa & a). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for applications such as seaweed cultivation. Yields and compositions are according to the composites prepared in Examples 15 and 16.

(63) TABLE-US-00022 TABLE 23 Effect of different reaction parameters and other variables in Example 23. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 9 0.02 1.5 This produced water non sensitive biodegradable composites (4) named as Agar/PVAc-composite (XXIIIb & b). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation Semi- 9 0.02 1.5 This produced water non sensitive biodegradable composites refined named as SRC/PVAc-composite (XXIIIc & c). It was carrageenan observed that the prepared composites having improved (SRC) hydrophobicity and low strength and thus not suitable to be (4) used for applications such as seaweed cultivation. Alginate 9 0.02 1.5 This produced water non sensitive biodegradable composites (4) named as Alginate/PVAc-composite (XXIIId & d). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 24

(64) The experiments of Examples 15 and 16 were repeated taking 4 wt % agarose. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 14 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 3.0 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXIVa & a). It was observed that the prepared composites were hydrophobic biodegradable and slippery thus not suitable to be used for applications such as seaweed cultivation. Yields and compositions are according to the composites prepared in Examples 15 and 16.

(65) TABLE-US-00023 TABLE 24 Effect of different reaction parameters and other variables in Example 24. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 14 0.02 3.0 This produced water non sensitive biodegradable (4) composites named as Agar/PVAc-composite (XXIVb & b). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation Semi-refined 14 0.02 3.0 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XXIVc & (SRC) c). It was observed that the prepared composites having (4) improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation. Alginate 14 0.02 3.0 This produced water non sensitive biodegradable (4) composites named as Alginate/PVAc-composite (XXIVd & d). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 25

(66) The experiments of Examples 15 and 16 were repeated taking 6 wt % agarose. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 12 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 5.0 wt % glycerol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXVa & a). It was observed that the prepared composites were hydrophobic biodegradable and leaching of plasticizer make them slippery and weaken thus not suitable to be used for applications such as seaweed cultivation. Yields and compositions are according to the composites prepared in Examples 15 and 16.

(67) TABLE-US-00024 TABLE 25 Effect of different reaction parameters and other variables in Example 25. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 12 0.02 5.0 This produced water non sensitive biodegradable (6) composites named as Agar/PVAc-composite (XXVb & b). It was observed that the prepared composites were hydrophobic biodegradable and leaching of plasticizer make them slippery and weaken thus not suitable to be used for applications such as seaweed cultivation. Semi-refined 12 0.02 5.0 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XXVc & (SRC) c). It was observed that the prepared composites were (6) hydrophobic biodegradable and leaching of plasticizer make them slippery and weaken thus not suitable to be used for applications such as seaweed cultivation. Alginate 12 0.02 5.0 This produced water non sensitive biodegradable (6) composites named as Alginate/PVAc-composite (XXVd & d). It was observed that the prepared composites were hydrophobic biodegradable and leaching of plasticizer make them slippery and weaken thus not suitable to be used for applications such as seaweed cultivation.

Example 26

(68) The experiments of Examples 15 and 16 were repeated taking 4 wt % agarose. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 12 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % sorbitol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXVIa & a). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for applications such as seaweed cultivation. Yields and compositions are according to the composites prepared in Examples 15 and 16.

(69) TABLE-US-00025 TABLE 26 Effect of different reaction parameters and other variables in Example 26. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 12 0.02 0.5 This produced water non sensitive biodegradable (4) composites named as Agar/PVAc-composite (XXVIb & b). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation Semi-refined 12 0.02 0.5 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XXVIc & (SRC) c). It was observed that the prepared composites (4) having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation. Alginate 12 0.02 0.5 This produced water non sensitive biodegradable (4) composites named as Alginate/PVAc-composite (XXVI d & d). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 27

(70) The experiments of Examples 15 and 16 were repeated taking 6 wt % agarose. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 14 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 1.5 wt % sorbitol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXVIIa & a). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for applications such as seaweed cultivation. Yields and compositions are according to the composites prepared in Examples 15 and 16.

