Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
  • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
  • A01N25/10—Macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C08L23/0853—Vinylacetate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/10—Other agents for modifying properties
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
  • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
• • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/12—Applications used for fibers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

• This invention relates to a high molecular weight integrated polymer.
• the invention relates to an integrated polymer having bioactive functions.
• Bioactive integrated material has wide demand in our daily life and manufacturing.
• Existing technologies normally refers to coating biocide material with polymer binder on product surface, to achieve bioactive effective.
• the active ingredients coated on product surface can be easily decomposed into surrounding air or water, which badly reduce the product effective life cycle.
• the product with bioactive coating may have direct contact with human beings, animal and plants. High concentration of biocide at the product surface may be harmful.
• biocide chemicals may be released drastically from product surface into environment as pollution. 4. At the latter stage, the product bioactive effect may drop significantly with the drastic loss of chemicals.
• a bioactive integrated polymer comprising: (a) a polymer resin; (b) ethylene-vinyl acetate (EVA); (c) a biocide as an active ingredient; and (d) at least one additive.
• EVA ethylene-vinyl acetate
• the polymer resin is a polyolefin. More preferably, the polymer resin includes polymer such as polyethylene, polypropylene etc.
• the biocide active ingredient is any one selected from the group- comprising: insecticide, fungicide, herbicide, algaecide, anti-fungal agents, anti-protozoan agents, molluscicides, acaricides, disinfectants, pyrethroid insecticide, such as cypermethrin, cyfluthrin, deltamethrin, permethrin, bifenthrin, chlorfenapyr, fipronil, copper dioxide, DCOIT, triphenylborane pyridine, pyridine copper sulfate, zinc sulfate, pyridine, I rga rol 1051, Econea, cuprous thiocya nate, ca psaicin a nd. dexmedetomidine.
• the fungicide is any one selected from the group comprising: Zineb, euparen, tolylfluanid, chlorothalonil, diuron and capsaicin.
• the additive is any one selected from the group comprising: a dye, anti- oxidising agent and UV chemical.
• the weight % of polymer resin present in the integrated polymer is between 80-97%. More preferably, the weight % of polymer resin present in the integrated polymer is between 85- 95%. The weight % of polymer resin present in the integrated polymer may be between 85-90%. Still more preferably, the weight % of polymer resin present in the integrated polymer is between 90- 95%.
• the weight % of ethylene-vinyl acetate (EVA) present in the integrated polymer is between 2-20%. More preferably, the weight % of ethylene-vinyl acetate present in the integrated polymer is between 2-15%. Still more preferably, the weight % of ethylene-vinyl acetate present in the integrated polymer is between 5-10%. Depending on the weight % of the polymer resin present in the composition, the EVA may be present between 10% to 15% (when polymer resin is present 85% to 90%), or 2% to 10% (when polymer resin is present 90% to 97%).
• the weight % of the biocide active ingredient present in the integrated polymer is between 0.01-4%.
• the biocide active ingredient present in the integrated polymer is between 0.1-2%. More preferably, the biocide active ingredient present in the integrated polymer is between 0.1-0.8%. Still more preferably, the biocide active ingredient present in the integrated polymer is between 0.4-0.8%.
• the biocide active ingredient present in the integrated polymer is between 1-4%. More preferably, the biocide active ingredient present in the integrated polymer is between 1-2%. .
• the weight % of the biocide active ingredient is ultimately dependent on the type of biocide.
• the weight % of pyrethroid insecticide may be between 0.1% to 0.8%.
• the weight % of fungicide may be between 1% to 4%.
• the weight % of the additive present in the integrated polymer is between 0.01-0.5%.
• a method for making a bioactive integrated polymer comprising: (a) blending a polymer resin, ethylene-vinyl acetate, a biocide, and at least one additive; (b) inputting the blend into an extrusion hopper; (c) extruding fibers from the blend; and (d) forming the extruded fibers into a net.
