WO2018192163A1 - 一种动态硫化阻燃tpv复合材料及其制备方法 - Google Patents

一种动态硫化阻燃tpv复合材料及其制备方法 Download PDF

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Publication number
WO2018192163A1
WO2018192163A1 PCT/CN2017/101939 CN2017101939W WO2018192163A1 WO 2018192163 A1 WO2018192163 A1 WO 2018192163A1 CN 2017101939 W CN2017101939 W CN 2017101939W WO 2018192163 A1 WO2018192163 A1 WO 2018192163A1
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Prior art keywords
flame retardant
parts
tpv composite
flame
retardant
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PCT/CN2017/101939
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English (en)
French (fr)
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何玮頔
郭建兵
周登凤
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贵州省材料产业技术研究院
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Priority to ZA2018/06326A priority Critical patent/ZA201806326B/en
Publication of WO2018192163A1 publication Critical patent/WO2018192163A1/zh

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/22—Component parts, details or accessories; Auxiliary operations
    • B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Definitions

  • the invention relates to the technical field of materials science, in particular to a dynamic vulcanization flame retardant TPV composite material and a preparation method thereof.
  • TPV is the abbreviation of Thermoplastic Vulcanizate.
  • the Chinese name is thermoplastic EPDM dynamic vulcanized elastomer or thermoplastic EPDM dynamic vulcanized rubber. It is a high-vulcanized ethylene propylene diene monomer EPDM microparticle dispersed in continuous polypropylene PP phase. Molecular elastomer material.
  • the physical properties and functions of TPV at room temperature are similar to those of thermosetting rubber, which is characterized by thermoplastics at high temperatures and can be processed quickly, economically and conveniently. Widely used in the fields of automobiles, wire and cable, interior decoration and insulation materials.
  • intumescent flame retardants are an important class of flame retardants.
  • the EPDM/PP system has a thermal decomposition temperature of 328-410 ° C due to the thermal decomposition temperature of the two, and the thermal decomposition temperature of EPDM is 507-900 ° C, so it is difficult to select the resistance that matches at the same time.
  • the dynamic vulcanized TPV material has poor flame retardancy, poor processing performance, difficult molding process, and affects material properties.
  • a first object of the present invention is to provide a dynamically vulcanized flame retardant TPV composite material, wherein the dynamic vulcanized flame retardant TPV composite material has uniform dispersion of a flame retardant, excellent flame retardancy, good processing performance, and easy processing and molding.
  • a second object of the present invention is to provide a method for preparing the dynamic vulcanized flame-retardant TPV composite material, which is simple in process, convenient in operation, high in efficiency, and suitable for industrial production.
  • a dynamic vulcanized flame retardant TPV composite material prepared by the following parts by mass:
  • the dynamic vulcanization and flame retardant TPV composite material of the invention is prepared by using a specific amount of polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, flame retardant, flow modifier, crosslinking agent, heat stabilizer and ultraviolet light absorber.
  • the flame retardant is uniformly dispersed in the obtained dynamic vulcanized flame-retardant TPV composite material, and the obtained dynamic vulcanized flame-retardant TPV composite material has excellent antibacterial property, good processing property and easy processing and molding.
  • the dynamically vulcanized flame retardant TPV composite is mainly prepared from the following parts by mass:
  • polypropylene 30-50 parts of EPDM rubber, 8-12 parts of thermoplastic polyurethane elastomer, 20-25 parts of flame retardant, 0.8-1.2 parts of flow modifier, 0.3-0.5 parts of cross-linking agent , heat stabilizer 0.4-0.6 parts and ultraviolet light absorber 0.4-0.6 parts.
  • the dynamically vulcanized flame retardant TPV composite is mainly prepared from the following parts by mass:
  • thermoplastic polyurethane elastomer has a melt flow rate of from 25 to 55 g/10 min at 200 ° C and a pressure of 2.16 Kg and a Rockwell hardness of from 45 to 65.
  • the flame retardant comprises one or more of a halogen-free flame retardant and an inorganic flame retardant, and preferably the halogen-free flame retardant comprises N,N-bis(2-hydroxyethyl)aminone One or more of diethyl phosphinate and ammonium polyphosphate, further preferably the halogen-free flame retardant comprises diethyl N,N-bis(2-hydroxyethyl)aminomethylenephosphonate and polyphosphoric acid Ammonium.
  • the mass ratio of the diethyl N,N-bis(2-hydroxyethyl)aminomethylenephosphonate and the ammonium polyphosphate is 1:0.5-2, preferably 1:0.8-1.2, further preferably It is 1:1.