(71) TABLE-US-00026 TABLE 27 Effect of different reaction parameters and other variables in Example 27. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 14 0.02 1.5 This produced water non sensitive biodegradable (6) composites named as Agar/PVAc-composite (XXVIIb & b). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation Semi-refined 14 0.02 1.5 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XXVIIc & (SRC) c). It was observed that the prepared composites having (6) improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation. Alginate 14 0.02 1.5 This produced water non sensitive biodegradable (6) composites named as Alginate/PVAc-composite (XXVII d & d). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 28

(72) The experiments of Examples 15 and 16 were repeated taking 6 wt % agarose. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 10 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 3.0 wt % sorbitol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXVIIIa & a). It was observed that the prepared composites were hydrophobic biodegradable and slippery thus not suitable to be used for applications such as seaweed cultivation. Yields and compositions are according to the composites prepared in Examples 15 and 16.

(73) TABLE-US-00027 TABLE 28 Effect of different reaction parameters and other variables in Example 28. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 10 0.02 3.0 This produced water non sensitive biodegradable (6) composites named as Agar/PVAc-composite (XXVIIIb & b). It was observed that the prepared composites were hydrophobic biodegradable and slippery thus not suitable to be used for applications such as seaweed cultivation. Semi-refined 10 0.02 3.0 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XXVIIIc & (SRC) c). It was observed that the prepared composites were (6) hydrophobic biodegradable and slippery thus not suitable to be used for applications such as seaweed cultivation. Alginate 10 0.02 3.0 This produced water non sensitive biodegradable (6) composites named as Alginate/PVAc-composite (XXVIII d & d). It was observed that the prepared composites were hydrophobic biodegradable and slippery thus not suitable to be used for applications such as seaweed cultivation.

Example 29

(74) The experiments of Examples 15 and 16 were repeated taking 4 wt % agarose. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 8 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 0.5 wt % ethylene glycol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXIXa & a). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for applications such as seaweed cultivation. Yields and compositions are according to the composites prepared in Examples 15 and 16.

(75) TABLE-US-00028 TABLE 29 Effect of different reaction parameters and other variables in Example 29. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 8 0.02 0.5 This produced water non sensitive biodegradable (4) composites named as Agar/PVAc-composite (XXIXb & b). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation Semi-refined 8 0.02 0.5 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XXIXc & (SRC) c). It was observed that the prepared composites having (4) improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation. Alginate 8 0.02 0.5 This produced water non sensitive biodegradable (4) composites named as Alginate/PVAc-composite (XXIXd & d). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 30

(76) The experiments of Examples 15 and 16 were repeated taking 8 wt % agarose. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 10 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 1.5 wt % ethylene glycol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXXa & a). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for applications such as seaweed cultivation. Yields and compositions are according to the composites prepared in Examples 15 and 16.

(77) TABLE-US-00029 TABLE 30 Effect of different reaction parameters and other variables in Example 30. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 10 0.02 1.5 This produced water non sensitive biodegradable (8) composites named as Agar/PVAc-composite (XXXb & b). It was observed that the prepared composites were hydrophobic biodegradable with high strength and thus suitable to be used for potential applications such as seaweed cultivation Semi-refined 10 0.02 1.5 This produced water non sensitive biodegradable carrageenan composites named as SRC/PVAc-composite (XXXc & (SRC) c). It was observed that the prepared composites having (8) improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation. Alginate 10 0.02 1.5 This produced water non sensitive biodegradable (8) composites named as Alginate/PVAc-composite (XXXd & d). It was observed that the prepared composites having improved hydrophobicity and low strength and thus not suitable to be used for applications such as seaweed cultivation.