• the step of extruding the fibers is carried out at a temperature below 240°C.More preferably, the step of extruding the fibers is carried out at a temperature between 120-210° C.
• the purpose of this invention is to tackle above problems a nd provide a practical solution with effective and constant bioactive integrated technology.
• the present invention particularly the amount of EVA present in the composition, achieves the result so that the biocide incorporated into polymer would not be easily decomposed or vaporized into air or water, hence to extend the product life cycle, minimize the usage of biocide chemical but with longer effectiveness.
• Figure 1 shows a net made from a polymer according to an embodiment of the present invention
• Figure 2 shows a flow chart for making a polymer net according to an embodiment of the present invention.
• FIGS 3 to 10 show raw data to support the results set out in Tables I and II below.
• the bioactive integrated polymer of the present invention is used to make a net as shown in Figure 1.
• the terms "bioactive polymer”, “im pregnated net”, or “net” may be used to refer to such a net.
• the EVA is first blended, mixed and processed together with the polymer resin.
• EVA has low melting temperature a nd ca n be blended with other polymer material easily, a nd is able to enhance the storage of biocide active ingredient.
• the lifespa n of the biocide varies but when they a re in the open air, probably within a couple of hours or maximum a couple of days. However, in the present invention, the lifespan can be extended to maxim um of 7 yea rs as active ingredient that is within the polymer will continue to be active.
• Blending with the EVA will help lower the process temperature to minimize the loss of biocide du ring process.
• the temperature is at between 220-240°C .
• H oweve r, i n the p rese nt i nve ntio n, th at temperature ca n be lowered to 120-200°C when blending with the EVA.
• the polymer material made with this invention does not only provide constant bioactive effect and prolonged life, but also has comparable strength level,
• the biocide active ingredient includes any one or combination of the chemicals such as insecticide, fungicides, herbicides, algaecide, antifungal agents, anti- protozoan agents, molluscicides, acaricides, disinfectants.
• the insecticide may be any one or combinations of the pyrethroid insecticide, such as cypermethrin, cyfluthrin, deltamethrin, permethrin, bifenthrin, chlorfenapyr,fipronil.
• Pyrethroid insecticide is a group of new insecticides which have been widely used in recent 50 years with following advantages: (1) high efficient and broad spectrum; (2) low toxicity; (3) less side effect; and (4) less residual and pollution.
• the biocide active ingredient could be any one or combinations of the fungicide, such as Zineb, euparen, tolylfluanid, chlorothalonil, diuron.
• the biocide active ingredient could be any one or combinations of the followings, such as copper dioxide, DCOIT, triphenylborane pyridine, pyridine copper sulfate, zinc sulfate, pyridine, Irgarol 1051, Econea, cuprous thiocyanate, Zineb, capsaicin, dexmedetomidine.
• Copper Dioxide has been actively used as antifouling chemical against most of creatures in sea.
• DCOIT is active against bacteria, fungi, algae and marine invertebrate.
• Pyridine triphenylborane is effective against sea creatures and diatoms.
• Irgarol 1051: is a herbicide widely used in agriculture, and also can be used as antifouling agent in aquaculture.
• Econea has a broad spectrum and excellent antifouling effect against invertebrates.
• the weight ratio of pyrethroid insecticide is from 0.1% to 0.8%.
• the weight ratio of pyrethroid insecticide is from 1% to 4%.
• the weight ratio of polymer resin is from 85% to 90%; the weight ratio of EVA being from 10% to 15%.
• the weight ratio of polymer resin is from 90% to 97%; the weight ratio of EVA being from 2% to 10%.
• the additives could be one or combinations of anti-oxidization agent or anti- UV agent.
• the process of above bioactive integrated polymer is: blending the formula above according to the particular weight ratio; input into hopper after mixture; injection, ext rusio n o r blow u nde r co ntro l la b le tem pe rature wh ich is not h ighe r tha n 240°C.
• the process is described in a flow chart shown in Figure 2.
• the polymer is extruded to filament form and then made to a net.
