WO2021134976A1 - 一种防咬剂、防咬材料、防咬物品及其制备方法 - Google Patents

一种防咬剂、防咬材料、防咬物品及其制备方法 Download PDF

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Publication number
WO2021134976A1
WO2021134976A1 PCT/CN2020/084787 CN2020084787W WO2021134976A1 WO 2021134976 A1 WO2021134976 A1 WO 2021134976A1 CN 2020084787 W CN2020084787 W CN 2020084787W WO 2021134976 A1 WO2021134976 A1 WO 2021134976A1
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Prior art keywords
bite
agent
biting
substance
inorganic carrier
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PCT/CN2020/084787
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English (en)
French (fr)
Inventor
秦强强
申会员
何洋
樊绍彦
陈泉
孔德玉
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公牛集团股份有限公司
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Publication of WO2021134976A1 publication Critical patent/WO2021134976A1/zh

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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01M—CATCHING, TRAPPING OR SCARING OF ANIMALS; APPARATUS FOR THE DESTRUCTION OF NOXIOUS ANIMALS OR NOXIOUS PLANTS
    • A01M29/00—Scaring or repelling devices, e.g. bird-scaring apparatus
    • A01M29/14—Scaring or repelling devices, e.g. bird-scaring apparatus using thermal effects
    • 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
    • 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
    • A01N25/22—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 ingredients stabilising the active ingredients
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof

Definitions

  • the invention relates to the field of chemicals, in particular to an anti-bite agent, an anti-bite material, an anti-bite article and a preparation method thereof.
  • Animals including domestic pets, like to bite objects.
  • electrical-related objects such as power cords, sockets, power converters, etc.
  • safety accidents such as electric shock and leakage. Therefore, it is necessary to treat the items to make them bite resistant to animals.
  • Capsaicin as an anti-bite substance, can be added to articles to give the articles a pungent taste, thereby realizing bite resistance. However, as the use time increases, the taste irritation of capsaicin-added items will gradually decrease, resulting in the gradual loss of its anti-bite effect.
  • the embodiments of the present application provide an anti-bite agent, an anti-bite material, an anti-bite article and a preparation method thereof, which can solve the above technical problems.
  • an anti-bite agent wherein the anti-bite agent includes: an inorganic carrier having a sheet structure and modified by an intercalating agent, and a sheet layer located on the inorganic carrier Anti-bite substances in the structure;
  • the anti-bite substance is a natural or artificial synthetic substance that can emit an animal's unpleasant or pungent odor, such as capsaicin, allicin, mustard, garlic powder, mustard powder, chili powder or pepper.
  • the intercalating agent includes, but is not limited to, hyperbranched polyamide, chitosan, ⁇ -aminopropyltriethoxysilane, and alkylammonium salts (such as tertiary amine salts or quaternary ammonium salts). Salt) at least one of.
  • the hyperbranched polyamide is an aliphatic amino-terminated hyperbranched polyamide, such as ethylene diamine (or propylene diamine) and acrylate (such as methyl acrylate or ethyl acrylate).
  • the amino-terminated hyperbranched polyamide; the tertiary amine salt can be, for example, dodecyl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, double Cetyl dimethyl ammonium bromide and so on.
  • the anti-bite agent provided in the present application also contains a heat sensation agent, for example selected from vanillyl butyl ether, vanillyl isobutyl ether, vanillyl n-propyl ether, vanillyl isopropyl ether, incense At least one of blue n-amino ether, vanillyl isoamyl ether, vanillyl n-hexyl ether, vanillyl methyl ether, vanillyl ethyl ether, ginger alcohol, succinyl phenol, and gingerone.
  • a heat sensation agent for example selected from vanillyl butyl ether, vanillyl isobutyl ether, vanillyl n-propyl ether, vanillyl isopropyl ether, incense At least one of blue n-amino ether, vanillyl isoamyl ether, vanillyl n-hexyl ether, vanillyl
  • the inorganic carrier is a layered silicate
  • the layered silicate is selected from at least one of magadiite, montmorillonite, kaolin, mica and sepiolite.
  • the anti-bite substance is located between the sheets of the inorganic carrier, for example, between the sheets of magadiite.
  • a method for preparing an anti-bite agent or a method for slowly releasing pungent odors in an anti-bite substance which includes preparing an inorganic carrier modified by an intercalating agent and an anti-bite agent.
  • the step of dissolving the substance and obtaining the solid solute in the dissolving solution is optionally followed by heating, centrifuging, and filtering to obtain the solid solute in the dissolving solution, that is, the anti-biting agent.
  • anti-bite agent and anti-bite substance may be as defined in the first aspect of the present application, for example.
  • the dissolving solution containing the inorganic carrier modified by the intercalation agent and the anti-bite substance is obtained by the following method:
  • the inorganic carrier modified by the intercalation agent is added to the above-mentioned dissolving solution containing the anti-bite substance.
  • the inorganic carrier modified by the intercalation agent is obtained by the following method:
  • Disperse the inorganic carrier in water for example, deionized water
  • water for example, deionized water
  • ultrasonic treatment to obtain a first mixed solution
  • the first mixed liquid and the second mixed liquid are mixed, and optionally heated, centrifuged, and filtered in sequence to obtain the inorganic carrier modified by the intercalation agent.
  • the pH value of the second mixed solution is in the range of 4-5.
  • the acid solution is selected from at least one of acetic acid, carbonic acid, citric acid, and phosphoric acid.
  • the mixing the first mixed liquid with the second mixed liquid includes:
  • the second mixed liquid is added dropwise to the first mixed liquid to mix the first mixed liquid with the second mixed liquid.
  • an anti-bite material wherein the anti-bite material includes any one of the above-mentioned anti-bite agents.
  • the anti-bite material is an electrically insulating material, such as a plastic material or rubber.
  • the anti-bite material includes a resin and an anti-bite agent, for example, contains the following raw material components in parts by weight:
  • the raw material component of the anti-bite material further includes 0.5-1.5 parts by weight of a thermosensitizer.
  • the resin is selected from at least one of PP resin, PVC resin and ABS resin.
  • the raw material component of the anti-bite material further includes additives, and the additives are selected from the group consisting of plasticizers, flame retardants, inorganic fillers, stabilizers, lubricants, antioxidants, and compatibilizers. At least one of an agent and an anti-copper pest.
  • the embodiments of the present application provide an anti-bite article, wherein the anti-bite article includes the anti-bite agent provided in the present application, or is prepared from any of the above-mentioned anti-bite materials.
  • the anti-bite article is a housing of an electrical appliance, a housing of a power converter, a housing of a socket, a housing of a wire, a cable sheath or a tire, etc., made of electrical insulating materials.
  • the present application provides an anti-bite agent, wherein the anti-bite agent includes: an inorganic carrier having a sheet structure and modified by an intercalating agent, and an anti-bite substance located in the sheet structure of the inorganic carrier.
  • the anti-bite substance is a natural or artificial synthetic substance that can emit an animal's unpleasant or pungent odor, such as capsaicin, allicin, mustard, garlic powder, mustard powder, chili powder or pepper powder.
  • the anti-bite agent provided in the examples of the application effectively reduces the migration of small-molecule anti-bite substances capsaicin, allicin, and mustard by placing the anti-bite substance in the sheet structure of the inorganic carrier modified by the intercalating agent. , To achieve the purpose of slow release and controlled release, to ensure that the anti-bite effect of anti-bite articles added with anti-bite substances is lasting and effective.
  • the anti-bite material is located in the sheet structure of the inorganic carrier, which also helps to improve the heat-resistant stability of the anti-bite material, effectively inhibits the volatilization or even decomposition of the above-mentioned anti-bite material, prevents the anti-bite material from volatilizing gas with irritating smell, and improves its applicability.
  • the anti-bite substance is added to the anti-bite article, which can achieve the purpose of preventing animals from biting, and the anti-bite effect is lasting and effective.
  • the inorganic carrier is modified by the intercalating agent, so that the intercalating agent can intercalate into the sheet structure of the inorganic carrier, so that the interlayer spacing of the inorganic carrier is increased, which is conducive to the smooth insertion of capsaicin and other anti-bite substances into the inorganic carrier.
  • the intercalating agent can intercalate into the sheet structure of the inorganic carrier, so that the interlayer spacing of the inorganic carrier is increased, which is conducive to the smooth insertion of capsaicin and other anti-bite substances into the inorganic carrier.
  • the lamella structure In the lamella structure.
  • mammals include but are not limited to domestic pets and wild animals, such as house mice.
  • the intercalating agent may be selected from at least one of hyperbranched polyamide, chitosan and ⁇ -aminopropyltriethoxysilane, alkyl ammonium salt (such as tertiary amine salt or quaternary ammonium salt), preferably
  • the hyperbranched polyamide is an aliphatic amino-terminated hyperbranched polyamide, such as an amino-terminated hyperbranched polyamide obtained by ethylene diamine (or propylene diamine) and acrylic ester (such as methyl acrylate or ethyl acrylate) ;
  • the tertiary amine salt is, for example, dodecyl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide, double hexadecyl dimethyl bromide Ammonium.
  • the above-mentioned intercalating agent is selected, the amino group contained in it can exist in the form of NH 3 + , and the cation exchange reaction with the inorganic cation between the inorganic carrier sheet is carried out, and then the intercalation can be inserted into the sheet structure of the inorganic carrier, so that the inorganic carrier sheet The lamella spacing increases.
  • the hyperbranched polyamide can be an aliphatic amino-terminated hyperbranched polyamide.
  • it can not only smoothly intercalate into the sheet structure of the inorganic carrier, but also can change the surface of the inorganic carrier from hydrophilic to Lipophilicity improves the compatibility with capsaicin and other anti-bite substances, and also facilitates the insertion of molecules of capsaicin and other anti-bite substances into the sheet structure of the inorganic carrier.
  • the molecular weight of the aliphatic amino-terminated hyperbranched polyamide is generally between 1000 and 2500, and it can be purchased directly from the market.
  • the inorganic carrier may be a layered silicate with an average particle size of 1nm-100nm.
  • the layered silicate may be selected from magadiite, montmorillonite, kaolin, mica and sepiolite At least one of them. All the above types of layered silicates have a good lamellar structure.
  • the anti-bite material is located between the sheet structure of the inorganic carrier, for example, between the sheet layers of magadiite.
  • the embodiment of the application uses the above-mentioned inorganic carrier with a lamellar structure to insert small molecule anti-bite substances such as capsaicin into the lamellar structure through the solution intercalation method, which effectively reduces the migration of the anti-bite substances, thereby achieving the purpose of slow release and controlled release. Ensure that the anti-bite effect of the prepared anti-bite article is lasting and effective.
  • the intercalation structure of the anti-bite substance and the inorganic carrier also improves the heat-resistant stability of capsaicin and other anti-bite substances, effectively reduces the volatilization or even decomposition of capsaicin and other anti-bite substances, and reduces the volatile irritating odor from the source. The production.
  • the above-mentioned types of inorganic carriers selected in the examples of this application have a large specific surface area and are also an excellent odor adsorbent, which can effectively remove the pungent odor in the anti-bite material, making the anti-bite material suitable for indoor environments.
  • the anti-bite material provided in the embodiments of the present application not only solves the problem that capsaicin and other anti-bite materials have high odor when added to the anti-bite material and cannot be used indoors, but also solves the problem that capsaicin and other anti-bite materials are easy to migrate and cause
  • the resulting anti-bite materials have poor durability against animal bites, and at the same time solves the problem of poor heat resistance stability of anti-bite materials such as capsaicin, and poor product batch stability due to volatilization.
  • aliphatic amino-terminated hyperbranched polyamides can be used as intercalating agents, while magadite with an average particle size of 1nm-100nm is used as an inorganic carrier, and aliphatic amino-terminated hyperbranched polyamides are selected.
  • magadite with an average particle size of 1nm-100nm
  • aliphatic amino-terminated hyperbranched polyamides are selected.
  • the terminal amino groups of the hyperbranched polyamide exist in the form of NH 3 + under acidic conditions, which can carry out cation exchange reaction with Na + between the magadiite layers.
  • the aliphatic amino-terminated hyperbranched polyamide can intercalate into the magadite lamella structure, which increases the interval between the magadite lamellae, which facilitates the subsequent smooth insertion of capsaicin and other anti-bite substances into the magadite Lamellar structure of sodalite.
