WO2017111711A1 - An antifouling polymer based composition - Google Patents

An antifouling polymer based composition Download PDF

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Publication number
WO2017111711A1
WO2017111711A1 PCT/TH2016/000104 TH2016000104W WO2017111711A1 WO 2017111711 A1 WO2017111711 A1 WO 2017111711A1 TH 2016000104 W TH2016000104 W TH 2016000104W WO 2017111711 A1 WO2017111711 A1 WO 2017111711A1
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Prior art keywords
polyethylene
parts
antifouling
weight
polymer based
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PCT/TH2016/000104
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French (fr)
Inventor
Nopphawan Phonthammachai
Wareerom POLRUT
Noppakun SANPO
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Scg Chemicals Company Limited
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Publication date
Priority claimed from TH1501007806A external-priority patent/TH167832A/en
Application filed by Scg Chemicals Company Limited filed Critical Scg Chemicals Company Limited
Publication of WO2017111711A1 publication Critical patent/WO2017111711A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/015—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/378—Thiols containing heterocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/325—Calcium, strontium or barium phosphate

Definitions

  • polyolefin has been used for various applications such as for producing packages, tubes, films, etc.
  • polyolefin cannot be applied for certain applications e.g. underwater pipes, roto-molding products for submarine applications, polymer based coatings, etc.
  • a number of efforts has been made to invent and develop polyolefin polymer based products capable of preventing fouling caused by aquatic organisms, for example, by coating the polymer surface with particles having such antifouling properties by e.g. heat spray coating.
  • such coating method is not suitable for producing products for submarine applications due to the leaching of the antifouling particles. Examples of such efforts to invent and develop self-antifouling polymer based compositions are shown by the following prior arts.
  • US 6,635,692 Bl discloses an antifouling polymer based composition
  • polymer is selected from a group consisting of ethylene-vinyl acetate copolymer (EVA), high density polyethylene (HDPE), sodium ionomer, copolymer of ethylene and acrylic acid and mixtures thereof
  • organic agent is selected from a group consisting o isothiazolone based agent (e.g.
  • UHMWPE ultra high molecular weight polyethylene
  • US 5.916,947 discloses an antifouling coating composition
  • an antifouling coating composition comprising zinc oxide which is coated with photosensitizer to increase the capability of zinc oxide to absorb visible light.
  • Said coating composition having 20 to 60 wt% of zinc oxide and said photosensitizer is selected from a group consisting of fumed anatase, strontium titanate, bianthrone, azulene, zinc pyrithione, terthiophene, hypericin and mixtures thereof.
  • Said coating further comprises additional polymers e.g. polyvinyl, polyalkyd, polyepoxide, polysiloxane, polyurethane, polyacrylonitrile, polyacrylate, polyester resin or mixtures thereof.
  • the present invention relates to a self-antifouling polyolefin based composite composition.
  • the present invention relates particularly to an antifouling polymer based composition
  • an antifouling polymer based composition comprising polyethylene (PE) and at least one antifouling-active filler selected from the group consisting of 2-methylthio-4-ethylamino-6-tert-butylamino-s-triazine, 2,4,4'-trichloro-2'- hydroxy diphenyl ether, 2-benzisothiazol-3-one, zinc oxide, bis(2-pyridylthio)zinc 1 ,1 '- dioxide, metal -doped hydroxyapatite, copper-containing chitosan and mixtures thereof, wherein the antifouling-active filler is present in a range of 0.1-5 parts by weight based on 100 parts by weight of polyethylene.
  • PE polyethylene
  • antifouling-active filler selected from the group consisting of 2-methylthio-4-ethylamino-6-tert-butylamino-s-triazine
  • the object of the present invention is to provide an antifouling polymer based composition capable of preventing fouling caused by aquatic organisms e.g. algae, barnacles, etc.
  • the composition offers technical advantages resulting from good dispersion and distribution of the antifouling-active filler in a polymer matrix, high stability due to the antifouling-active filler according to the present invention still remaining highly stable after mixing with the polymer, low leaching rate o the antifouling-active filler of the polymer based composition from the polymer matrix, environmental-friendly, long service life, and persistent mechanical properties of the polymer or the plastic products, etc.
  • Fig. 1 shows the microstructure (rnicrostructure) of the cross-sectional surface of the polymer based composition according to the present invention.
  • Fig. 2 is a graph showing the relationship between the antifouling-active fillers and the mechanical properties of the polymer based compositions.
  • Fig. 3 shows the antibacterial test: (a) the antibacterial property against S. aureus cultured by agar diffusion method; (b) a graph showing the relationship between the inhibition zone for S. aureus and the types of antifouling-active filler in the polymer based composition.
  • Fig. 4 shows the antibacterial test: (a) antibacterial property against S. aureus cultured by broth dilution method; (b) a graph showing the relationship between the amount of S. aureus in the broth solution and types of the antifouling-active fillers in the polymer based compositions.