• the formulation allow the process to be done in much lower temperature, hence preserve the effectiveness of the active ingredient.
• the active ingredient will decompose at higher temperature.
• Example 1 Insecticide integrated net
• the bioactive integrated polymer has be following composition:
• the biocide active ingredient is cypermethrin.
• the following process is carried out for making a net made from the bioactive polymer: blending the above formula; inputting to an extrusion hopper after fully blended; Extruding fibers under controllable temperature not higher than 240°C; and making the net.
• the bioactive integrated polymer, or impregnated net is then used to carry out the following tests.
• the various components are blended for about 10-15 minutes in a blender. After blending, the blended mixture is put into an extrusion hopper to extrude fibers under a controlled temperature of about 120°C to 210°C. Testing the net (experimental conditions)
• the test was carried out in a closed room measuring 50m 3 to create the conditions of a confined space as commonly encountered when treating storage premises.
• the room represents the average conditions of a house. It was sheltered from draughts and separate from the place where the typical surfaces treated were transferred and stored. It allowed treatments to be performed at constant temperature (+ 2°C) at between 20 and 25°C. 1.2 Test sample
• the size of the net (sample size) may be 15 cm x 15 cm.
• Each sample is covered by the cover of a PETRI dish of a 14 cm diameter.
• the nets were kept at a temperature of 25°C +/- 2°C and relative humidity of 70 +/- 10%, with no ventilation (passive air exchanges ⁇ lm 3 /h), without any contact between them to avoid any transfer of the preparation up to the date when they were brought into contact with the target species.
• test product Given the intended use of the test product, it was chosen to store the panels under a photoperiod of 16 hours light and 8 hours darkness. The net parts were stored flat on the fjoor of an enclosure to allow even lighting by florescent tubes placed 2.5 m from the ground. For the tests, tubes were selected that are typical of agri-food premises, covered with a protective plastic film and of which part of the light spectrum emitted is in the ultraviolet range.
• the organisms / pests were bred in controlled climatic conditions kept at 20 +/- 1°C, 70 +/- 10% HR, light 700 lux 16 hours + darkness 8 hours.
• the organisms were bred in 35 cm x 20 cm x 15 cm plastic boxes containing a shelter, a water source and food (depending on the species).
• batches were used as follows: 25+/-1, i.e. between 24 to 26 organisms were used in each batch. 4 replicates were conducted, this means a total of 100+/-4 insects were exposed to the product and to the ; untreated.
• Control batches The batches of target species constituting controls were placed on the same material but untreated. By “untreated”, it is meant to refer to those polymer nets that do not contain the biocide active ingredient.
• treated is meant to refer to those polymer nets according to the present claimed invention that includes the biocide active ingredient.
• control batches were intended to check the quality of the batches used for the tests and unintentional effects introduced by handling and experimental conditions. If applicable, mortality observed on the control batches allowed the mortality observed on batches subject to the treatment to be corrected and thus validated the overall test.
• Example 1 The net mentioned in Example 1 was used as test sample.
• Each experimental unit includes the bioactive polymer of the present invention and the insects.
• an efficacy test was performed. It consisted of installing the pests on the treated surfaces for a period of 1 hour.
• the persistence was measured by performing the same efficacy test after 6 months of storage of the units (cf storage conditions at 1:2.4.).
• the actual temperature and hygrometry during the tests were from 22.1°C to 22.5°C, 63% to 71% RH, light 1200 lux.
• the mortality of the insects were recorded at regular time intervals (1, 2 or 4 hours, depending on how long the mortality takes to be recorded) in order to know the short-term kinetics of the effect the bioactive polymer has on the organisms.
• the insects were removed from the typical surfaces by gentle suction using any suction means/ such as a vacuum cleaner, and transferred to untreated inert surfaces with a nutritious substratum and water available. This was placed under climatic breeding conditions.
• the paralysis phase may appear more or less rapidly (shock action) according to the type of insecticide or acaricide substance and according to the dose. Recovery of normal behaviour may occur after a fairly long knock down period (e.g. several days), still in relation to the dose of treatment and the duration of contact between the animal and the preparation deposit.