  • the aliphatic amino-terminated hyperbranched polyamide macromolecules are distributed in the lamellar structure of the magadite, so that the surface of the magadite turns from hydrophilic to lipophilic, and improves the molecular resistance of capsaicin and other anti-bite substances. Compatibility is also conducive to the insertion of capsaicin and other anti-bite substances into the lamellar structure of magadiite.
  • the aliphatic amino-terminated hyperbranched polyamide is intercalated in the magadiite sheet structure. Due to its ellipsoidal structure and flexible long molecular chains, the surface of the magadiite nanoparticles is wrapped by flexible molecular chains, which effectively hinders The agglomeration between the nanoparticles improves the dispersion of the nanoparticles in the resin.
  • the anti-bite agent provided in the embodiments of the present application also contains a heat sensation agent, for example, selected from vanillyl butyl ether, vanillyl isobutyl ether, vanillyl n-propyl ether, vanillyl isopropyl ether , At least one of vanillyl n-amino ether, vanillyl isoamyl ether, vanillyl n-hexyl ether, vanillyl methyl ether, vanillyl ethyl ether, ginger alcohol, gingerenol, gingerone, It can further improve the taste irritation of the anti-bite agent and improve the avoidance effect of animals.
  • a heat sensation agent for example, selected from vanillyl butyl ether, vanillyl isobutyl ether, vanillyl n-propyl ether, vanillyl isopropyl ether , At least one of vanillyl n-amino ether, vanilly
  • the embodiments of the present application provide a method for preparing any of the above-mentioned anti-bite agents, or a method for slowly releasing the pungent odor in the anti-bite substance, wherein the preparation method includes: preparing an intercalating agent containing The step of modifying the dissolving liquid of the modified inorganic carrier and the anti-biting substance and obtaining the solid solute in the dissolving liquid is optionally followed by heating, centrifuging and filtering to obtain the solid solute in the dissolving liquid, and the solid solute is the anti-biting agent.
  • anti-bite agent and anti-bite substance may be as defined in the first aspect of the present application, for example.
  • the inorganic carrier is mixed with the dissolving liquid containing the anti-bite substance, and the solution intercalation method is adopted to allow the anti-bite substance to enter the layer structure of the inorganic carrier, effectively reducing the small molecule anti-bite substance capsaicin and allicin.
  • the migration of mustard to achieve the purpose of slow release and controlled release, to ensure the anti-bite effect of anti-bite articles added with anti-bite substances lasting and effective.
  • the anti-bite material is located in the sheet structure of the inorganic carrier, which also helps to improve the heat-resistant stability of the anti-bite material, effectively inhibits the volatilization or even decomposition of the above-mentioned anti-bite material, prevents the anti-bite material from volatilizing gas with irritating smell, and improves its applicability.
  • the inorganic carrier is modified by the intercalating agent so that the intercalating agent intercalates into the sheet structure of the inorganic carrier, which increases the interlayer spacing of the inorganic carrier, which is beneficial to the subsequent smooth insertion of capsaicin and other anti-bite substances into the inorganic carrier.
  • the intercalating agent intercalates into the sheet structure of the inorganic carrier, which increases the interlayer spacing of the inorganic carrier, which is beneficial to the subsequent smooth insertion of capsaicin and other anti-bite substances into the inorganic carrier.
  • the lamella structure In the lamella structure.
  • the dissolving liquid containing the anti-bite substance can be obtained by the following method: dissolving the anti-bite substance in a solvent to obtain a dissolving liquid containing the anti-bite substance;
  • the above-mentioned solvent is selected from at least one of ethanol, methanol, and acetone.
  • the use of the above-mentioned volatile solvent can realize the sufficient and uniform dissolution of the anti-bite substance, and obtain a solution with uniform composition.
  • the above-mentioned solvent is volatilized during the subsequent heating process to ensure that it will not remain.
  • Anti-bite substances such as capsaicin, solvents such as ethanol, and inorganic carriers (including inorganic carriers modified by intercalation), the mass ratio between the three can be 1:50-80:0.5-1.2, which can ensure The anti-bite substance is distributed as much as possible in all the layer spaces of the inorganic carrier to increase its loading capacity.
  • the inorganic carrier is mixed with the dissolving liquid containing the anti-bite substance, it is heated to react.
  • the heating temperature can be 40°C-80°C, such as 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, etc., this not only ensures the smooth volatilization of the above solvents, but also avoids the decomposition or volatilization of anti-bite substances.
  • the reaction is stirred for a set time, for example, 3-10 hours, to ensure that the anti-bite material is smoothly inserted into the sheet structure of the inorganic carrier.
  • the inorganic carrier modified by the intercalating agent is obtained by the following method: the inorganic carrier is dispersed in dewatered water, such as ionized water, and optionally ultrasonically treated to obtain the first mixed solution.
  • the intercalating agent is dissolved in an acid solution to obtain a second mixed solution.
  • the first mixed liquid and the second mixed liquid are mixed, and optionally heated, centrifuged, and filtered in sequence to obtain an inorganic carrier modified by the intercalating agent.
  • the second mixed liquid can be added dropwise to the first mixed liquid to mix the two, which facilitates the sufficient and smooth insertion of the intercalating agent into the sheet structure of the inorganic carrier.
  • the mass ratio of the inorganic carrier to the deionized water is 1:30-60
  • the mass ratio of the intercalating agent to the acid liquid is 1:80-100. It is obtained that the first mixed liquid and the second mixed liquid reach a suitable concentration, which is beneficial to the modification process.
  • the first mixed liquid and the second mixed liquid After the first mixed liquid and the second mixed liquid are mixed, they can be heated to 60-100°C. In this way, under the premise of ensuring the smooth progress of the modification process, the deionized water and acid liquid can be volatilized in time to avoid residue. After being heated to the above appropriate temperature, the reaction is stirred for a set time, such as 2-8 hours, to ensure that the inorganic carrier is fully modified.
  • the intercalation agent is dissolved in a medium acid solution to create an acidic environment and provide an environment for the cation exchange between the inorganic carrier and the intercalation agent.
  • the pH value of the second mixed liquid can be adjusted by alkali solution, such as NaOH solution, so that the pH value of the second mixed liquid is in the range of 4-5, for example, 5.
  • the amino groups contained in intercalating agents such as polysaccharides and ⁇ -aminopropyltriethoxysilane exist in the form of NH 3 + to carry out cation exchange reaction with the inorganic cations between the layers of the inorganic carrier sheet to make the intercalation process proceed smoothly.
  • the acid solution is selected from at least one of acetic acid, carbonic acid, citric acid, and phosphoric acid.
  • the embodiment of the present application provides a preparation method of such an anti-bite agent, which includes the following steps:
  • an embodiment of the present application also provides an anti-bite material, wherein the anti-bite material includes any of the above-mentioned anti-bite agents.
  • the anti-bite material is prepared by the anti-bite agent provided in the embodiments of the present application, which can prevent animals from biting, and has the advantage of long-lasting and effective anti-bite effect.
  • the anti-bite material can be made of multiple materials, for example, it can be an electrical insulating material including: plastic material, rubber, composite wood, paper, and the like.
  • the embodiment of the present application provides an anti-bite material made of plastic or rubber, and the anti-bite material can be capsaicin.
  • the anti-bite material of plastic material provided in the embodiment of the present application includes a resin and an anti-bite agent, for example, contains the following raw material components in parts by weight:
  • the above resin may be selected from at least one of PP (Polypropylene) resin, PVC (Polyvinyl chloride, polyvinyl chloride) resin, and ABS (Acrylonitrile Butadiene Styrene, acrylonitrile-butadiene-styrene copolymer) resin.
  • PP Polypropylene
  • PVC Polyvinyl chloride, polyvinyl chloride
  • ABS Acrylonitrile Butadiene Styrene, acrylonitrile-butadiene-styrene copolymer
  • the above-mentioned PP resin may include 30-45 parts by weight of homo-PP resin and 30-45 parts by weight of copolymerized PP resin.
  • PP resin is used as the basic resin of the formula system to give the anti-bite material good mechanical strength, chemical resistance and electrical insulation properties.
  • the examples of this application use a combination of homo-PP and copolymer PP.
  • the homo-PP gives the anti-bite material good Rigid, copolymerized PP endows the anti-bite material with good impact performance and low temperature toughness.
  • melt index of the homopolymer PP resin used is 15-25 g/10 min.
  • melt index of the copolymer PP resin used is 5-10 g/10 min.
  • the raw material components of the plastic anti-bite material provided in the embodiments of the present application further include: 0.5-1.5 parts by weight of the thermal agent.
  • the animal nerve endings can be stimulated to produce a heat sensation.
  • the heat sensation effect is several times that of general capsaicin and other anti-bite substances, and the heat sensation effect is long-lasting. Therefore, when pets feel the spicy taste of capsaicin , The heat sensation agent will play a synergistic effect, enhance the spicy effect and improve the anti-biting effect.
  • the heat sensation agent may be vanillyl butyl ether, which is suitable for synergistic action with anti-bite substances such as capsaicin, allicin or mustard to improve the anti-bite effect.
  • the raw material components of the anti-bite material provided in the embodiments of the application further include additives, which are selected from plasticizers, flame retardants, inorganic fillers, stabilizers, lubricants, antioxidants, At least one of a compatibilizer and an anti-copper harmful agent.
  • the additives added in the raw material components and their weight ratio are as follows: flame retardant 2-6 parts, inorganic filler 10-20 parts, compatibilizer 5-15 parts , Lubricant 0.3-0.8 parts, antioxidant 0.2-0.6 parts, anti-copper harmful agent 0.2-0.6 parts.
  • the flame retardant can be a compound containing phosphorus, nitrogen, and bromine.
  • the mass ratio of phosphorus, nitrogen and bromine is 10:0.5-4.2:1.2-8.4, so that the anti-bite material can pass the UL94V-2 level and pass the glow wire GWFI At 775°C, compared with traditional brominated flame retardants, there is no need to add antimony trioxide, and the amount of such flame retardants added is small, which not only effectively guarantees the flame retardancy of anti-bite materials, but also effectively reduces the cost of anti-bite materials.
  • the flame retardant may be one or more of EPFR-2000, EP700A, and Lydorflam5014.
  • the compatibilizer may be one or more of PP-g-MAH, PE-g-MAH, POE-g-MAH, SEBS-g-MAH, EPDM-g-MAH, and SMA.
  • the inorganic filler can be talc powder, and the mesh number of talc powder can be 1250-2500 mesh, which is used to improve the hardness and heat resistance of anti-bite materials, and reduce molding shrinkage; in addition, it can also reduce resin consumption and reduce product costs.
  • the lubricant is one or more of polyethylene wax, oxidized polyethylene wax, paraffin wax, stearic acid amide, oleic acid amide, stearic acid and its esters, and stearates.
  • the function of the lubricant is to form a smooth interface on the contact surface of the material and the processing equipment to reduce friction; at the same time, it can reduce the melt viscosity of the anti-bite material, reduce the friction between the internal molecules of the anti-bite material, and improve the processing performance of the anti-bite material. Increase productivity.
  • the antioxidant may be at least one of the antioxidant 1010 and the antioxidant 168, for example, a mixture of the two, and the antioxidant 1010 and the antioxidant 168 may be mixed in any mass ratio, such as 1:1.
  • Antioxidant 1010 and Antioxidant 168 are used in combination, which has a good synergistic effect and prolongs the service life of anti-bite materials.
  • the above-mentioned anti-copper harmful agent may be N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine (abbreviated as MD-1024).
  • Anti-copper harmful agent also known as copper ion inhibitor, has two functional groups, hindered phenol and hydrazide.
  • the hindered phenol structure can prevent polymer materials from aging due to heat and oxygen, and the hydrazide structure can complex metal ions (such as copper ions).
  • the reaction making it lose its destructive effect, can improve the premature aging phenomenon due to the catalytic effect of copper ions. Therefore, when PP composite resin is used in copper wire products, it protects the shell in contact with the copper wire and copper terminals.
  • the anti-bite material prepared by using PP resin as the resin matrix can be prepared by the following method: mixing each raw material component, melting and extruding through a twin-screw extruder, and water-cooling and hot-cutting pelletizing.
  • the process parameters of the twin-screw extruder are: the temperature of the first zone is 150 ⁇ 155°C, the temperature of the second zone is 165 ⁇ 170°C, the temperature of the third zone is 165 ⁇ 170°C, the temperature of the fourth zone is 160 ⁇ 175°C, and the temperature of the fifth zone is 160 ⁇ 175. °C, six zone temperature 160 ⁇ 175°C, seven zone temperature 160 ⁇ 175°C, eight zone temperature 160 ⁇ 175°C, nine zone temperature 180 ⁇ 185°C, die temperature 190 ⁇ 195°C, twin screw extruder speed is 300 ⁇ 500r/min.