  • Fig. 5 shows the antibacterial test: (a) antibacterial property against E. coli cultured by agar diffusion method; (b) a graph showing the relationship between the inhibition zone for E. coli and types of antifoul ing-active filler in the polymer based compositions.
  • Fig. 6 shows the antibacterial test: (a) antibacterial property against E. coli cultured by broth dilution method; (b) a graph showing the relationship between the amount of E. coli in the broth solution and types of the antifouling-active fillers in the polymer based compositions.
  • Fig. 7 shows fouling profile of marine organisms on the sample polymer sheets.
  • the antifouling polymer based composition according to the present invention comprises: polyethylene (PE) selected from low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE) or mixtures thereof; and at least one antifouling-active filler selected from a group consisting of 2-methylthio-4- ethylamino-6-tert-butylamino-s-triazine, 2,4,4 ' -trichloro-2 ' -hydroxy diphenyl ether, 2- benzisothiazol-3-one, zinc oxide, bis(2-pyridilthio)zinc 1 ,1 '-dioxide or zinc pyrithione, metal- doped hydroxyapatite, copper-containing chitosan and mixtures thereof.
  • the antifouling-active filler is present in a range of
  • the antifouling-active filler is preferably present in a range of 0.1- 3 parts by weight based on 100 parts by weight of polyethylene.
  • the antifouling-active filler according to the present invention is an antifouling-active filler acting against fouling caused by algae, barnacles, etc.
  • polyethylene preferably has a density in a range of 0.95- 0.98 g/cm 3 and has a flow index in a range of 0.25 -0.50 g/10 minutes.
  • the metal -doped hydroxyapatite herein is hydroxyapatite with added metal which is selected from a group consisting of Ag-doped hydroxyapatite (Ag-doped hydroxyapatite), Ni-doped hydroxyapatite (Ni-doped hydroxyapatite) and mixtures thereof.
  • the antifouling polymer based composition may further comprise a polymer additives including a lubricant facilitating good mixing and acid scavenger neutralizing catalyst residue in the polymer as well as antioxidant in order to prevent polymer degradation from oxidation reaction of the polymer containing said antifouling-active filler. This would lengthen the service life time of the product and prevent the yellowing of the product during the molding process.
  • the additive according to the present invention is selected from a group consisting of calcium stearate, zinc stearate, antioxidant and mixtures thereof. According to the present invention, said additive may be present in the polymer based composition in a range of 0.1 -5 parts by weight based on 100 parts by weight of polyethylene.
  • antioxidants in case of primary antioxidant or phenolic antioxidant.
  • primary antioxidants are pentaerythritol tetrakis (3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate), etc.
  • secondary antioxidant or peroxide decomposers examples of secondary antioxidant are tris(2,4-di-tert-butylphenyl)phosphite, etc.
  • the antioxidant according to the present invention is selected from a group consisting of tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy)hydrocinnamatejmethane, tris(2,4-di-tert- butylphenyl)phosphite and mixtures thereof. Said antioxidant is present in a range of 0.1 -5 parts by weight based on 100 parts by weight of polyethylene.
  • the antifouling polymer based composition may further comprise at least one polymer selected from the group consisting of poly(methyI methacrylate) (PMMA), polypropylene (PP), polyurethane (PU), melamine (melamine), polyvinyl chloride (PVC) and mixtures thereof in a range of 5-30 parts by weight based on 100 parts by weight of polyethylene.
  • PMMA poly(methyI methacrylate)
  • PP polypropylene
  • PU polyurethane
  • melamine melamine
  • PVC polyvinyl chloride
  • the term "antifouling” as described above is not limited only to preventing the fouling caused by algae and/or barnacles but also microorganism such as microbes, bacteria or macroorganism which is involved in or cause algae and/or barnacle fouling.
  • said antifouling polymer based composition can be molded into a variety of products, for example, submarine pipe for transferring oil or gas.
  • the antifouling polymer based composition according to the present invention can be prepared by mixing polyethylene e.g. high density polyethylene with 3 wt% of anti ouling- active filler, and other additives may be added. The mixing is carried out using a high speed mixer to obtain the polymer based composition in the form of homogenous powder. The obtained product is then subjected to extrusion process in a twin screw extruder under a condition which homogenous plastic pellet can be obtained. Samples of the polymer based compositions prepared by mixing with each of the antifouling-active additives are
  • Z a polymer based composition having zinc oxide
  • Zl is a polymer based composition having nanoparticle zinc oxide
  • Z2 is a polymer based composition having microparticle zinc oxide
  • ZP a polymer based composition having bis(2-pyridilthio)zinc 1 , 1 '-dioxide or zinc pyrithione, herein abbreviated as ZP;
  • melt flow index as carried out by melting plastic pellet in a cylinder at a determined temperature then applying weight on the piston allowing the piston to act on the melted plastic in the cylinder, making the melted plastic flo out of the die head. The flown-out plastic is then weighed for 10 minutes to determine the flow rate of the melted plastic in gram per 10 minutes.