• the lethal effect does not necessarily occur after the known down period.
• instantaneous effect it is meant that the day of opening of the bag containing the sample (Day 0), the arthropods were put in contact with it to measure the instantaneous effect of the sample on the insects.
• persistence it is meant that the persistence of action of the sample was judged by putting the target arthropods in contact with the sample for about 6, 9 and 12 months of storage.
• Tables I and II below show the summary of the results obtained. The raw data that supports the results shown in Figures 3 to 10.
• Table I A summary of the data in KT100
• KT100 time from the beginning of the experiment - including the 1 hour exposure time of the insects onto the treated surfaces - required to knockdown/kill 100% of the insects.
• T.b Tlneala bisselltella (clothe moth)
• A.a Aedes alboplctus (Tiger mosquito)
• M.d Musca domestlca (common house fly)
• E.k Ephestia kuehntella (mediterranean flour moth)
• R.d Rhizopertha domlnlca (lesser grain borer)
• T.b Tlneola blsselliella (clothe moth)
• A.a Aedes alboplctus (Tiger mosquito)
• M.d Musca domestica (common house fly)
• E.k Ephestla kuehnlella (mediterranean flour moth)
• S.g Sltophllus granarius (grain weevil)
• R.d Rhizopartha do lnlca (lesser grain borer)
• O.s Oryzaephllus surinamansis (saw-tooth beetle)
• Bioactive integrated polymer which contains following contents: Polyethylene 90%, EVA 9.89%, deltamethrin 0.1%, anti oxidization agent 0.01%. Preparation of the polymer:
• Example 3 Bioactive integrated polymer, which contains following contents: Polyethylene 80%, EVA 19.9%, bifenthrin 0.05%, anti oxidization agent 0.05%.
• Preparation of the polymer Blending above formula; Input to extrusion hopper after fully blended; Extruding, injecting or blowing under controllable temperature not higher than 240°C.
• Bioactive integrated polymer which contains following contents: Polyethylene 85%, EVA 12.95%, Chlorfenapyr 2%, anti oxidization agent 0.05%. Preparation of the polymer:
• Bioactive integrated polymer which contains following contents: Polypropylene 97%, EVA 2.45%, Fipronil 0.5%, anti UV agent 0.05%.
• Example 6 Bioactive integrated polymer, which contains following co ntents: Polypropylene 84.55%, EVA 15%, Cypermethrin 0.4%, anti UV agent 0.05%.
• Preparation of the polymer Blending above formula; Input to extrusion hopper after fully blended; Extrudi ng, injecting or blowing under controllable temperature not higher than 240°C.
• Bioactive integrated polymer which contains following contents: Polypropylene 40%, Polyethylene 40%, EVA 18.95%, Permethrin 1%, anti UV agent 0.05%. Preparation of the polymer:
• Example 8 Bioactive integrated polymer, which contains following contents: Polyethylene 80%, EVA 19%, Tolylfluanid 0.95%, anti oxidization agent 0.05%.
• Preparation of the polymer Blending above formula; Input to extrusion hopper after fully blended; Extruding, injecting or blowing under controllable temperature not higher than 240°C.
• Bioactive integrated polymer which contains following contents: Polyethylene 95%, EVA 4%, DCOIT 0.95%, anti oxidization agent 0.05%. Preparation of the polymer:
• Bioactive integrated polymer which contains following contents: Polyethylene 90%, EVA 7.2%, Tolylfluanid 2.75%, anti oxidization agent 0.05%. Preparation of the polymer:
• the net made of above polymer has anti-fouling effect.
• the comparison test was conducted against controlled sample, which is made of normal PE fiber. The samples were mounted on metal frame and dipped into sea water at the same location. After 9 months, the controlled sample was attached with huge amount of fouling creatures, mainly shells, while the surface of antifouling bioactive net remains clean.

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