  • the intercalating agent is an aliphatic amino-terminated hyperbranched polyamide
  • the intercalation is intercalated in the wheat during the melt extrusion process.
  • the aliphatic amino-terminated hyperbranched polyamide in the nano-sheet structure of magadite nanosheets has a chemical reaction between its amino group and the maleic anhydride group in the compatibilizer, and it is in situ on the surface of the magadite nano-particles.
  • the branch macromolecular chain improves the compatibility of the magadiite nanoparticles in the PP resin matrix, which not only improves the mechanical properties of the anti-bite material, but also facilitates the dispersion of capsaicin and other anti-bite substances, and improves the capsaicin
  • the effective utilization rate of anti-bite materials reduces costs At the same time, this anchoring effect further reduces the mobility of capsaicin and other anti-bite substances.
  • the aliphatic amino-terminated hyperbranched polyamide molecule has a highly branched structure, showing high flow, no chain entanglement, and low viscosity. It can also be used as a flow modifier for PP resin to improve the anti-bite material during preparation. The overall flow performance.
  • the resin is a PVC resin
  • the PVC resin can be 30-60 parts by weight, and the degree of polymerization of the PVC resin used is 1000-1400.
  • PVC resin is used as the basic resin to give the anti-bite material good mechanical strength, chemical resistance, flame retardancy and electrical insulation properties.
  • the raw material component of the anti-bite material also includes but is not limited to at least one of plasticizers, flame retardants, inorganic fillers, stabilizers, lubricants, and antioxidants.
  • plasticizer for example, in parts by weight, 15-40 parts of plasticizer, 5-12 parts of flame retardant, 10-30 parts of inorganic filler, 1.5-5 parts of stabilizer, 0.4-1.0 part of lubricant, and 0.2 part of antioxidant. -0.6 servings.
  • the plasticizer may include dioctyl adipate plasticizer, trioctyl trimellitate, dioctyl terephthalate, dioctyl adipate, dioctyl sebacate, and epoxidized soybean oil.
  • dioctyl adipate plasticizer trioctyl trimellitate, dioctyl terephthalate, dioctyl adipate, dioctyl sebacate, and epoxidized soybean oil.
  • the functions of plasticizers are: improve processing and forming performance; increase material plasticity and increase flexibility.
  • plasticizer molecule is inserted between the molecular chains of the PVC, which weakens the force between the molecular chains and reduces the flow viscosity of the melt, thereby greatly reducing the processing temperature, which is conducive to the molding process, and Improve the molding quality; at the same time, plasticizers can increase the plasticity of PVC, increase flexibility, and improve low-temperature brittleness.
  • the flame retardant can be one or more of antimony trioxide, sodium antimonate, zinc stannate, zinc hydroxystannate, aluminum hydroxide, and magnesium hydroxide. Flame retardants can further improve the flame retardant properties of PVC. PVC resin itself has a higher chlorine content and has certain flame retardant properties. However, the addition of plasticizers reduces the flame retardancy, so additional flame retardants need to be added. Flame retardants are generally inorganic substances such as antimony trioxide, sodium antimonate, zinc stannate, zinc hydroxystannate, aluminum hydroxide, magnesium hydroxide, etc., which have a synergistic effect with the chlorine element in the PVC resin, and do not need to be added Other halogen flame retardants.
  • the inorganic filler may be one or more of calcium carbonate, talc, barium sulfate, and calcined kaolin.
  • the main function of inorganic fillers such as calcium carbonate is to reduce product cost and reduce resin consumption. In addition, it can increase product hardness, improve heat deformation resistance, improve kneading performance, and reduce mold shrinkage.
  • the stabilizer can be an environmentally-friendly calcium-zinc composite stabilizer.
  • the calcium-zinc composite stabilizer mainly acts as a thermal stabilizer. It can capture the autocatalytic HCl released by the PVC resin, or it can be added to the unstable polyene structure produced by the PVC resin. To prevent or reduce the decomposition of PVC resin.
  • the lubricant may be one or more of stearic acid and its esters, stearates, polyethylene wax, oxidized polyethylene wax, paraffin wax, stearic acid amide, and oleic acid amide.
  • the function of the lubricant is to form a smooth interface on the contact surface of the anti-bite material and the processing machine to reduce friction; at the same time, it can reduce the melt viscosity of the anti-bite material, reduce the friction between the internal molecules of the anti-bite material, and improve the processing of the anti-bite material. Performance, improve production efficiency, and prevent resin decomposition due to excessive frictional heat.
  • the antioxidant may be at least one of the antioxidant 1010 and the antioxidant 168, such as a mixture of the two, and the antioxidant 1010 and the antioxidant 168 may be mixed in any mass ratio, such as 1:1.
  • the combination of antioxidants 1010 and 168 has a good synergistic effect, which can effectively inhibit or reduce the thermal oxidative aging of PVC and prolong the service life of the material.
  • the anti-bite material prepared by using PVC resin as the resin matrix can be prepared by the following method: adding each raw material component into a high-speed kneader and mixing, the kneading temperature is 120-150°C, the kneading time is 8-15min, and then pass the conventional The twin-screw extruder is melted and extruded, water-cooled and hot-cut to pelletize.
  • the process parameters of the twin-screw extruder are: the temperature in the first zone is 140 ⁇ 145°C, the temperature in the second zone is 155 ⁇ 160°C, the temperature in the third zone is 155 ⁇ 160°C, the temperature in the fourth zone is 150 ⁇ 165°C, and the temperature in the fifth zone is 150 ⁇ 155°C, six zone temperature 150 ⁇ 155°C, seven zone temperature 150 ⁇ 155°C, eight zone temperature 150 ⁇ 155°C, nine zone temperature 160 ⁇ 165°C, head temperature 165 ⁇ 170°C, twin screw speed 300 ⁇ 500r /min.
  • an embodiment of the present application also provides an anti-bite article, wherein the anti-bite article contains any one of the above-mentioned anti-bite agents, or is prepared from any one of the above-mentioned anti-bite materials.
  • anti-bite articles can be prepared by using the aforementioned anti-bite materials provided in the embodiments of the present application, and a good and long-lasting anti-bite effect of animals can be obtained.
  • the anti-bite article is the housing of electrical appliances made of electrically insulating materials, such as the housings of sockets, power cords, power converters and other electrical accessories, the housings of wires, and cable sheaths.
  • various types of electrical appliances such as the housing of TVs, refrigerators, air conditioners, electric fans, etc.
  • the embodiment of the present application provides an anti-bite agent, the anti-bite agent includes: magadite modified by aliphatic amino-terminated hyperbranched polyamide, and magadite in the modified magadite lamella structure Capsaicin.
  • the anti-bite agent provided in the examples of the application is prepared by the following method:
  • magadite suspension ie the first mixed solution
  • mass ratio of the magadite to the deionized water is 1: 50.
  • the average particle size of magadite is 30nm.
  • the aliphatic amino-terminated hyperbranched polyamide was added to a 1% volume fraction of acetic acid solution, and after being fully dissolved, the pH value was adjusted to 5.0 with a 1 mol/L NaOH solution to obtain a second mixed solution. Then slowly add the second mixture dropwise to the first mixture, heat to 80°C, stir the reaction for 6 hours, centrifuge the reaction mixture at 5000r/min for 10min, then filter with a 0.45 ⁇ m microporous membrane and wash with distilled water To neutrality, the magadiite modified by the intercalating agent is obtained.
  • the mass ratio of the aliphatic amino-terminated hyperbranched polyamide to the acetic acid solution is 1:100; the aliphatic amino-terminated hyperbranched polyamide has a molecular weight of 2000, which can be purchased directly from the market.
  • an aliphatic amino-terminated hyperbranched polyamide is used as an intercalant to organically modify the inorganic carrier magadiite.
  • the hyperbranched polyamide-terminated amino group exists in the form of -NH 3 + , which can interact with wheat
  • the Na + between the sillite layers undergoes cation exchange reaction, and the hyperbranched polyamide can intercalate into the magadite lamella structure, which increases the interval of the magadite lamella, which is beneficial to the subsequent capsaicin molecules.
  • the aliphatic hyperbranched polyamide macromolecules are distributed in the lamellar structure, so that the surface of the magadiite turns from hydrophilic to lipophilic, improving the compatibility with capsaicin molecules, and also Facilitate the insertion of capsaicin molecules into the sheet structure.
  • the embodiment of the present application provides an anti-bite agent, which includes: montmorillonite modified by aliphatic amino-terminated hyperbranched polyamide, and capsaicin in the layer structure of the modified montmorillonite.
  • the anti-bite agent provided in the examples of the application is prepared by the following method:
  • montmorillonite suspension ie the first mixture.
  • the mass ratio of montmorillonite to deionized water is 1:50, and the average particle size of montmorillonite is It is 30nm.
  • the aliphatic amino-terminated hyperbranched polyamide was added to a 1% volume fraction of acetic acid solution, and after being fully dissolved, the pH value was adjusted to 5.0 with 1 mol/L NaOH solution to obtain a second mixed solution. Then slowly add the second mixture dropwise to the first mixture, heat to 80°C, stir the reaction for 6 hours, centrifuge the reaction mixture at 5000r/min for 10min, then filter with a 0.45 ⁇ m microporous membrane and wash with distilled water To neutrality, the montmorillonite modified by the intercalating agent is obtained.
  • the mass ratio of the aliphatic amino-terminated hyperbranched polyamide to the acetic acid solution is 1:100; the aliphatic amino-terminated hyperbranched polyamide has a molecular weight of 2000, which can be purchased directly from the market.
  • Example 1 The only difference from Example 1 is that the inorganic carrier in this example is sepiolite modified with aliphatic amino-terminated hyperbranched polyamide.
  • Example 1 The only difference from Example 1 is that the inorganic carrier in this example is chitosan-modified magadite.
  • Example 1 The only difference from Example 1 is that the inorganic carrier in this example is sepiolite modified with chitosan.
  • Example 1 The only difference from Example 1 is that the inorganic carrier in this example is ⁇ -aminopropyltriethoxysilane modified magadiite.
  • Example 1 The only difference from Example 1 is that the anti-bite substance used in this example is allicin.
  • Example 1 The only difference from Example 1 is that the anti-bite substance used in this example is mustardin.
  • the raw material components of the anti-bite material include: 35 parts of homo-PP resin, 35 parts of copolymerized PP resin, and 5 parts of the anti-bite agent in Example 1.
  • the preparation method of the anti-bite material provided in this embodiment is as follows: the above-mentioned raw material components are mixed, and then melted and extruded through a conventional twin-screw extruder, and then water-cooled and hot-cut to granulate.
  • zone one temperature is 152°C
  • zone two temperature is 166°C
  • zone three temperature is 168°C
  • zone four temperature is 168°C
  • zone five temperature is 169°C
  • zone six temperature is 170°C
  • the zone temperature is 172°C
  • the eight zone temperature is 172°C
  • the nine zone temperature is 182°C
  • the die temperature is 192°C
  • twin-screw extruder speed is 400r/min.
  • the anti-bite material prepared in this embodiment can be used to prepare a power converter housing.
  • the raw material components of the anti-bite material include: 36.5 parts of homopolymer PP resin, 36.5 parts of copolymer PP resin, and 3 parts of the anti-bite agent in Example 1.
  • the preparation method of the anti-bite material provided in this embodiment is as follows: the above-mentioned raw material components are mixed, and then melted and extruded by a conventional twin-screw extruder, and then water-cooled and hot-cut to pelletize.
  • the process parameters of the twin-screw extruder during extrusion are as follows: the temperature in the first zone is 150°C, the temperature in the second zone is 165°C, the temperature in the third zone is 165°C, the temperature in the fourth zone is 160°C, the temperature in the fifth zone is 160°C, and the temperature in the sixth zone is 160°C.
  • the zone temperature is 160°C
  • the eight zone temperature is 160°C
  • the nine zone temperature is 180°C, the die temperature is 190°C
  • the twin-screw extruder speed is 300r/min.
  • the anti-bite material prepared in this embodiment can be used to prepare a power converter housing.
  • the raw material components of the anti-bite material include: 33.5 parts of homopolymer PP resin, 33.5 parts of copolymer PP resin, and 8 parts of the anti-bite agent in Example 1.