  • melt flow index and mechanical properties refer to the viscosity, the molecular weight and the mechanical strength of the polymer based compositions containing each of the antifouling-active fillers.
  • the antibacterial test of the polymer based composition comprising each of the antifouling-active filler according to the present invention was carried out using 2 types of general bacteria which are not severely harmful to living organisms and easy to use for the test i.e. Staphylococcus aureus (S. aureus) representing gram positive bacteria and Escherichia coli (E. coli) representing gram positive bacteria.
  • the test has 2 following sections.
  • Section 1 Agar diffusion method— the test was carried out by placing a fixed volume of circular specimen on the agar having a concentration of 1.5 to 2 wt% on which the bacteria was cultured. If the filler is capable of inhibiting the growth of the test bacteria, an inhibition zone or a clear zone will appear. The bigger the clear zone is, the greater the inhibition efficiency will be. This method can be carried out easily, conveniently and fast and allows testing multiple substances at the same time. This method is suitable for bacteria taking 18-24 hr of incubation.
  • Section 2 Broth dilution method was used for confirming the result from agar diffusion method. This test was carried out by conducting two-fold serial dilution to obtain diluted solutions with different bacteria concentrations. The obtained diluted solutions were adjusted to achieve 0.5 turbidity (McFarland standard), then incubated at 37°C for 24 hours. The results were read by observing the growth of the test bacteria based on the turbidity present. If bacterial inhibiting plastic specimen has great efficiency, no turbidity will appear in the test samples.
  • Fig. 3(a) shows that the polymer based composition comprising the antifouling-active filler according to the present invention were capable of significantly inhibiting the growth of S. aureus.
  • the polymer based composition comprising the antifouling-active filler, 2-benzisothiazol-3-one (2 BO) and copper-containing chitosan (CCu) shows the biggest clear zone having the average diameter of 5.5 cm as shown in Fig. 3(b).
  • the polymer based composition comprising the antifouling-active filler according to the present invention is capable of significantly inhibiting the growth of bacteria in the broth solution. Furthermore, the results from a quantitative analysis carried out by measuring the turbidity of the test solutions using UV visible spectroscopy at the wavelength of 600 run as shown in Fig. 4(b). In conclusion, the polymer based composition comprising the antifouling-active filler according to the present invention is capable of significantly inhibiting the growth of the bacteria in the broth solution.
  • the polymer based composition comprising the antifouling-active filler according to the present invention is capable of significantly inhibiting the growth of E. coli.
  • the polymer based composition comprising the antifouling-active filler of copper-containing chitosan (CCu) shows the biggest clear zone of an average diameter of 5 cm as shown in Fig. 5(b).
  • the solution containing the polymer based composition comprising the antifouling-active filler according to the present invention is capable of significantly inhibiting the growth of the test bacteria in the broth solution compared to the solution containing polymer without antifouling- active filler (control sample).
  • the polymer based composition comprising the antifouling-active filler according to the present invention is capable of significantly inhibiting the growth of bacteria.
  • the immersion test of the sample of polymer based composition comprising different antifouling-active fillers according to the present invention was carried out by subjecting the sample polymer based composition to compression molding to obtain square polymer sheet. Said polymer sheet were then tested in the sea water to observe the fouling profile compared with the polymer sheet control sample as shown in Fig. 7.
  • test results show that extensive barnacles and algae fouling was found on the surface of the polymer sheet control sample (i.e. the polymer sheet without active filler) after 4 weeks while only slight fouling were found on the surface of most of the polymer sheet obtained from compressing the pellets of the polymer based composition comprising the antifouling-active filler according to the present invention. This shows the capability of the present invention in preventing aquatic fouling.
  • the polymer based composition having antifouling- active filler according to the present invention is a result of the components, particular amount of the components, process steps including other elements which yield the above advantages.
  • the antifouling polymer based composition according to the present invention is not limited to said components, particular amount of the components, process steps and elements detailed above. Modifications or variations can still be made to the present invention without departing from the scope and the spirit of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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Abstract

The present invention relates particularly to an antifouling polymer based composition comprising polyethylene (PE) and at least one antifouling-active filler selected from the group consisting of 2-methylthio-4-ethylamino-6-tert-butylamino-s-triaz.ine, 2,4,4'-trichloro-2'-hydroxy diphenyl ether, 2-benzisothiazol-3-one, zinc oxide, bis(2-pyridilthio)zinc 1,1'-dioxide, metal-doped hydroxyapatite, copper-containing chitosan or mixtures thereof, wherein the anti fouling-active filler is present in a range of 0.1-5 parts by weight based on 100 parts by weight of polyethylene.