Example 31

(78) The experiments of Examples 15 and 16 were repeated taking 8 wt % agarose. To this 0.02 wt % potassium persulphate (KPS) was added under stirring, followed by addition of 10 wt % vinyl acetate (VAc). The reaction mixture was heated in aqueous medium under reflux conditions at 80 degree Celsius for 5 h with constant stirring. 3.0 wt % ethylene glycol was added into the reaction mixture and then transferred into the desired hollow vessels/devices/moulds to obtain the desired shapes. The resulting moulded composites were treated with organic solvent at a temperature of 25 degree Celsius to remove the unreacted homopolymer followed by air drying. This produced water non sensitive biodegradable composites named as Agarose/PVAc-composites (XXXIa & a). It was observed that the prepared composites were hydrophobic biodegradable and slippery thus not suitable to be used for applications such as seaweed cultivation. Yields and compositions are according to the composites prepared in Examples 15 and 16.

(79) TABLE-US-00030 TABLE 31 Effect of different reaction parameters and other variables in Example 31. Seaweed phycocolloid VAc KPS Plasticizer (wt %) (wt %) (wt %) (wt %) Remarks/Observations Agar 10 0.02 3.0 This produced water non sensitive biodegradable composites (8) named as Agar/PVAc-composite (XXXIb & b). It was observed that the prepared composites were hydrophobic biodegradable and slippery thus not suitable to be used for applications such as seaweed cultivation. Semi- 10 0.02 3.0 This produced water non sensitive biodegradable composites refined named as SRC/PVAc-composite (XXXIc & c). It was observed carrageenan that the prepared composites were hydrophobic biodegradable (SRC) and slippery thus not suitable to be used for applications such as (8) seaweed cultivation. Alginate 10 0.02 3.0 This produced water non sensitive biodegradable composites (8) named as Alginate/PVAc-composite (XXXId & d). It was observed that the prepared composites were hydrophobic biodegradable and slippery thus not suitable to be used for applications such as seaweed cultivation.

Example 32

(80) The hydrophobic biodegradable composites prepared in Examples 14-31 were treated with color reducing food grade dyes namely Brilliant Blue FCF, Allura Red AC, and Tartrazine, etc. to obtain desired colored ropes for making decorative or attractive household items (FIG. 1).

Example 33

(81) Reaction mixtures obtained in Examples 14-20 were tested for their biodegradability using moist soil test after casting in the form of films and ropes. The films got degraded within 20-45 days; whiles ropes took longer duration in the range of 90 to 600 day to degrade completely. This Example revealed that materials obtained in the above Examples are biodegradable and eco-friendly.

Example 34

(82) The hydrophobic biodegradable composites prepared in Examples 15 and 16 were used for seaweed cultivation in seawater environment. For this, Kappaphycus alvarezii was collected from south east coast (Thoniturai, 79 1029E-9 1621N), Mandapam-623 519, Tamil Nadu, India, and was cultivated at Thoniturai, 79 1029E-9 1621N on the biodegradable hydrophobic ropes prepared from the composites of Examples 15 and 16 and fixed with planting rope (8 mm diameter which was Garware polypropylene rope). The plant was allowed to grow in open sea water and periodical observations were made to ensure the acclimatization of the biodegradable rope in marine environment. It was observed that the growth of the plants was normal and was comparable with plants grown by common methods adopted for commercial cultivation of Kappaphycus using 0.5 mm dia braider for tie-tie method. After 35 days the total biomass and daily growth rate (DGR %) were 480 grams and 4.48% respectively in the biodegradable ropes. The same plant was also grown in braider as well as on the combination of braider and biodegradable ropes, and the total biomass was observed to be 390 (DGR 3.88%) and 425.5 (DGR 4.13%), respectively, which was lesser as compared to seaweed phycocolloids based ropes (Table 32 & FIG. 2).

(83) TABLE-US-00031 TABLE 32 Performance of hydrophobic ropes during seaweed cultivation (Kappaphycus alvarezii) in the open Sea at Mandapam, Tamil Nadu. Braider & Biodegradable Biodegradable Sr. No. Braider rope rope Initial weight (gm) 100.0 100.0 100.0 Fresh weight after 35 days 390.0 425.5 480.0 DGR %/day 3.88 4.13 4.48

Example 35

(84) The hydrophobic biodegradable composites prepared in Examples 14-20 were used as handles of carry bags, which have capacity to carry 2-5 kg weight (FIG. 3). Seaweed polysaccharides based handles offers superior feeling when carrying bags compared to synthetic handles. No adverse effects were observed on using handles of ropes prepared in Examples 14-20 up to 3 months. After 3 months there is no considerable effect on the performance and quality of biodegradable ropes. These are eco-friendly and easy to dispose off in the open environment.