  • the preparation method of the anti-bite material provided in this embodiment is as follows: the above-mentioned raw material components are mixed, and then melted and extruded by a conventional twin-screw extruder, and then water-cooled and hot-cut to pelletize.
  • zone one temperature is 155°C
  • zone two temperature is 170°C
  • zone three temperature is 170°C
  • zone four temperature is 175°C
  • zone five temperature is 175°C
  • zone six temperature is 175°C
  • the zone temperature is 175°C
  • the eight zone temperature is 175°C
  • the nine zone temperature is 185°C
  • the die temperature is 195°C
  • twin-screw extruder speed is 500r/min.
  • the anti-bite material prepared in this embodiment can be used to prepare a power converter housing.
  • This embodiment provides an anti-bite material that can be used to prepare a power converter housing.
  • the difference from Embodiment 9 is that the raw material component of the anti-bite material provided in this embodiment does not contain a thermal agent.
  • the raw material components of the anti-bite material include: 40 parts of PVC resin, 20 parts of dioctyl adipate plasticizer, and 1.5 parts of epoxy soybean oil, 1.5 parts of antimony trioxide, 8 parts of aluminum hydroxide, 20 parts of calcium carbonate, 5 parts of anti-bite agent in Example 1, 1 part of heat-sensitizing agent vanillyl butyl ether, 2 parts of calcium zinc stabilizer, hard lubricant 0.5 parts of calcium fatty acid, 0.5 parts of a mixture of antioxidant 1010 and antioxidant 168 at a mass ratio of 1:1.
  • the preparation method of the anti-bite material provided in this embodiment is as follows: the above-mentioned raw material components are sequentially added to a high-speed kneader and mixed, the kneading temperature is 145°C, and the kneading time is 8 minutes; and then the mixed materials are melted through a twin-screw extruder Extrusion, water cooling and hot cutting to pelletize.
  • the process parameters of the twin-screw extruder are: zone one temperature 142°C, zone two temperature 158°C, zone three temperature 158°C, zone four temperature 152°C, zone five temperature 152°C, zone six temperature 152°C, zone seven temperature 155 °C, the temperature in the eight zones is 155°C, the temperature in the nine zones is 162°C, the head temperature is 170°C, and the speed of the twin-screw extruder is 400r/min.
  • the anti-bite material prepared in this embodiment can be used to prepare a cable sheath.
  • the raw material components of the anti-bite material include: 42 parts of PVC resin, 20 parts of dioctyl terephthalate plasticizer, and 1.5 parts of epoxy soybean oil. , 1.0 part of antimony trioxide, 10 parts of magnesium hydroxide, 20 parts of calcium carbonate, 3 parts of anti-bite agent in Example 2, 1 part of heat-sensitizing agent vanillyl butyl ether, 2 parts of calcium zinc stabilizer, lubricant 0.5 part of calcium stearate, 0.5 part of a mixture of antioxidant 1010 and antioxidant 168 at a mass ratio of 1:1.
  • the preparation method of the anti-bite material provided in this embodiment is as follows: the above-mentioned raw material components are sequentially added to a high-speed kneader and mixed, the kneading temperature is 135°C, and the kneading time is 10 minutes; and then the mixed materials are melted through a twin-screw extruder Extrusion, water cooling and hot cutting to pelletize.
  • the process parameters of the twin-screw extruder are: zone one temperature 145°C, zone two temperature 160°C, zone three temperature 160°C, zone four temperature 155°C, zone five temperature 155°C, zone six temperature 155°C, zone seven temperature 155 °C, the temperature in the eight zones is 155°C, the temperature in the nine zones is 165°C, the head temperature is 170°C, and the speed of the twin-screw extruder is 500r/min.
  • the anti-bite material prepared in this embodiment can be used to prepare a cable sheath.
  • the raw material components of the anti-bite material include: 34.5 parts of PVC resin, 20 parts of trioctyl trimellitate plasticizer, and 1.5 parts of epoxy soybean oil. , 1.5 parts of sodium antimonate, 8 parts of magnesium hydroxide, 20 parts of talc, 10 parts of anti-bite agent in Example 3, 1.5 parts of heat-sensitizing agent vanillyl butyl ether, 2 parts of calcium zinc stabilizer, lubricant poly 0.8 parts of ethylene wax, 0.5 parts of a mixture of antioxidant 1010 and antioxidant 168 at a mass ratio of 1:1.
  • the preparation method of the anti-bite material provided in this example is as follows: the above-mentioned raw material components are sequentially added to a high-speed kneader and mixed, the kneading temperature is 125°C, and the kneading time is 15 minutes; and then the mixed materials are melted through a twin-screw extruder Extrusion, water cooling and hot cutting to pelletize.
  • the process parameters of the twin-screw extruder are: zone one temperature 140°C, zone two temperature 155°C, zone three temperature 155°C, zone four temperature 150°C, zone five temperature 150°C, zone six temperature 150°C, zone seven temperature 155 °C, the temperature in the eight zones is 155°C, the temperature in the nine zones is 160°C, the head temperature is 170°C, and the speed of the twin-screw extruder is 300r/min.
  • the anti-bite material prepared in this embodiment can be used to prepare a cable sheath.
  • This embodiment provides an anti-bite material that can be used to prepare a cable sheath material.
  • the difference from Embodiment 13 is that this embodiment does not contain a thermal agent.
  • Example 9 A housing material for a power converter is provided. The only difference from Example 9 is that the comparative example does not contain the anti-bite material in Example 1 of the present application.
  • a power converter housing material is provided.
  • the only difference from Example 9 is that the comparative example does not contain the anti-bite substance in Example 1 of the present application, but contains 5 parts of capsaicin.
  • a cable sheath material is provided.
  • the difference from Example 13 is that the comparative example does not contain the anti-bite material in Example 1 of the present application.
  • a cable sheathing material is provided, which is different from Example 13 only in that the comparative example does not contain the anti-bite substance in Example 1 of the present application, but contains 5 parts of capsaicin.
  • the anti-bite material using PP resin as the resin matrix is tested in accordance with the bull group enterprise technical standard Q/GN J032043-2018.
  • the anti-bite material using PVC resin as the resin matrix is tested in accordance with the Bull Group Enterprise Technical Standard Q/GM J031022-2019.
  • This experiment uses beagle dogs as experimental animals. Beagle dogs are lively, curious, and like to grab and bite things.
  • the power converter housing and cable sheath products processed from the anti-bite materials in the above Examples 9-16 and Comparative Examples 1-4 into the animal test cage, and observe the animal's biting of the above products Situation, the observation period is 15 days, during which the animals are fed normally. Observe animal activity and diet every day, make records, and evaluate according to Table 1. Among them, the above-mentioned power converter housing and cable sheath products are collectively referred to as anti-bite materials in the following description.
  • the samples of the PP converter shells and PVC power cords processed in Comparative Example 1 and Comparative Example 3 were used as comparative samples.
  • the power converter housing and cable sheath products processed from the materials in the foregoing Examples 9-16 and Comparative Examples 1-4 were subjected to an aging test of 100°C-168h, and then placed in an animal test cage to observe The gnawing situation of the animal on the product, the observation period is 15 days, during which the animal is fed normally. Observe animal activity and diet every day, make records, and evaluate according to Table 1.
  • the above-mentioned power converter housing and cable sheath products are collectively referred to as anti-bite materials in the following description.
  • the power converter housing and cable sheath products processed from the materials in the foregoing Examples 9-16 and Comparative Examples 1-4 are placed in a glass bottle container with a volume of 2L, and then placed at a temperature of 70°C. In an oven at °C, take it out after processing for 1 hour, and quickly open the bottle cap for sniffing.
  • the 7 evaluators remove the highest and lowest scores according to the evaluation criteria in Table 2, and take the average value. Non-integer numbers are rounded off as the final evaluation result.
  • the above-mentioned power converter housing and cable sheath products are collectively referred to as anti-bite materials in the following description.
  • the rigidity of the anti-bite material provided by Examples 9-12 is improved, which is a manifestation of the strengthening effect of inorganic carrier nanoparticles on the material, while the toughness of the anti-bite material provided by Examples 9-12 is not reduced.
  • this is due to the chemical reaction between the hyperbranched polyamide terminal amino group in the intercalation structure and the maleic anhydride group in the compatibilizer, and the macromolecular chain is grafted on the surface of the nanoparticle in situ, which improves the nanomaterials in PP. Therefore, it has little effect on the toughness of the system.
  • the material of Comparative Example 1 did not add any anti-bite material, and the plastic casing of the converter was bitten, and there was a serious risk of electric shock; while the anti-bite materials of Examples 9-12 were added with anti-bite material, the power converter casing was anti-bite.
  • the bite effect is good, indicating that the anti-bite agent prepared in this application has good repellency to animals; compared with Examples 9-11, the anti-bite material of Example 12 has lower bite resistance and durability, because In Example 12, no heat sensation agent was added.
  • the heat sensation agent can stimulate the nerve endings of pets to produce heat sensation at a very low dosage.
  • the heat sensation effect is several times that of general capsaicin, and the heat sensation effect is long lasting. In the case of vegetarian spicy taste, the thermal sensitizer will have a synergistic effect and enhance the spicy effect.
  • the anti-bite property of the outer shell of the device is gradually lost; while the anti-bite grade of the anti-bite material provided in Examples 9-12 does not change before and after aging, indicating that the capsaicin molecule modified by the intercalation agent has significantly increased resistance to migration; in terms of odor,
  • the material provided in Comparative Example 2 was added with capsaicin without any treatment, and the prepared power converter product emitted a strong pungent odor; while the power converter prepared from the anti-bite material of Examples 9-12 had only a slight odor It illustrates that the preparation process of the anti-bite agent provided in the embodiments of the application effectively reduces the generation of pungent odors, so that the anti-bite material can be used in an indoor environment.
  • the material of Comparative Example 3 did not add any anti-bite material, and the cable sheath was bitten, and there was a serious risk of electric shock; while the anti-bite materials of Examples 13-16 were added with anti-bite materials, the power supply sheath had an anti-bite effect Well, it shows that the anti-bite agent prepared in the examples of this application has good repellency to pets; compared with Examples 13-15, the anti-bite material of Example 16 has lower bite resistance and durability, because The anti-bite material of Example 16 did not add a heat sensation agent.
  • the heat sensation agent can stimulate the nerve endings of pets to produce heat at a very low dosage.
  • the heat sensation effect is several times that of general capsaicin, and the heat sensation effect is long lasting. When pets feel the pungent taste of capsaicin, the heat sensitizer will have a synergistic effect and enhance the spiciness effect.
  • the anti-bite agent provided in the embodiments of the present application not only solves the problem that capsaicin is added to the anti-bite material, which has a high odor and cannot be used indoors, but also solves the problem of the easy migration of capsaicin caused by the anti-bite material.
  • the anti-bite material provided by the embodiments of the present application has a good anti-biting effect of animals, and can be applied to the preparation of anti-bite articles such as power converter housings, small household appliance housings, and cable sheaths.