Description

AN ANTIFOULING POLYMER BASED COMPOSITION
TECHNICAL FIELD
Chemistry related to an antifouling polymer based composition
BACKGROUND OF THE INVENTION In present days, polyolefin has been used for various applications such as for producing packages, tubes, films, etc. However, due to the limitation in anti-fouling caused by aquatic organisms such as algae, barnacles, etc., polyolefin cannot be applied for certain applications e.g. underwater pipes, roto-molding products for submarine applications, polymer based coatings, etc. Accordingly, a number of efforts has been made to invent and develop polyolefin polymer based products capable of preventing fouling caused by aquatic organisms, for example, by coating the polymer surface with particles having such antifouling properties by e.g. heat spray coating. However, such coating method is not suitable for producing products for submarine applications due to the leaching of the antifouling particles. Examples of such efforts to invent and develop self-antifouling polymer based compositions are shown by the following prior arts.
US 6,635,692 Bl discloses an antifouling polymer based composition comprising polymer and one or more organic antifouling active agent wherein said polymer is selected from a group consisting of ethylene-vinyl acetate copolymer (EVA), high density polyethylene (HDPE), sodium ionomer, copolymer of ethylene and acrylic acid and mixtures thereof, and said organic agent is selected from a group consisting o isothiazolone based agent (e.g. 4,5- dichloro-2-n-octyl-4-isothiazoline-3-one), furanone and combinations thereof, wherein said antifouling in the furanone group is selected from mixtures of (l 'RS,5E)-3-(l r-bromoethyl)-4- bromo-5-(bromomethylidene)-2(5H)-furanone and (1 'RS)-3-( 1 '-bromoethyl)-5- (dibromomethylidene)-2(5H)-furanone or (l 'RS,5Z)-3-( r-bromohexyl)-4-bromo-5- (bromomethylidene)-2(5H)-furanone and (1 'RS)-3-(l '-bromohexyl)-5-(bromomethylidene)- 2(5H)-furanone.
US 201 1/0070454 Λ 1 discloses an ultra high molecular weight polyethylene (UHMWPE) composition having antifouling properties comprising ultra high molecular weight polyethylene, polychlorophenoxyphenol (particularly, 2,4,4,-trichloro-2'-hydroxy- diphenylether), organopolysiloxane and a silver-containing biocide.
US 5.916,947 discloses an antifouling coating composition comprising zinc oxide which is coated with photosensitizer to increase the capability of zinc oxide to absorb visible light. Said coating composition having 20 to 60 wt% of zinc oxide and said photosensitizer is selected from a group consisting of fumed anatase, strontium titanate, bianthrone, azulene, zinc pyrithione, terthiophene, hypericin and mixtures thereof. Said coating further comprises additional polymers e.g. polyvinyl, polyalkyd, polyepoxide, polysiloxane, polyurethane, polyacrylonitrile, polyacrylate, polyester resin or mixtures thereof. However, the developments and improvements of antifouling polymer based compositions as shown in the above prior arts are still insufficient to address various application requirements and the following issues regarding the resulting product e.g. instability of antifouling active agent, rapid leaching rate, environmental toxicity in case where a composition contains tin and short service life etc., have not been contemplated. SUMMARY OF THE INVENTION
The present invention relates to a self-antifouling polyolefin based composite composition.
The present invention relates particularly to an antifouling polymer based composition comprising polyethylene (PE) and at least one antifouling-active filler selected from the group consisting of 2-methylthio-4-ethylamino-6-tert-butylamino-s-triazine, 2,4,4'-trichloro-2'- hydroxy diphenyl ether, 2-benzisothiazol-3-one, zinc oxide, bis(2-pyridylthio)zinc 1 ,1 '- dioxide, metal -doped hydroxyapatite, copper-containing chitosan and mixtures thereof, wherein the antifouling-active filler is present in a range of 0.1-5 parts by weight based on 100 parts by weight of polyethylene. The object of the present invention is to provide an antifouling polymer based composition capable of preventing fouling caused by aquatic organisms e.g. algae, barnacles, etc. The composition offers technical advantages resulting from good dispersion and distribution of the antifouling-active filler in a polymer matrix, high stability due to the antifouling-active filler according to the present invention still remaining highly stable after mixing with the polymer, low leaching rate o the antifouling-active filler of the polymer based composition from the polymer matrix, environmental-friendly, long service life, and persistent mechanical properties of the polymer or the plastic products, etc.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows the microstructure (rnicrostructure) of the cross-sectional surface of the polymer based composition according to the present invention.
Fig. 2 is a graph showing the relationship between the antifouling-active fillers and the mechanical properties of the polymer based compositions.
Fig. 3 shows the antibacterial test: (a) the antibacterial property against S. aureus cultured by agar diffusion method; (b) a graph showing the relationship between the inhibition zone for S. aureus and the types of antifouling-active filler in the polymer based composition.
Fig. 4 shows the antibacterial test: (a) antibacterial property against S. aureus cultured by broth dilution method; (b) a graph showing the relationship between the amount of S. aureus in the broth solution and types of the antifouling-active fillers in the polymer based compositions. Fig. 5 shows the antibacterial test: (a) antibacterial property against E. coli cultured by agar diffusion method; (b) a graph showing the relationship between the inhibition zone for E. coli and types of antifoul ing-active filler in the polymer based compositions.