Example 36

(85) The hydrophobic biodegradable composites prepared as per the procedure of Example 14-31 were used as biodegradable design e.g. in designing belts, bags and other leather or cloth items (FIG. 4). It offers very smooth and soft feeling while wearing belts with biodegradable design compared to synthetic handles. Even after 2 months, there was no considerable change in the performance and quality of these designs.

Example 37

(86) The hydrophobic biodegradable composites prepared as per the procedure of Example 14-31 were used as biodegradable cap of studs (FIG. 5). Stud cap of biodegradable ropes offers superior feeling when worn in ear compared to synthetic one. Even after 2 months there was no adverse effect or any allergic effect on the skin of the ear.

Example 38

(87) The hydrophobic biodegradable composites prepared as per the procedure of Example 14-31 were used for the preparation of biodegradable bowl, which has capacity to carry 2-5 kg weight (FIG. 6). It was observed that it offer attractive look while in use of keeping vegetables and fruits in biodegradable bowl compared to synthetic. Even after 9 months there was no considerable change in the performance and quality of the biodegradable bowls.

Example 39

(88) The bowl prepared as per Example 38 was used as biodegradable bowl for storage of vegetable and fruits items, which has the capacity to carry 2-5 kg weight (FIG. 7). It was observed that it offers attractive look in house when vegetable and fruits were kept in biodegradable bowl as compared to synthetic. Even after 9 months there was no considerable change in the performance and quality of the biodegradable bowls.

Example 40

(89) The bowl prepared as per Example 38 was used as biodegradable bowl for storage of biscuits, chips and other food packets, which has the capacity to carry 2-5 kg weight (FIG. 8). It was observed that it offers attractive look in house when biscuit and chips and other food packets were kept in biodegradable bowl as compared to synthetic. Even after 9 months there was no considerable change in the performance and quality of the biodegradable bowls.

Example 41

(90) The hydrophobic biodegradable composites prepared as per the procedure of Examples 14-20 were used as biodegradable flower pots/jars, which provided good looks and feeling (FIGS. 9 and 10). It was observed that it offers attractive look in house when flowers were kept in biodegradable pots/jars. Even after 11 months there was no considerable change in the performance and quality of the biodegradable flower pots/jars.

Example 42

(91) The hydrophobic biodegradable composites prepared in Examples 14-31 were used for making biodegradable gift items including hand belts (FIG. 11). It was observed that it offered attractive look in hands. Even after 6 months there was no adverse effect on the skin as well as the performance and quality of the biodegradable hand belts.

Example 43

(92) The hydrophobic biodegradable composites prepared in Examples 15 and 16 were used for drying of cloths in environmental conditions (FIG. 12). It was observed that it offered attractive look in houses and no rusting was observed even after 3 months of use. After 3 months there was no adverse change on the smoothness as well as on the performance and quality of the hydrophobic biodegradable composites.

Advantages of the Invention

(93) Recognizing the fact that seaweed cultivation inevitably requires use of ropes and that non-biodegradability of available ropes can pose a serious environmental threat where cultivation is undertaken on a very large scale, leading to massive problem of pollution with the generated solid waste, the present invention provides a solution to said problem by providing biodegradable hydrophobic composites which can be moulded in form of ropes that can be well used for seaweed cultivation.

(94) By blending monomers such as vinyl acetate onto the seaweed polymers it is possible to impart enhanced hydrophobicity to the prepared composites without compromising excessively on their biodegradability, especially in soil.

(95) The prepared biodegradable hydrophobic composites exhibit high thermal stability which allows them to be sterilized at high temperature for wider applications such as in pharmaceutical applications.

(96) The prepared biodegradable hydrophobic composites exhibit stability in water up to 90 degree Celsius which may be used for wider aqueous applications such as cultivation of seaweeds in open sea water.