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Abstract

本申请公开了一种防咬剂、防咬材料、防咬物品及制备方法。防咬剂包括：具有片层结构且经插层剂改性的无机载体、位于无机载体的片层结构中的防咬物质，其包括能够散发动物讨厌或刺激性气味的天然或人工合成物质：辣椒素、大蒜素、芥末素、大蒜粉、芥末粉、辣椒粉或胡椒粉。通过使防咬物质置于无机载体的片层结构中，可降低小分子防咬物质的迁移，达到缓释控释目的，确保添加有防咬物质的防咬物品的防咬效果持久有效。防咬物质位于无机载体的片层结构中，也利于提高防咬物质的耐热稳定性，有效遏制上述防咬物质的挥发甚至分解，防止防咬物质挥发具有刺激气味的气体。该防咬物质添加于防咬物品中，能够防止动物啃咬，且防咬效果持久有效。

Description

一种防咬剂、防咬材料、防咬物品及其制备方法
本申请要求于2019年12月31日提交的申请号为201911416688.0、发明名称为“一种防宠物剂及其制备方法以及应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及化学用品领域，特别涉及一种防咬剂、防咬材料、防咬物品及其制备方法。
背景技术
包括家养宠物在内的动物喜欢啃咬物品，特别地，当动物啃咬诸如电源线、插座、电源转换器之类的与电相关的物品时，容易引发触电、漏电等安全事故。所以，有必要对物品进行处理使其对动物产生防咬性。
辣椒素作为一种防咬物质可以被加入至物品中，赋予物品口感刺激性，进而实现防咬。然而，随着使用时间的延长，添加有辣椒素的物品的口感刺激性会逐渐降低，导致其防咬效果逐渐丧失。
申请内容
本申请实施例提供了一种防咬剂、防咬材料、防咬物品及其制备方法，可以解决上述技术问题。
具体而言，包括以下技术方案：
在本申请的第一方面，提供了一种防咬剂，其中，所述防咬剂包括：具有片层结构且经插层剂改性的的无机载体、以及位于所述无机载体的片层结构中的防咬物质；
所述防咬物质是能够散发动物讨厌或刺激性气味的天然或人工合成物质，例如辣椒素、大蒜素、芥末素、大蒜粉、芥末粉、辣椒粉或胡椒粉。
在一种可能的实施方式中，所述插层剂包括但不限于超支化聚酰胺、壳聚糖、γ-氨丙基三乙氧基硅烷和烷基铵盐(如叔胺盐或季铵盐)中的至少一种。
在一种可能的实施方式中，所述超支化聚酰胺为脂肪族端氨基超支化聚酰 胺，例如乙二胺(或丙二胺)与丙烯酸酯(例如丙烯酸甲酯或丙烯酸乙酯)所得到的端氨基超支化聚酰胺；所述叔胺盐例如可为十二烷基三甲基溴化铵、十六烷基三甲基溴化铵和十八烷基三甲基溴化铵、双十六烷基二甲基溴化铵等。
进一步地，本申请提供的防咬剂还含有热感剂，例如选自香兰基丁醚、香兰基异丁基醚、香兰基正丙基醚、香兰基异丙基醚、香兰基正氨基醚、香兰基异戊基醚、香兰基正己基醚、香兰基甲醚、香兰基乙醚、姜醇、姜烯酚、姜油酮中的至少一种。
在一种可能的实施方式中，所述无机载体为层状硅酸盐，层状硅酸盐选自麦羟硅钠石、蒙脱土、高岭土、云母和海泡石中的至少一种。
在一种可能的实施方式中，所述防咬物质位于无机载体的片层之间，例如麦羟硅钠石的片层之间。
在本申请的第二个方面，提供了一种防咬剂的制备方法或使防咬物质中的刺激性气味缓慢释放的方法，其包括制备包含经插层剂改性的无机载体与防咬物质的溶解液，并获得溶解液中的固体溶质的步骤，任选地依次经加热、离心、过滤得到溶解液中的固体溶质，即所述防咬剂。
其中，所述防咬剂和防咬物质例如可为本申请的第一方面所定义的那样。
在一种可能的实施方式中，所述包含经插层剂改性的无机载体与防咬物质的溶解液通过如下方法获取：
将所述防咬物质溶解于溶剂中，得到所述包含防咬物质的溶解液，所述溶剂选自乙醇、甲醇、丙酮中的至少一种；和，
将经插层剂改性的无机载体加入至上述包含防咬物质的溶解液中。
在一种可能的实施方式中，所述经插层剂改性的无机载体通过如下方法获取：
将所述无机载体分散于水(例如去离子水)中，并任选地经过超声处理，得到第一混合液；
将所述插层剂溶解于酸液中，得到第二混合液；
将所述第一混合液与所述第二混合液混合，并任选地依次经加热、离心、过滤，得到所述经插层剂改性的无机载体。
在一种可能的实施方式中，所述第二混合液的pH值范围为4-5。
在一种可能的实施方式中，所述酸液选自醋酸、碳酸、柠檬酸、磷酸中的至少一种。
在一种可能的实施方式中，所述将所述第一混合液与所述第二混合液混合，包括：
将所述第二混合液滴加至所述第一混合液中，使所述第一混合液与所述第二混合液混合。
在本申请的第三方面，提供了一种防咬材料，其中，所述防咬材料包括上述的任一种防咬剂。
在一种可能的实施方式中，所述防咬材料为电绝缘材料，例如塑料材质或橡胶。
在一种可能的实施方式中，所述防咬材料包括树脂和防咬剂，例如包含以下重量份的原料组分：
树脂30-90份；和防咬剂3-10份。
在一种可能的实施方式中，所述防咬材料的原料组分还包括0.5-1.5重量份的热感剂。
在一种可能的实施方式中，所述树脂选自PP树脂、PVC树脂和ABS树脂中的至少一种。
在一种可能的实施方式中，所述防咬材料的原料组分还包括添加剂，所述添加剂选自增塑剂、阻燃剂、无机填料、稳定剂、润滑剂、抗氧剂、相容剂和抗铜害剂中的至少一种。
在本申请的第四方面，本申请实施例提供了一种防咬物品，其中，所述防咬物品包含本申请提供的防咬剂，或由上述的任一种防咬材料制备得到。
在一种可能的实施方式中，所述防咬物品为由电绝缘材料制备的电气用品的外壳、电源转换器的外壳、插座的外壳、导线的外壳、电缆护套或轮胎等。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚，下面将对本申请实施方式作进一步地详细描述。
一方面，本申请提供了一种防咬剂，其中，该防咬剂包括：具有片层结构且经插层剂改性的无机载体、以及位于无机载体的片层结构中的防咬物质。
其中，防咬物质是能够散发动物讨厌或刺激性气味的天然或人工合成物质，例如辣椒素、大蒜素、芥末素、大蒜粉、芥末粉、辣椒粉或胡椒粉。
本申请实施例提供的防咬剂，通过使防咬物质置于经插层剂改性的无机载 体的片层结构中，有效降低了小分子防咬物质辣椒素、大蒜素、芥末素的迁移，达到缓释控释目的，确保添加有防咬物质的防咬物品的防咬效果持久有效。同时，防咬物质位于无机载体的片层结构中，也利于提高防咬物质的耐热稳定性，有效遏制上述防咬物质的挥发甚至分解，防止防咬物质挥发具有刺激气味的气体，提高其适用性。该防咬物质添加于防咬物品中，能够达到防止动物啃咬的目的，且防咬效果持久有效。
其中，无机载体经插层剂改性，使得插层剂得以插层进入无机载体的片层结构中，使得无机载体片层间距增大，有利于辣椒素等防咬物质顺利插入到无机载体的片层结构中。
可以理解的是，本申请实施例所涉及的“动物”，包括但不限于家养宠物、野生动物，例如家鼠等。
作为示例，插层剂可以选自超支化聚酰胺、壳聚糖和γ-氨丙基三乙氧基硅烷、烷基铵盐(如叔胺盐或季铵盐)中的至少一种，优选地，所述超支化聚酰胺为脂肪族端氨基超支化聚酰胺，例如乙二胺(或丙二胺)与丙烯酸酯(例如丙烯酸甲酯或丙烯酸乙酯)所得到的端氨基超支化聚酰胺；所述叔胺盐例如为十二烷基三甲基溴化铵、十六烷基三甲基溴化铵和十八烷基三甲基溴化铵、双十六烷基二甲基溴化铵。
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选用上述种类的插层剂，其中包含的氨基可以NH3 + 形式存在，与无机载体片层间的无机阳离子进行阳离子交换反应，进而得以插层进入无机载体的片层结构中，使无机载体片片层间距增大。
其中，该超支化聚酰胺可以为脂肪族端氨基超支化聚酰胺，一方面，其不仅能顺利插层进入无机载体的片层结构中，而且还可以使无机载体的表面由亲水性转变为亲油性，提高与辣椒素等防咬物质的相容性，也有利于辣椒素等防咬物质的分子插入到无机载体的片层结构中。
脂肪族端氨基超支化聚酰胺的分子量一般在1000～2500之间，可从市场上直接购买得到。
作为示例，无机载体可以为层状硅酸盐，其平均粒径可以为1nm-100nm，例如，层状硅酸盐可以选自麦羟硅钠石、蒙脱土、高岭土、云母和海泡石中的至少一种。以上各类层状硅酸盐均具有良好的片层结构。
本申请实施例中，防咬物质位于无机载体的片层结构之间，例如麦羟硅钠石的片层之间。
本申请实施例使用上述具有片层结构的无机载体，通过溶液插层法将辣椒素等小分子防咬物质插入片层结构中，有效降低了防咬物质迁移，从而达到缓释控释目的，确保制备得到的防咬物品的防咬效果持久有效。同时，防咬物质与无机载体的这种插层结构也提高了辣椒素等防咬物质的耐热稳定性，有效降低了辣椒素等防咬物质挥发甚至分解，从源头上降低挥发性刺激气味的产生。另外本申请实施例选用的上述种类的无机载体，比表面积大，也是一种优良的气味吸附剂，可以有效去除防咬材料中的刺激性气味，使防咬材料适用于室内环境。
可见，本申请实施例提供的防咬物质不仅解决了辣椒素等防咬物质添加到防咬材料中时气味性大，无法应用于室内的问题，还解决了辣椒素等防咬物质容易迁移而导致的防咬材料防动物啃咬持久性差的问题，同时也解决了辣椒素等防咬物质耐热稳定性差，易挥发导致产品批次稳定性差的问题。
[根据细则91更正 16.04.2020]　
举例来说，本申请实施例可以脂肪族端氨基超支化聚酰胺作为插层剂，同时以平均粒径为1nm-100nm的麦羟硅钠石作为无机载体，选用脂肪族端氨基超支化聚酰胺作为插层剂对无机载体麦羟硅钠石进行有机改性，在酸性条件下超支化聚酰胺端氨基以NH3 +形式存在，可以与麦羟硅钠石层间Na +进行阳离子交换反应，脂肪族端氨基超支化聚酰胺得以插层进入麦羟硅钠石片层结构中，使麦羟硅钠石片层间距增大，有利于后续辣椒素等防咬物质分子顺利插入到麦羟硅钠石的片层结构中。同时脂肪族端氨基超支化聚酰胺大分子分布在麦羟硅钠石的片层结构中，使麦羟硅钠石表面由亲水性转变为亲油性，提高与辣椒素等防咬物质分子的相容性，也有利于辣椒素等防咬物质分子插入到麦羟硅钠石的片层结构中。
脂肪族端氨基超支化聚酰胺插层于麦羟硅钠石片层结构中，由于其椭球形结构和柔性长分子链段，使麦羟硅钠石纳米粒子表面被柔性分子链包裹，有效阻碍纳米粒子之间的团聚，提高了纳米粒子在树脂中的分散性。
进一步地，本申请实施例提供的防咬剂还含有热感剂，例如选自香兰基丁醚、香兰基异丁基醚、香兰基正丙基醚、香兰基异丙基醚、香兰基正氨基醚、香兰基异戊基醚、香兰基正己基醚、香兰基甲醚、香兰基乙醚、姜醇、姜烯酚、姜油酮中的至少一种，能够进一步提高防咬剂的口感刺激性，提高动物趋避效果。
另一方面，本申请实施例提供了上述的任一种防咬剂的制备方法，或者使 防咬物质中的刺激性气味缓慢释放的方法，其中，该制备方法包括：制备包含经插层剂改性的无机载体与防咬物质的溶解液，并获得溶解液中的固体溶质的步骤，任选地依次经加热、离心、过滤得到溶解液中的固体溶质，固体溶质即为防咬剂。
其中，所述防咬剂和防咬物质例如可为本申请的第一方面所定义的那样。
本申请实施例通过使无机载体与包含防咬物质的溶解液混合，采用溶液插层法，防咬物质得以进入无机载体的片层结构中，有效降低了小分子防咬物质辣椒素、大蒜素、芥末素的迁移，达到缓释控释目的，确保添加有防咬物质的防咬物品的防咬效果持久有效。同时，防咬物质位于无机载体的片层结构中，也利于提高防咬物质的耐热稳定性，有效遏制上述防咬物质的挥发甚至分解，防止防咬物质挥发具有刺激气味的气体，提高其适用性。