Fig. 6 shows the antibacterial test: (a) antibacterial property against E. coli cultured by broth dilution method; (b) a graph showing the relationship between the amount of E. coli in the broth solution and types of the antifouling-active fillers in the polymer based compositions.
Fig. 7 shows fouling profile of marine organisms on the sample polymer sheets.
DETAILED DESCRIPTION
The following details describe the specification of the invention.
The antifouling polymer based composition according to the present invention comprises: polyethylene (PE) selected from low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE) or mixtures thereof; and at least one antifouling-active filler selected from a group consisting of 2-methylthio-4- ethylamino-6-tert-butylamino-s-triazine, 2,4,4 ' -trichloro-2 ' -hydroxy diphenyl ether, 2- benzisothiazol-3-one, zinc oxide, bis(2-pyridilthio)zinc 1 ,1 '-dioxide or zinc pyrithione, metal- doped hydroxyapatite, copper-containing chitosan and mixtures thereof. According to the present invention, the antifouling-active filler is present in a range of
0.1 - 5 parts by weight based on 100 parts by weight of polyethylene.
According to the present invention, the antifouling-active filler is preferably present in a range of 0.1- 3 parts by weight based on 100 parts by weight of polyethylene.
The antifouling-active filler according to the present invention is an antifouling-active filler acting against fouling caused by algae, barnacles, etc.
According to the present invention, polyethylene preferably has a density in a range of 0.95- 0.98 g/cm3 and has a flow index in a range of 0.25 -0.50 g/10 minutes.
According to the present invention, the metal -doped hydroxyapatite herein is hydroxyapatite with added metal which is selected from a group consisting of Ag-doped hydroxyapatite (Ag-doped hydroxyapatite), Ni-doped hydroxyapatite (Ni-doped hydroxyapatite) and mixtures thereof.
According to the present invention, the antifouling polymer based composition may further comprise a polymer additives including a lubricant facilitating good mixing and acid scavenger neutralizing catalyst residue in the polymer as well as antioxidant in order to prevent polymer degradation from oxidation reaction of the polymer containing said antifouling-active filler. This would lengthen the service life time of the product and prevent the yellowing of the product during the molding process.
The additive according to the present invention is selected from a group consisting of calcium stearate, zinc stearate, antioxidant and mixtures thereof. According to the present invention, said additive may be present in the polymer based composition in a range of 0.1 -5 parts by weight based on 100 parts by weight of polyethylene.
Such antioxidant functions as follow: ( 1 ) in case of primary antioxidant or phenolic antioxidant. Examples of primary antioxidants are pentaerythritol tetrakis (3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate), etc.; and (2) in case of secondary antioxidant or peroxide decomposers. Examples of secondary antioxidant are tris(2,4-di-tert-butylphenyl)phosphite, etc.
The antioxidant according to the present invention is selected from a group consisting of tetrakis[methylene(3,5-di-tert-butyl-4-hydroxy)hydrocinnamatejmethane, tris(2,4-di-tert- butylphenyl)phosphite and mixtures thereof. Said antioxidant is present in a range of 0.1 -5 parts by weight based on 100 parts by weight of polyethylene.
According to the present invention, the antifouling polymer based composition may further comprise at least one polymer selected from the group consisting of poly(methyI methacrylate) (PMMA), polypropylene (PP), polyurethane (PU), melamine (melamine), polyvinyl chloride (PVC) and mixtures thereof in a range of 5-30 parts by weight based on 100 parts by weight of polyethylene.
According to the present invention, the term "antifouling" as described above is not limited only to preventing the fouling caused by algae and/or barnacles but also microorganism such as microbes, bacteria or macroorganism which is involved in or cause algae and/or barnacle fouling.
According to the present invention, said antifouling polymer based composition can be molded into a variety of products, for example, submarine pipe for transferring oil or gas.
The present invention will now be described in further detail with the following examples. However, these examples should not be construed as limiting the scope of the present invention.
1. Preparation of the polymer based composition
The antifouling polymer based composition according to the present invention can be prepared by mixing polyethylene e.g. high density polyethylene with 3 wt% of anti ouling- active filler, and other additives may be added. The mixing is carried out using a high speed mixer to obtain the polymer based composition in the form of homogenous powder. The obtained product is then subjected to extrusion process in a twin screw extruder under a condition which homogenous plastic pellet can be obtained. Samples of the polymer based compositions prepared by mixing with each of the antifouling-active additives are
- a polymer based composition having 2-methylthio-4-ethylamino-6-tert-butylamino-s- triazine, herein abbreviated as 2MT; - a polymer based composition having 2-benzisothiazol-3-one, herein abbreviated as
2BO;
- a polymer based composition having zinc oxide, herein abbreviated as Z, Zl is a polymer based composition having nanoparticle zinc oxide and Z2 is a polymer based composition having microparticle zinc oxide; - a polymer based composition having bis(2-pyridilthio)zinc 1 , 1 '-dioxide or zinc pyrithione, herein abbreviated as ZP;
- a polymer based composition having Ag-doped hydroxyapatite, herein abbreviated as
HAgl ;
- a polymer based composition having copper-containing chitosan, herein abbreviated as CCu.