其中，无机载体经插层剂改性，使得插层剂插层进入无机载体的片层结构中，使得无机载体片层间距增大，有利于后续辣椒素等防咬物质顺利插入到无机载体的片层结构中。
其中，本申请实施例中，包含防咬物质的溶解液可以通过如下方法获取：将防咬物质溶解于溶剂中，得到包含防咬物质的溶解液；
其中，上述溶剂选自乙醇、甲醇、丙酮中的至少一种。
利用上述挥发性的溶剂可以实现防咬物质充分且均匀的溶解，得到成分均一的溶解液，同时，上述溶剂在后续加热过程中被挥发，确保不会残留。
防咬物质，例如辣椒素，溶剂，例如乙醇，以及无机载体(包括经插层改性的无机载体)，三者之间的质量比可以为1：50-80：0.5-1.2，如此可以确保防咬物质尽可能地分布于无机载体的所有片层空间中，提高其负载量。
无机载体与包含防咬物质的溶解液混合后，加热反应，其加热的温度可以为40℃-80℃，例如45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃等，如此不仅能保证上述溶剂顺利挥发，且避免造成防咬物质的分解或挥发。待加热至上述合适温度后，搅拌反应设定时间，例如3-10小时，以确保防咬物质顺利插入无机载体的片层结构中。
其中，经插层剂改性的无机载体通过如下方法获取：将无机载体分散于去水，例如离子水中，并任选地经超声处理，得到第一混合液。
将插层剂溶解于酸液中，得到第二混合液。
将第一混合液与第二混合液混合，并任选地依次经加热、离心、过滤，得 到经插层剂改性的无机载体。
通过上述方法，可以获得纯净的经插层剂改性的无机载体。其中，可以采用将第二混合液滴加第一混合液中的方式使两者混合，如此利于插层剂充分且顺利地插入无机载体的片层结构中。
其中，在第一混合液中，无机载体与去离子水的质量比为1:30-60，在第二混合液中，插层剂与酸液的质量比为1:80-100，如此可以得到使第一混合液和第二混合液达到合适的浓度，利于改性过程的进行。
第一混合液与第二混合液混合后，可以加热至60-100℃，如此，在确保改性过程顺利进行的前提下，还可以使去离子水和酸液及时被挥发掉，避免残留。待加热至上述合适温度后，搅拌反应设定时间，例如2-8小时，以确保无机载体被充分改性。
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将插层剂溶解于中酸液，以创造酸性环境，为无机载体与插层剂之间的阳离子交换提供环境。进一步地，还可以通过碱液，例如NaOH溶液调节第二混合液的pH值，使第二混合液的pH值范围为4-5，例如为5，如此可以进一步保证诸如超支化聚酰胺、壳聚糖和γ-氨丙基三乙氧基硅烷等插层剂中包含的氨基以NH3+形式存在，来与无机载体片层间的无机阳离子进行阳离子交换反应，使插层过程顺利进行。
作为示例，酸液选自醋酸、碳酸、柠檬酸、磷酸中的至少一种。
举例来说，本申请实施例提供了这样一种防咬剂的制备方法，其包括如下步骤：
(1)将无机载体分散在去离子水中，并任选地经过超声处理得第一混合液；
(2)将插层剂溶解到醋酸溶液中以调节pH值，得第二混合液；
(3)将第二混合液滴加第一混合液中，依次经加热、离心、过滤，得插层剂改性后的无机载体；
(4)将防咬物质，例如辣椒素完全溶解在有机溶剂中，得到包含防咬物质的溶解液，然后向其中加入经插层剂改性的无机载体，依次加热、离心、过滤，得防咬剂。
再一方面，本申请实施例还提供了一种防咬材料，其中，该防咬材料包括上述的任一种防咬剂。
通过本申请实施例提供的防咬剂制备防咬材料，其可以防止动物啃咬，且具有防啃咬效果持久有效的优势。
本申请实施例中，防咬材料可以为多种材质，例如可以为电绝缘材料包括：塑料材质、橡胶、复合木质、纸质等。
举例来说，本申请实施例提供了一种塑料材质或橡胶材质的防咬材料，并且，可以使防咬物质为辣椒素。
在一种可能的实现方式中，本申请实施例提供的塑料材质的防咬材料包括包含树脂和防咬剂，例如包含以下重量份的原料组分：
树脂30-90份、防咬剂3-10份。
作为示例，上述树脂可以选自PP(Polypropylene，聚丙烯)树脂、PVC(Polyvinyl chloride，聚氯乙烯)树脂和ABS(Acrylonitrile Butadiene Styrene，丙烯腈-丁二烯-苯乙烯共聚物)树脂中的至少一种。
例如，上述PP树脂又可以包括均聚PP树脂30-45重量份和共聚PP树脂30-45重量份。PP树脂作为配方体系的基础树脂，赋予防咬材料良好的机械强度、耐化学性能和电绝缘性能，本申请实施例采用均聚PP和共聚PP的复配，均聚PP赋予防咬材料良好的刚性，共聚PP赋予防咬材料良好的冲击性能和低温韧性。
进一步地，所采用的均聚PP树脂的熔融指数为15-25g/10min。
进一步地，所采用的共聚PP树脂的熔融指数为5-10g/10min。
进一步地，本申请实施例提供的塑料材质的防咬材料的原料组分还包括：0.5-1.5重量份的热感剂。
利用上述极低用量的热感剂，即可刺激动物神经末梢产生热感，热感效果是一般辣椒素等防咬物质的数倍，热感效果持久，因此当宠物感受到辣椒素辛辣味道时，热感剂会起到协效作用，增强辣感效果，提高防啃咬效果。
其中，该热感剂可以为香兰基丁醚，其适用于与辣椒素、大蒜素或者芥末素等防咬物质协同作用，提高防啃咬效果。
为了提高防咬材料的综合性能，本申请实施例提供的防咬材料的原料组分还包括添加剂，添加剂选自增塑剂、阻燃剂、无机填料、稳定剂、润滑剂、抗氧剂、相容剂和抗铜害剂中的至少一种。
当树脂为PP树脂时，按重量份数计，原料组分中添加的添加剂及其重量配比分别如下：阻燃剂2～6份、无机填料10～20份、相容剂5～15份、润滑剂0.3～0.8份、抗氧剂0.2～0.6份、抗铜害剂0.2～0.6份。
阻燃剂可以为含磷、氮、溴的复配物，磷、氮、溴质量比为10:0.5-4.2:1.2-8.4， 如此可保证防咬材料通过UL94V-2级别和通过灼热丝GWFI 775℃，与传统溴系阻燃剂相比，不需要添加三氧化二锑，同时此类阻燃剂添加量少，不仅有效保证防咬材料的阻燃性同时有效降低防咬材料的成本。
举例来说，阻燃剂可以为EPFR-2000、EP700A、Lydorflam5014中的一种或多种。
相容剂可以为为PP-g-MAH、PE-g-MAH、POE-g-MAH、SEBS-g-MAH、EPDM-g-MAH以及SMA中的一种或多种。
无机填料可以为滑石粉，滑石粉目数可以为1250目-2500目，其用来提高防咬材料硬度和耐热性，减少成型收缩率；另外还可以降低树脂消耗，降低产品成本等。
润滑剂为聚乙烯蜡、氧化聚乙烯蜡、石蜡、硬脂酸酰胺、油酸酰胺、硬脂酸及其酯类、硬脂酸盐类中的一种或多种。润滑剂的作用是在材料与加工设备接触面形成光滑界面，降低摩擦作用；同时能降低防咬材料的熔融粘度，减少防咬材料内部分子之间的摩擦，改善了防咬材料的加工性能，提高生产效率。
抗氧剂可以为抗氧剂1010与抗氧剂168中的至少一种，例如可以为两者的混合物，抗氧剂1010与抗氧剂168可以任意质量比混合，例如1:1。抗氧剂1010和抗氧剂168复配使用，具有良好的协效作用，延长防咬材料的使用寿命。
上述抗铜害剂可以为为N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼(简称MD-1024)。抗铜害剂又称铜离子抑制剂，具有受阻酚和酰肼两种官能基团，受阻酚结构能阻止高分子材料受热氧老化，酰肼结构能对金属离子(如铜离子)进行络合反应，使其失去破坏作用，可改善由于铜离子的催化作用而出现的过早老化现象。因此当PP复合树脂用于铜线产品中，对于与铜线和铜端子接触的外壳起到保护作用。
以PP树脂作为树脂基体制备得到的防咬材料，可以通过如下方法制备得到：将各原料组分混合，经双螺杆挤出机熔融挤出，水冷热切造粒，即可制得。
其中，双螺杆挤出机的工艺参数为：一区温度150～155℃，二区温度165～170℃，三区温度165～170℃，四区温度160～175℃，五区温度160～175℃，六区温度160～175℃，七区温度160～175℃，八区温度160～175℃，九区温度180～185℃，机头温度190～195℃，双螺杆挤出机转速为300～500r/min。
在一种可能的实现方式中，当树脂为PP树脂，无机载体为麦羟硅钠石，且插层剂为脂肪族端氨基超支化聚酰胺时，在熔融挤出过程中，插层于麦羟硅钠 石纳米片层结构中的脂肪族端氨基超支化聚酰胺，其端氨基基团与相容剂中马来酸酐基团发生化学反应，原位在麦羟硅钠石纳米粒子表面接枝大分子链，提高了麦羟硅钠石纳米粒子在PP树脂基体中的相容性，这样既可以提高防咬材料的机械性能，也有利于辣椒素等防咬物质的分散，提高辣椒素等防咬物质的有效利用率，降低成本。同时这种锚固作用也进一步降低了辣椒素等防咬物质分子的迁移性。
脂肪族端氨基超支化聚酰胺分子具有高度支化结构，表现出高流动、无链缠结、低黏度的特性，其还可以可以作为PP树脂的流动改性剂，提高防咬材料在制备时的整体流动性能。
当树脂为PVC树脂时，PVC树脂可以为30-60重量份，所使用的PVC树脂的聚合度为1000-1400。PVC树脂作为基础树脂，赋予防咬材料良好的机械强度、耐化学性能、阻燃性能和电绝缘性能。
当树脂为PVC树脂时，防咬材料的原料组分还包括但不局限于增塑剂、阻燃剂、无机填料、稳定剂、润滑剂、抗氧剂中的至少一种。
示例地，按重量份数计，增塑剂15-40份、阻燃剂5-12份、无机填料10-30份、稳定剂1.5-5份、润滑剂0.4-1.0份、抗氧剂0.2-0.6份。
增塑剂可以包括己二酸二辛酯增塑剂、偏苯三酸三辛酯、对苯二甲酸二辛酯、己二酸二辛酯、癸二酸二辛酯和环氧大豆油中的一种或多种。增塑剂的作用有：改善加工成型性能；增加材料塑性，增加柔韧性。
在PVC中加入增塑剂，增塑剂分子插入到PVC分子链之间，削弱了分子链间的作用力，降低了熔体的流动粘度，从而大大降低了加工温度，有利于成型加工，而且提高了成型质量；同时增塑剂可以增加PVC的可塑性，增加柔软性，改善低温脆性。
阻燃剂可以为三氧化二锑、锑酸钠、锡酸锌、羟基锡酸锌、氢氧化铝、氢氧化镁中的一种或多种。阻燃剂可进一步提升PVC的阻燃性能，PVC树脂本身具有较高的氯含量，具有一定的阻燃特性，但是由于增塑剂的加入使得阻燃性降低，因此需要额外添加阻燃剂，阻燃剂一般为诸如三氧化二锑、锑酸钠、锡酸锌、羟基锡酸锌、氢氧化铝、氢氧化镁等与PVC树脂中氯元素产生协效作用的无机物，而无需再加入其它卤系阻燃剂。
无机填料可以为碳酸钙、滑石粉、硫酸钡、煅烧高岭土中的一种或多种。无机填料如碳酸钙等主要作用是降低产品成本，降低树脂消耗，另外还可以提 高产品硬度，提高耐热变形性，改善捏合性能，减少成型收缩率等。
稳定剂可以为环保型钙锌复合稳定剂，钙锌复合稳定剂主要起热稳定作用，能够捕捉PVC树脂释放出的具有自催化作用的HCl，或者与PVC树脂产生的不稳定聚烯结构起加成反应，以阻止或减轻PVC树脂的分解。
润滑剂可以为硬脂酸及其酯类、硬脂酸盐类、聚乙烯蜡、氧化聚乙烯蜡、石蜡、硬脂酸酰胺、油酸酰胺中的一种或者多种。润滑剂的作用是在防咬材料与加工机械接触面形成光滑界面，降低摩擦作用；同时能降低防咬材料的熔融粘度，减少防咬材料料内部分子之间的摩擦，改善防咬材料的加工性能，提高生产效率，防止因摩擦热过大而造成树脂分解。
抗氧剂可以为为抗氧剂1010与抗氧剂168重的至少一种，例如两者的混合物，抗氧剂1010与抗氧剂168可以任意质量比混合，例如1:1。抗氧剂1010和168复配使用，具有良好的协效作用，可以有效地抑制或降低PVC热氧老化，延长材料的使用寿命。
以PVC树脂作为树脂基体制备得到的防咬材料，可以通过如下方法制备得到：将各原料组分加入高速捏合机中混合，捏合温度为120～150℃，捏合时间为8～15min，再通过常规的双螺杆挤出机熔融挤出，水冷热切造粒制成。
作为示例，双螺杆挤出机的工艺参数为：一区温度140～145℃，二区温度155～160℃，三区温度155～160℃，四区温度150～165℃，五区温度150～155℃，六区温度150～155℃，七区温度150～155℃，八区温度150～155℃，九区温度160～165℃，机头温度165～170℃，双螺杆转速为300～500r/min。
再一方面，本申请实施例还提供了一种防咬物品，其中，该防咬物品包含上述的任一种防咬剂，或由上述的任一种防咬材料制备得到。
利用本申请实施例提供的上述防咬材料可以制备得到多种类型的防咬物品，获得良好且持久的防动物啃咬效果。
在一种可能的实现方式中，该防咬物品为由电绝缘材料制备的电气用品的外壳，例如，插座、电源线、电源转换器等各种电器附件的外壳，导线的外壳、电缆护套，以及，各种类型的电器，例如，电视、冰箱、空调、电扇等的外壳等。
以下将通过具体实施例进一步描述本申请：
实施例1
本申请实施例提供了一种防咬剂，该防咬剂包括：经脂肪族端氨基超支化聚酰胺改性的麦羟硅钠石，以及位于改性麦羟硅钠石片层结构中的辣椒素。
本申请实施例提供的防咬剂通过如下方法制备：
将麦羟硅钠石分散在去离子水中，搅拌3h，超声30min，得到麦羟硅钠石悬浮液(即第一混合液)，其中，麦羟基硅钠石与去离子水质量比为1:50，麦羟硅钠石的平均粒径为30nm。
将脂肪族端氨基超支化聚酰胺加入到体积分数为1％的醋酸溶液中，充分溶解后，用1mol/L的NaOH溶液调节pH值至5.0，得到第二混合液。然后将第二混合液缓慢滴加到第一混合液中，加热至80℃，搅拌反应6h，将反应混合液以5000r/min离心10min，然后用0.45μm的微孔滤膜过滤，并用蒸馏水洗涤至中性，得到经插层剂改性的麦羟硅钠石。其中，脂肪族端氨基超支化聚酰胺与醋酸溶液质量比为1:100；脂肪族端氨基超支化聚酰胺的分子量为2000，可从市场上直接买到。
将辣椒素分散在乙醇中，搅拌0.5h，使辣椒素完全溶解，得到包含辣椒素的溶解液。然后加入经插层剂改性的麦羟硅钠石，加热至60℃，搅拌反应3h，将混合液以5000r/min离心10min，然后用0.45μm的微孔滤膜过滤，将离心后得到的沉淀物在真空干燥箱中干燥并研磨成粉末，即得防咬剂。其中，辣椒素、改性麦羟硅钠石和乙醇质量比为1.5：1.2：60。
本实施例选用脂肪族端氨基超支化聚酰胺作为插层剂对无机载体麦羟硅钠石进行有机改性，在酸性条件下超支化聚酰胺端氨基以-NH 3 +形式存在，可以与麦羟硅钠石层间Na +进行阳离子交换反应，超支化聚酰胺得以插层进入麦羟硅钠石片层结构中，使麦羟硅钠石片层间距增大，有利于后续辣椒素分子顺利插入到片层结构中；同时脂肪族超支化聚酰胺大分子分布在片层结构中，使麦羟硅钠石表面由亲水性转变为亲油性，提高与辣椒素分子的相容性，也有利于辣椒素分子插入到片层结构中。
实施例2
本申请实施例提供了一种防咬剂，该防咬剂包括：经脂肪族端氨基超支化聚酰胺改性的蒙脱土，以及位于改性蒙脱土片层结构中的辣椒素。
本申请实施例提供的防咬剂通过如下方法制备得到：
将蒙脱土分散在去离子水中，搅拌3h，超声30min，得到蒙脱土悬浮液(即第一混合液)，蒙脱土与去离子水质量比为1:50，蒙脱土平均粒径为30nm。
将脂肪族端氨基超支化聚酰胺加入到体积分数为1％的醋酸溶液中，充分溶解后用1mol/L NaOH溶液调节PH值至5.0，得到第二混合液。然后将第二混合液缓慢滴加到第一混合液中，加热至80℃，搅拌反应6h，将反应混合液以5000r/min离心10min，然后用0.45μm的微孔滤膜过滤，并用蒸馏水洗涤至中性，得到经插层剂改性的蒙脱土。其中，脂肪族端氨基超支化聚酰胺与醋酸溶液质量比为1:100；脂肪族端氨基超支化聚酰胺的分子量为2000，可从市场上直接买到。
将辣椒素分散在乙醇中，搅拌0.5h，使辣椒素完全溶解，得到包含辣椒素的溶解液。然后加入经插层剂改性的蒙脱土，加热至60℃，搅拌反应3h，将混合液以5000r/min离心10min，然后用0.45μm的微孔滤膜过滤，将离心后得到的沉淀物在真空干燥箱中干燥并研磨成粉末，即得防咬剂。其中，辣椒素、改性蒙脱土和乙醇质量比为1.5：1.2：60。
实施例3
与实施例1的区别仅在于，该实施例中的无机载体为脂肪族端氨基超支化聚酰胺改性的海泡石。
实施例4
与实施例1的区别仅在于，该实施例中的无机载体为壳聚糖改性的麦羟硅钠石。
实施例5
与实施例1的区别仅在于，该实施例中的无机载体为壳聚糖改性的海泡石。
实施例6
与实施例1的区别仅在于，该实施例中的无机载体为γ-氨丙基三乙氧基硅烷改性的麦羟硅钠石。
实施例7
与实施例1的区别仅在于，该实施例使用的防咬物质为大蒜素。
实施例8
与实施例1的区别仅在于，该实施例使用的防咬物质为芥末素。
实施例9
本实施例提供了一种防咬材料，按重量份计，该防咬材料的原料组分包括：均聚PP树脂35份，共聚PP树脂35份，实施例1中的防咬剂5份，相容剂PP-g-MAH 8份，阻燃剂EPFR-2000 3份，2500目滑石粉12份，热感剂香兰基丁醚1份，润滑剂聚乙烯蜡0.4份，抗氧剂1010与抗氧剂168按质量比1：1的混合物0.4份，抗铜害剂N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼0.2份。
本实施例提供的防咬材料的制备方法如下：将上述各原料组分混合，再通过常规的双螺杆挤出机熔融挤出，水冷热切造粒即可制成。挤出时双螺杆挤出机的工艺参数如下：一区温度152℃，二区温度166℃，三区温度168℃，四区温度168℃，五区温度169℃，六区温度170℃，七区温度172℃，八区温度172℃，九区温度182℃，机头温度192℃，双螺杆挤出机转速为400r/min。
本实施例制备的防咬材料可用于制备电源转换器外壳。
实施例10
本实施例提供了一种防咬材料，按重量份计，该防咬材料的原料组分包括：均聚PP树脂36.5份，共聚PP树脂36.5份，实施例1中的防咬剂3份，相容剂PP-g-MAH 8份，阻燃剂EP700A 3份，2500目滑石粉12份，热感剂香兰基丁醚1份，润滑剂氧化聚乙烯蜡0.4份，抗氧剂1010与抗氧剂168按质量比1：2的混合物0.4份，抗铜害剂N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼0.2份。
本实施例提供的防咬材料的制备方法如下：将上述原料组分混合，再通过常规的双螺杆挤出机熔融挤出，水冷热切造粒即可制成。挤出时双螺杆挤出机的工艺参数如下：一区温度150℃，二区温度165℃，三区温度165℃，四区温度160℃，五区温度160℃，六区温度160℃，七区温度160℃，八区温度160℃，九区温度180℃，机头温度190℃，双螺杆挤出机转速为300r/min。
本实施例制备的防咬材料可用于制备电源转换器外壳。
实施例11
本实施例提供了一种防咬材料，按重量份计，该防咬材料的原料组分包括：均聚PP树脂33.5份，共聚PP树脂33.5份，实施例1中的防咬剂8份，相容剂 PE-g-MAH 8份，阻燃剂Lydorflam5014 3份，2500目滑石粉12份，热感剂香兰基丁醚1份，润滑剂石蜡0.4份，抗氧剂1010与抗氧剂168按质量比2：1的混合物0.4份，抗铜害剂N,N'-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰]肼0.2份。
本实施例提供的防咬材料的制备方法如下：将上述原料组分混合，再通过常规的双螺杆挤出机熔融挤出，水冷热切造粒即可制成。挤出时双螺杆挤出机的工艺参数如下：一区温度155℃，二区温度170℃，三区温度170℃，四区温度175℃，五区温度175℃，六区温度175℃，七区温度175℃，八区温度175℃，九区温度185℃，机头温度195℃，双螺杆挤出机转速为500r/min。
本实施例制备的防咬材料可用于制备电源转换器外壳。
实施例12
本实施例提供了一种防咬材料，可用于制备电源转换器外壳，与实施例9的区别仅在于，该实施例提供的防咬材料的原料组分中不含有热感剂。
实施例13
本实施例提供了一种防咬材料，按重量份计，该防咬材料的原料组分包括：PVC树脂40份，己二酸二辛酯增塑剂20份，环氧大豆油1.5份，三氧化二锑1.5份，氢氧化铝8份，碳酸钙20份，实施例1中的防咬剂5份，热感剂香兰基丁醚1份，钙锌稳定剂2份，润滑剂硬脂酸钙0.5份，抗氧剂1010与抗氧剂168按质量比1：1的混合物0.5份。
本实施例提供的防咬材料的制备方法如下：将上述原料组分依次加入高速捏合机中混合，捏合温度为145℃，捏合时间为8min；再将混合好的物料经过双螺杆挤出机熔融挤出，水冷热切造粒。双螺杆挤出机的工艺参数为：一区温度142℃，二区温度158℃，三区温度158℃，四区温度152℃，五区温度152℃，六区温度152℃，七区温度155℃，八区温度155℃，九区温度162℃，机头温度170℃，双螺杆挤出机的转速为400r/min。
本实施例制备的防咬材料可用于制备电缆护套。
实施例14
本实施例提供了一种防咬材料，按重量份计，该防咬材料的原料组分包括：PVC树脂42份，对苯二甲酸二辛酯增塑剂20份，环氧大豆油1.5份，三氧化 二锑1.0份，氢氧化镁10份，碳酸钙20份，实施例2中的防咬剂3份，热感剂香兰基丁醚1份，钙锌稳定剂2份，润滑剂硬脂酸钙0.5份，抗氧剂1010与抗氧剂168按质量比1：1的混合物0.5份。
本实施例提供的防咬材料的制备方法如下：将上述原料组分依次加入高速捏合机中混合，捏合温度为135℃，捏合时间为10min；再将混合好的物料经过双螺杆挤出机熔融挤出，水冷热切造粒。双螺杆挤出机的工艺参数为：一区温度145℃，二区温度160℃，三区温度160℃，四区温度155℃，五区温度155℃，六区温度155℃，七区温度155℃，八区温度155℃，九区温度165℃，机头温度170℃，双螺杆挤出机的转速为500r/min。
本实施例制备的防咬材料可用于制备电缆护套。
实施例15
本实施例提供了一种防咬材料，按重量份计，该防咬材料的原料组分包括：PVC树脂34.5份，偏苯三酸三辛酯增塑剂20份，环氧大豆油1.5份，锑酸钠1.5份，氢氧化镁8份，滑石粉20份，实施例3中的防咬剂10份，热感剂香兰基丁醚1.5份，钙锌稳定剂2份，润滑剂聚乙烯蜡0.8份，抗氧剂1010与抗氧剂168按质量比1：1的混合物0.5份。
本实施例提供的防咬材料的制备方法如下：将上述原料组分依次加入高速捏合机中混合，捏合温度为125℃，捏合时间为15min；再将混合好的物料经过双螺杆挤出机熔融挤出，水冷热切造粒。双螺杆挤出机的工艺参数为：一区温度140℃，二区温度155℃，三区温度155℃，四区温度150℃，五区温度150℃，六区温度150℃，七区温度155℃，八区温度155℃，九区温度160℃，机头温度170℃，双螺杆挤出机的转速为300r/min。
本实施例制备的防咬材料可用于制备电缆护套。
实施例16