2. Dispersion, distribution, and mechanical properties
According to the present invention, when subjecting samples of the polymer based composition comprising high density polyethylene and different antifouling-active fillers in the form of plastic pellets to study the mixability between the polymer and each of the fillers using a scanning electron microscope (SEM), it was found that the filler in the polymer based compositions exhibited good dispersion and distribution as shown in Fig. 1.
Furthermore, when plastic pellet are subjected to mechanical properties testing e.g. tensile properties, i.e. tensile strength at yield— the tensile strength requiring to reach the elongation at yield— and elongation at yield -— the elongation of testing specimen begin to lose its completely reversible deformation— and melt flow index as carried out by melting plastic pellet in a cylinder at a determined temperature then applying weight on the piston allowing the piston to act on the melted plastic in the cylinder, making the melted plastic flo out of the die head. The flown-out plastic is then weighed for 10 minutes to determine the flow rate of the melted plastic in gram per 10 minutes. Those melt flow index and mechanical properties refer to the viscosity, the molecular weight and the mechanical strength of the polymer based compositions containing each of the antifouling-active fillers.
Based on the above tests, it was found that most of the polymer based compositions comprising the antifouling-active filler according to the present invention exhibit mechanical properties and a melt flow rate comparable to polymer resins without antifouling-active filler (control sample) as shown in Fig. 2.
3. Antibacterial test
The antibacterial test of the polymer based composition comprising each of the antifouling-active filler according to the present invention was carried out using 2 types of general bacteria which are not severely harmful to living organisms and easy to use for the test i.e. Staphylococcus aureus (S. aureus) representing gram positive bacteria and Escherichia coli (E. coli) representing gram positive bacteria. The test has 2 following sections.
Section 1 : Agar diffusion method— the test was carried out by placing a fixed volume of circular specimen on the agar having a concentration of 1.5 to 2 wt% on which the bacteria was cultured. If the filler is capable of inhibiting the growth of the test bacteria, an inhibition zone or a clear zone will appear. The bigger the clear zone is, the greater the inhibition efficiency will be. This method can be carried out easily, conveniently and fast and allows testing multiple substances at the same time. This method is suitable for bacteria taking 18-24 hr of incubation.
Section 2: Broth dilution method was used for confirming the result from agar diffusion method. This test was carried out by conducting two-fold serial dilution to obtain diluted solutions with different bacteria concentrations. The obtained diluted solutions were adjusted to achieve 0.5 turbidity (McFarland standard), then incubated at 37°C for 24 hours. The results were read by observing the growth of the test bacteria based on the turbidity present. If bacterial inhibiting plastic specimen has great efficiency, no turbidity will appear in the test samples.
3.1 Antibacterial test results for S. aureus The results from the test using agar diffusion method (Fig. 3(a)) shows that the polymer based composition comprising the antifouling-active filler according to the present invention were capable of significantly inhibiting the growth of S. aureus. Particularly, the polymer based composition comprising the antifouling-active filler, 2-benzisothiazol-3-one (2 BO) and copper-containing chitosan (CCu) shows the biggest clear zone having the average diameter of 5.5 cm as shown in Fig. 3(b).
Based on the antibacterial test conducted on S. aureus cultured by broth dilution method (Fig. 4(a)), it was found that the solution containing the polymer based composition comprising the antifouling-active filler according to the present invention was clear. On the contrary, the solution containing polymer without antifouling-active filler (control sample) was turbid. Therefore, it can be concluded that the polymer based composition comprising the antifouling-active filler according to the present invention is capable of significantly inhibiting the growth of bacteria in the broth solution. Furthermore, the results from a quantitative analysis carried out by measuring the turbidity of the test solutions using UV visible spectroscopy at the wavelength of 600 run as shown in Fig. 4(b). In conclusion, the polymer based composition comprising the antifouling-active filler according to the present invention is capable of significantly inhibiting the growth of the bacteria in the broth solution.
3.2 Antibacterial test for E. coli
The results from the test using agar diffusion method (Fig. 5(a)), it was found that the polymer based composition comprising the antifouling-active filler according to the present invention is capable of significantly inhibiting the growth of E. coli. The polymer based composition comprising the antifouling-active filler of copper-containing chitosan (CCu) shows the biggest clear zone of an average diameter of 5 cm as shown in Fig. 5(b).
Based on the antibacterial test using broth dilution method (Fig. 6(a)), it was found that the solution containing the polymer based composition comprising the antifouling-active filler according to the present invention is capable of significantly inhibiting the growth of the test bacteria in the broth solution compared to the solution containing polymer without antifouling- active filler (control sample). When subjecting a portion of the solution from the test to a quantitative analysis by measuring light absorption at a wavelength of 600 nm using UV visible spectroscopy as shown in Fig. 6(b), it was found that the polymer based composition comprising the antifouling-active filler according to the present invention is capable of significantly inhibiting the growth of bacteria.