本实施例提供了一种防咬材料，可用于制备电缆护套材料，与实施例13的区别仅在于，该实施例中不含有热感剂。
对比例1
提供了一种电源转换器外壳材料，与实施例9的区别仅在于，该对比例中 不含有本申请实施例1中的防咬物质。
对比例2
提供了一种电源转换器外壳材料，与实施例9的区别仅在于，该对比例中不含有本申请实施例1中的防咬物质，但是含有辣椒素5份。
对比例3
提供了一种电缆护套材料，与实施例13的区别仅在于，该对比例中不含有本申请实施例1中的防咬物质。
对比例4
提供一种电缆护套材料，与实施例13的区别仅在于，该对比例中不含有本申请实施例1中的防咬物质，但是含有辣椒素5份。
通过如下方法对实施例9-16以及对比例1-4中提供的防咬材料进行性能测试：
1、材料通用性能测试方法
以PP树脂作为树脂基体的防咬材料按照公牛集团企业技术标准Q/GN J032043-2018进行测试。
以PVC树脂作为树脂基体的防咬材料按照公牛集团企业技术标准Q/GM J031022-2019进行测试。
2、防动物啃咬性能评价
本实验选用比格犬作为实验动物，比格犬活泼好动，好奇心重，而且喜欢抓咬东西。
如上所述，将上述实施例9-16以及对比例1-4中的防咬材料加工成的电源转换器外壳、以及电缆护套产品放入动物试验笼中，观察动物对以上产品的啃咬情况，观察期为15天，期间正常对动物喂食。每天观察动物活动和饮食情况，并做好记录，按照表1进行评价。其中，上述电源转换器外壳、电缆护套产品在以下描述中统一称为防咬材料。
表1：防咬材料防动物啃咬等级划分
Figure PCTCN2020084787-appb-000001
其中，防护率＝(啃咬表面积对比样-啃咬表面积实验样)/总表面积，如果产品被咬穿以及某一部分被咬断，则啃咬表面积＝总表面积；对比样指未加入防咬物质的样品，分别以对比例1、对比例3加工而成的PP转换器外壳、PVC电源线作为对比样。
3、防动物啃咬耐久性评价
如上所述，将上述实施例9-16以及对比例1-4中的材料加工而成的电源转换器外壳、电缆护套产品进行100℃-168h老化实验，然后放入动物试验笼中，观察动物对产品的啃咬情况，观察期为15天，期间正常对动物喂食。每天观察动物活动和饮食情况，并做好记录，按照表1进行评价。其中，上述电源转换器外壳、电缆护套产品在以下描述中统一称为防咬材料。
4、产品气味性评价
如上所述，将上述实施例9-16以及对比例1-4中的材料加工而成的电源转换器外壳、电缆护套产品放入体积为2L的玻璃瓶容器中，然后放入温度为70℃烘箱中，处理1h后取出，迅速打开瓶盖进行嗅辨。由7位评价员按照表2评价标准去掉最高分和最低分，取平均值，非整数按照四舍五入法作为最终评价结果。其中，上述电源转换器外壳、电缆护套产品在以下描述中统一称为防咬材料。
表2：材料气味等级划分
等级 气味描述
1级 感觉不到气味
2级 可轻微感觉到气味，但是不令人反感
3级 可明显感觉到，有轻微不适感
4级 有强烈刺激性气味，令人厌恶
5级 令人无法接受
表3：防咬材料性能测试结果
Figure PCTCN2020084787-appb-000002
从表3中可以看出，本申请以上各实施例提供的防咬材料的物性均满足公牛集团企业标准Q/GN J032043-2018中关于转换器塑胶原材料技术要求；实施例9-12提供的防咬材料流动性增加明显，这是由于防咬剂中改性剂超支化聚酰胺高度支化结构，表现出与传统线性高分子完全不同的特性黏度特征，可以作为PP流动改性剂，提高了材料流动性能。
与对比例1相比，实施例9-12提供的防咬材料刚性方面有提升，这是无机载体纳米粒子对材料增强作用的体现，而实施例9-12提供的防咬材料韧性方面下降不明显，这是由于插层结构中超支化聚酰胺端氨基基团与相容剂中马来酸酐基团发生化学反应，原位在纳米粒子表面接枝大分子链，提高了纳米材料在PP中的相容性，因此对体系韧性影响不大。
对比例1的材料中未加任何防咬物质，转换器塑料外壳被咬破，存在严重的触电风险；而实施例9-12的防咬材料中均加入了防咬物质，电源转换器外壳防咬效果好，说明本申请所制备的防咬剂对动物具有良好的趋避性；与实施例9-11相比，实施例12的防咬材料的防咬性和耐久性较低，这是因为实施例12中并未加入热感剂，热感剂在极低用量下即可刺激宠物神经末梢产生热感，热感效果是一般辣椒素的数倍，热感效果持久，当宠物感受到辣椒素辛辣味道时， 热感剂会起到协效作用，增强辣感效果。
电源转换器外壳经过100℃，168h老化处理后，对比例2防咬等级由2级下降至4级，这是由于未经处理的辣椒素小分子容易迁移和挥发，随着时间延长，电源转换器外壳防咬特性逐渐丧失；而实施例9-12提供的防咬材料老化前后防咬等级未发生变化，说明经过插层剂改性处理的辣椒素分子耐迁移性明显增加；气味性方面，对比例2提供的材料中加入未经任何处理的辣椒素，制备的电源转换器产品散发出强烈的刺激性气味；而实施例9-12的防咬材料制备得到的电源转换器仅有轻微气味，说明本申请实施例提供的防咬剂的制备工艺有效降低刺激性气味的产生，使防咬材料可以用于室内环境中。
表4：防咬材料在老化前后的性能测试结果
Figure PCTCN2020084787-appb-000003
Figure PCTCN2020084787-appb-000004
从表4中可以看出，本申请各实施例提供的防咬材料的物性均满足公牛集团企业标准Q/GM J031022-2019中关于PVC电缆护套塑胶原材料技术要求；
对比例3的材料中未加任何防咬物质，电缆护套被咬破，存在严重的触电风险；而实施例13-16的防咬材料中均加入了防咬物质，电源护套防咬效果好，说明本申请实施例所制备的防咬剂对宠物具有良好的趋避性；与实施例13-15相比，实施例16的防咬材料的防咬性和耐久性较低，这是因为实施例16的防咬材料中并未加入热感剂，热感剂在极低用量下即可刺激宠物神经末梢产生热感，热感效果是一般辣椒素的数倍，热感效果持久，当宠物感受到辣椒素辛辣味道时，热感剂会起到协效作用，增强辣感效果。
利用对比例4的材料制备的电缆护套经过100℃，168h老化处理后，其防咬等级由2级下降至4级，这是由于未经处理的辣椒素小分子容易迁移和挥发，随着时间延长，电缆护套防咬特性逐渐丧失。而实施例13-16的防咬材料在老化前后，其防咬等级未发生变化，说明经过插层处理的辣椒素分子耐迁移性明显增加。气味性方面，对比例4材料中加入未经任何处理的辣椒素，制备的电缆护套散发出强烈的刺激性气味；而实施例13-16的防咬材料制备的电缆护套仅有轻微气味，说明本申请实施例提供的防咬剂的制备工艺有效降低刺激性气味的产生，使防咬材料可以用于室内环境中。
综上所述，本申请实施例提供的防咬剂不仅解决了辣椒素添加到防咬材料中气味性大，无法应用于室内的问题，还解决了辣椒素容易迁移而导致的防咬材料防动物啃咬持久性差的问题；同时也解决了辣椒素耐热稳定性差，易挥发导致产品批次稳定性差的问题。本申请实施例提供的防咬材料具备良好的防动物啃咬效果，可应用于电源转换器外壳、小家电外壳、电缆护套等防咬物品的制备中。
以上所述仅为本申请的较佳实施例，并不用以限制本申请，凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (20)

  1. 一种防咬剂，其中，所述防咬剂包括：具有片层结构且经插层剂改性的的无机载体、以及位于所述无机载体的片层结构中的防咬物质；
    所述防咬物质是能够散发动物讨厌或刺激性气味的天然或人工合成物质，例如辣椒素、大蒜素、芥末素、大蒜粉、芥末粉、辣椒粉或胡椒粉。
  2. 根据权利要求1所述的防咬剂，其中，所述插层剂选自超支化聚酰胺、壳聚糖、γ-氨丙基三乙氧基硅烷和烷基铵盐(如叔胺盐或季铵盐)中的至少一种，优选地，所述超支化聚酰胺为脂肪族端氨基超支化聚酰胺，例如乙二胺(或丙二胺)与丙烯酸酯(例如丙烯酸甲酯或丙烯酸乙酯)所得到的端氨基超支化聚酰胺；所述叔胺盐例如为十二烷基三甲基溴化铵、十六烷基三甲基溴化铵和十八烷基三甲基溴化铵、双十六烷基二甲基溴化铵。
  3. 根据权利要求2所述的防咬剂，其中，所述防咬剂还含有热感剂，例如选自香兰基丁醚、香兰基异丁基醚、香兰基正丙基醚、香兰基异丙基醚、香兰基正氨基醚、香兰基异戊基醚、香兰基正己基醚、香兰基甲醚、香兰基乙醚、姜醇、姜烯酚、姜油酮中的至少一种。
  4. 根据权利要求1-3任一项所述的防咬剂，其中，所述无机载体为层状硅酸盐。
  5. 根据权利要求4所述的防咬剂，其中，所述层状硅酸盐选自麦羟硅钠石、蒙脱土、高岭土、云母和海泡石中的至少一种。
  6. 权利要求1-5任一项所述的防咬剂的制备方法，其中，所述制备方法包括：制备包含经插层剂改性的无机载体与防咬物质的溶解液，并获得溶解液中的固体溶质的步骤，任选地依次经加热、离心、过滤得到溶解液中的固体溶质，即所述防咬剂。
  7. 根据权利要求6所述的防咬剂的制备方法，其中，所述包含防咬物质的 溶解液通过如下方法获取：
    将所述防咬物质溶解于溶剂中，得到所述包含防咬物质的溶解液；
    所述溶剂选自乙醇、甲醇、丙酮中的至少一种。
  8. 根据权利要求6所述的防咬剂的制备方法，其中，所述经插层剂改性的无机载体通过如下方法获取：
    将所述无机载体分散于水中，超声处理，得到第一混合液；
    将所述插层剂溶解于酸液中，得到第二混合液；
    将所述第一混合液与所述第二混合液混合，依次经加热、离心、过滤，得到所述经插层剂改性的无机载体。
  9. 根据权利要求8所述的防咬剂的制备方法，其中，所述第二混合液的pH值范围为4-5。
  10. 根据权利要求8所述的防咬剂的制备方法，其中，所述酸液选自醋酸、碳酸、柠檬酸、磷酸中的至少一种。
  11. 根据权利要求8所述的防咬剂的制备方法，其中，所述将所述第一混合液与所述第二混合液混合，包括：
    将所述第二混合液滴加至所述第一混合液中，使所述第一混合液与所述第二混合液混合。
  12. 一种防咬材料，其中，所述防咬材料包括权利要求1-5任一项所述的防咬剂。
  13. 根据权利要求12所述的防咬材料，其中，所述防咬材料为塑料材质或橡胶。
  14. 根据权利要求13所述的防咬材料，其中，所述防咬材料包括以下重量份的原料组分：
    树脂30-90份、防咬剂3-10份。
  15. 根据权利要求14所述的防咬材料，其中，所述树脂选自PP树脂、PVC树脂和ABS树脂中的至少一种。
  16. 根据权利要求14所述的防咬材料，其中，所述防咬材料的原料组分还包括0.5-1.5重量份的热感剂。
  17. 根据权利要求14-16任一项所述的防咬材料，其中，所述防咬材料的原料组分还包括添加剂，所述添加剂选自增塑剂、阻燃剂、无机填料、稳定剂、润滑剂、抗氧剂、相容剂和抗铜害剂中的至少一种。
  18. 一种防咬物品，其中，所述防咬物品包含权利要求1-5中任一项所述的防咬剂，或由权利要求12-17任一项所述的防咬材料制备得到。
  19. 根据权利要求18所述的防咬物品，其中，所述防咬物品为电气用品的外壳。
  20. 根据权利要求19所述的防咬物品，其中，所述防咬物品为电源转换器的外壳、插座的外壳、导线的外壳、电缆护套。
PCT/CN2020/084787 2019-12-31 2020-04-14 一种防咬剂、防咬材料、防咬物品及其制备方法 WO2021134976A1 (zh)

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