4. Immersion test results
The immersion test of the sample of polymer based composition comprising different antifouling-active fillers according to the present invention was carried out by subjecting the sample polymer based composition to compression molding to obtain square polymer sheet. Said polymer sheet were then tested in the sea water to observe the fouling profile compared with the polymer sheet control sample as shown in Fig. 7.
The test results show that extensive barnacles and algae fouling was found on the surface of the polymer sheet control sample (i.e. the polymer sheet without active filler) after 4 weeks while only slight fouling were found on the surface of most of the polymer sheet obtained from compressing the pellets of the polymer based composition comprising the antifouling-active filler according to the present invention. This shows the capability of the present invention in preventing aquatic fouling.
According to the above description, the polymer based composition having antifouling- active filler according to the present invention is a result of the components, particular amount of the components, process steps including other elements which yield the above advantages. However, the antifouling polymer based composition according to the present invention is not limited to said components, particular amount of the components, process steps and elements detailed above. Modifications or variations can still be made to the present invention without departing from the scope and the spirit of the present invention.
BEST MODE OF THE INVENTIO
Best mode o the invention is as disclosed in the detailed description.

Claims

WHAT IS CLAIMED IS:
1. An anti fouling polymer based composition comprising;
- polyethylene (PE); and
- at least one antifouling-active filler selected from the group consisting of 2-methylthio- 4-ethylamino-6-tert-butylamino-s-triazine, 2,4,4"-trichloro-2 '-hydroxy di phenyl ether, 2- benzisothiazol-3-one, zinc oxide, bis(2-pyridilthio)zinc 1 ,1 * -dioxide, metal -doped hydroxyapatite, copper-containing chitosan and mixtures thereof wherein the antifouling-active filler is present in a range of 0.1-5 parts by weight based on 100 parts by weight of polyethylene.
2. The polymer based composition according to claim 1 wherein the antifouling-active filler is preferably present in a range of 0.1 -3 parts by weight based on 100 parts by weight of polyethylene.
3. The polymer based composition according to claim 1 wherein polyethylene is selected from low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE) or mixtures thereof.
4. The polymer based composition according to claim 1 or 3 wherein polyethylene preferably has a density in a range of 0.95-0.98 g/cm and has a melt flow index in a range of 0.25 -0.50 g/10 minutes.
5. The composition according to claim 1, wherein metal-doped hydroxyapatite is selected from a group consisting of Ag-doped hydroxyapatite, Mi-doped hydroxyapatite (Mi-doped hydroxyapatite) and mixtures thereof.
6. The composition according to any one of the preceding claims further comprising an additive selected from a group consisting of calcium stearate, zinc stearate, antioxidant or mixtures thereof in a range o from 0.1 -5 parts by weight based on 100 parts by weight of polyethylene.
7. The composition according to claim 6, wherein antioxidant is selected from a group consisting of tetrakis [methylene(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate]methane, tris(2,4- di-tert-buty]phenyl)phosphite and mixtures thereof, said antioxidant is present in a range of from 0.1-5 parts by weight based on 100 parts by weight of polyethylene.
8. The composition according to any one of the preceding claims further comprising at least one polymer selected from a group consisting of poly(methyl methacrylate) (PMMA), polypropylene (PP), polyurethane (PU), melamine, polyvinyl chloride (PVC) and mixtures thereof in a range of from 5-30 parts by weight based on 100 parts by weight of polyethylene.
9. A molding product from the composition according to any one of the preceding claims, wherein the molding product is a pipe, preferably underwater transportation pipe.
PCT/TH2016/000104 2015-12-24 2016-12-23 An antifouling polymer based composition WO2017111711A1 (en)

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TH1501007806A TH167832A (en) 2015-12-24 Polymer compositions with anti-binding activity of organisms that grow in water.

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06263916A (en) * 1993-03-12 1994-09-20 Toagosei Chem Ind Co Ltd Antimicrobial agent and antimicrobial resin composition
JPH0892019A (en) * 1994-09-27 1996-04-09 Sekisui Chem Co Ltd Antimicrobial resin composition
JPH08239507A (en) * 1995-03-07 1996-09-17 Toppan Printing Co Ltd Antimicrobial resin composition
JPH10237329A (en) * 1996-12-24 1998-09-08 Sumitomo Chem Co Ltd Antimicrobial resin composition
US5916947A (en) 1994-12-02 1999-06-29 Cape Cod Research, Inc. Zinc oxide photoactive antifoulant material
US6528556B1 (en) * 1999-06-01 2003-03-04 Ciba Speciality Chemicals Corporation Process for the biocidal finishing of plastic materials
US20030157176A1 (en) * 2001-09-14 2003-08-21 Kenji Nakamura Antimicrobially treated material and methods of preventing coloring thereof
US6635692B1 (en) 1997-07-04 2003-10-21 Aquaculture Crc Limited Antifouling polymers
DE202010003123U1 (en) * 2009-03-06 2010-05-27 Ke-Kelit Kunststoffwerk Gmbh Tube made of a polymer, in particular a two-layered corrugated tube
US20110070454A1 (en) 2009-09-22 2011-03-24 Quadrant Epp Ag Anti-fouling ultrahigh molecular weight polyethylene compositions and methods of using the same
US20130122226A1 (en) * 2011-09-09 2013-05-16 Chevron Phillips Chemical Company Lp Polyethylene Additive Compositions and Articles Made From Same
CN104387655A (en) * 2014-11-24 2015-03-04 苏州市贝克生物科技有限公司 Medical nano-zinc oxide antibacterial PE and preparation method thereof
CN103073769B (en) * 2011-10-26 2015-04-15 中国石油化工股份有限公司 Antibacterial polyethylene composition and preparation method thereof

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06263916A (en) * 1993-03-12 1994-09-20 Toagosei Chem Ind Co Ltd Antimicrobial agent and antimicrobial resin composition
JPH0892019A (en) * 1994-09-27 1996-04-09 Sekisui Chem Co Ltd Antimicrobial resin composition
US5916947A (en) 1994-12-02 1999-06-29 Cape Cod Research, Inc. Zinc oxide photoactive antifoulant material
JPH08239507A (en) * 1995-03-07 1996-09-17 Toppan Printing Co Ltd Antimicrobial resin composition
JPH10237329A (en) * 1996-12-24 1998-09-08 Sumitomo Chem Co Ltd Antimicrobial resin composition
US6635692B1 (en) 1997-07-04 2003-10-21 Aquaculture Crc Limited Antifouling polymers
US6528556B1 (en) * 1999-06-01 2003-03-04 Ciba Speciality Chemicals Corporation Process for the biocidal finishing of plastic materials
US20030157176A1 (en) * 2001-09-14 2003-08-21 Kenji Nakamura Antimicrobially treated material and methods of preventing coloring thereof
DE202010003123U1 (en) * 2009-03-06 2010-05-27 Ke-Kelit Kunststoffwerk Gmbh Tube made of a polymer, in particular a two-layered corrugated tube
US20110070454A1 (en) 2009-09-22 2011-03-24 Quadrant Epp Ag Anti-fouling ultrahigh molecular weight polyethylene compositions and methods of using the same
US20130122226A1 (en) * 2011-09-09 2013-05-16 Chevron Phillips Chemical Company Lp Polyethylene Additive Compositions and Articles Made From Same
CN103073769B (en) * 2011-10-26 2015-04-15 中国石油化工股份有限公司 Antibacterial polyethylene composition and preparation method thereof
CN104387655A (en) * 2014-11-24 2015-03-04 苏州市贝克生物科技有限公司 Medical nano-zinc oxide antibacterial PE and preparation method thereof

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
ATTHAPONG GITCHAIWAT ET AL: "Anti-Algal Performances for Biocide-Enhanced Low-Density Polyethylene Film", ADVANCED MATERIALS RESEARCH, vol. 747, 30 August 2013 (2013-08-30), CH, pages 481 - 484, XP055368822, ISSN: 1022-6680, DOI: 10.4028/www.scientific.net/AMR.747.481 *
ATTHAPONG GITCHAIWAT ET AL: "Assessment and characterization of antifungal and antialgal performances for biocide-enhanced linear low-density polyethylene", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 128, no. 1, 5 April 2013 (2013-04-05), US, pages 371 - 379, XP055368853, ISSN: 0021-8995, DOI: 10.1002/app.37675 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; KOBILINS'KII, S. M. ET AL: "Effect of chitosan metal complexes on degradation properties of polyethylene", XP002769830, retrieved from STN Database accession no. 2015:312539 *
DATABASE WPI Week 201531, Derwent World Patents Index; AN 2015-25286N, XP002769829 *
JOHN Z. LU ET AL: "Chelating efficiency and thermal, mechanical and decay resistance performances of chitosan copper complex in wood-polymer composites", BIORESOURCE TECHNOLOGY., vol. 99, no. 13, 1 September 2008 (2008-09-01), GB, pages 5906 - 5914, XP055368990, ISSN: 0960-8524, DOI: 10.1016/j.biortech.2007.09.086 *
KARN SILAPASORN ET AL: "Effect of chemical structure of thermoplastics on antibacterial activity and physical diffusion of triclosan doped in vinyl thermoplastics and their composites with CaCO3", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 121, no. 1, 5 July 2011 (2011-07-05), US, pages 253 - 261, XP055368947, ISSN: 0021-8995, DOI: 10.1002/app.33555 *
KOBILINS'KII, S. M. ET AL: "Effect of chitosan metal complexes on degradation properties of polyethylene", UKRAINSKII KHIMICHESKII ZHURNAL (RUSSIAN EDITION) , 80(11), 52-55 CODEN: UKZHAU; ISSN: 0041-6045, 2014 *

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