  • the flow modifier comprises one or more of an internal lubricant, an external lubricant, and a composite lubricant.
  • the internal lubricant comprises a higher fatty alcohol, a fatty acid ester, and a long chain polyfunctional group.
  • the esters, further preferably the long chain polyfunctional ester comprises an AM-80 flow modifier.
  • the crosslinking agent comprises one or more of external crosslinking agents, preferably including di-(tert-butylperoxyisopropyl)benzene and triallyl isocyanurate, diacrylic acid- One or more of 1,4-butanediol ester and dicumyl peroxide More preferably, it includes bis-(tert-butylperoxyisopropyl)benzene and triallyl isocyanurate.
  • external crosslinking agents preferably including di-(tert-butylperoxyisopropyl)benzene and triallyl isocyanurate, diacrylic acid- One or more of 1,4-butanediol ester and dicumyl peroxide More preferably, it includes bis-(tert-butylperoxyisopropyl)benzene and triallyl isocyanurate.
  • the mass ratio of the di-(tert-butylperoxyisopropyl)benzene and the triallyl isocyanurate is 1:0.5-2, preferably 1:0.8-1.2, further preferably 1 :1.
  • the heat stabilizer comprises one or more of antioxidants, preferably including 2,6-tert-butyl-4-methylphenol, tetrakis(4-hydroxy-3,5-di-tert-butyl)
  • antioxidants preferably including 2,6-tert-butyl-4-methylphenol, tetrakis(4-hydroxy-3,5-di-tert-butyl)
  • One or more of pentaerythritol ester, pentaerythritol 3,5-di-tert-butyl-4-hydroxyphenylpropionate, triphenyl phosphite and tridecyl phenyl phosphite further It preferably comprises 2,6-tert-butyl-4-methylphenol.
  • the ultraviolet light absorber comprises one or more of a benzophenone ultraviolet light absorber, a benzotriazole ultraviolet light absorber, and a piperidine ultraviolet light absorber, preferably including 2- Hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2(2-hydroxy-3',5'-di-tert-butylphenyl)- One or more of 5-chlorobenzotriazole and bis(2,2,6,6-tetramethylpiperidine) sebacate, further preferably including 2-hydroxy-4-methoxydi Benzophenone.
  • a dynamic vulcanized flame-retardant TPV composite material which comprises polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, flame retardant, flow modifier, crosslinking agent, heat stabilizer and ultraviolet
  • the light absorber is thoroughly mixed and extruded to obtain a dynamic vulcanized flame retardant TPV composite.
  • the preparation method of the dynamic vulcanization flame retardant TPV composite material of the invention has the advantages of simple process, convenient operation and high benefit, and is suitable for industrial production.
  • the preparation method of the dynamic vulcanized flame retardant TPV composite material comprises:
  • the ethylene propylene diene monomer, the thermoplastic polyurethane elastomer and the flame retardant are kneaded in proportion, and then polypropylene, a flow modifier, a crosslinking agent, a heat stabilizer and an ultraviolet light absorber are added, and the mixture is thoroughly mixed and extruded.
  • a dynamic vulcanized flame retardant TPV composite was obtained.
  • the thermoplastic polyurethane elastomer and the flame retardant are kneaded in proportion, a crosslinking agent, a polypropylene, a flow modifier, a heat stabilizer and an ultraviolet light absorber are sequentially added at intervals.
  • the mixture is thoroughly mixed, wherein the interval time is 1 min or more, preferably 2-5 min, further preferably 3 min; the mixing time is 10 min or more, preferably 20-30 min, and further preferably 25 min.
  • the sequential addition and sequential addition ensure the uniformity of mixing of the raw materials, and the obtained dynamic vulcanized flame-retardant TPV composite has good uniformity, good processing performance and easy processing.
  • the flame retardant is divided into three parts, the ethylene propylene diene rubber is added to the first flame retardant, and after mixing uniformly, the second flame retardant is added by stirring, and then the thermoplastic polyurethane elastomer is added, and after being uniformly mixed, , the remaining third flame retardant is added again, and the mass ratio of the three flame retardants is 1:1-2:1-2; preferably 1:1:2.
  • the ethylene propylene diene monomer, the thermoplastic polyurethane elastomer and the flame retardant are kneaded by an internal mixer, and after the kneading, the rubber is discharged, cooled for 20-24 hours, and then the polypropylene and the flow modifier are mixed with an internal mixer.
  • the cooling debinding comprises cooling at a cooling rate of 5-6 ° C / h, after cooling for 6-8 h, cooling at a cooling rate of 1-2 ° C / h for 14-16 h.
  • the kneading temperature is 50-80 ° C, preferably 60-70 ° C, and further preferably 60 ° C.
  • the kneading time is 20 min or more, preferably 20-40 min, further preferably 30 min.
  • the extrusion mixture comprises: preheating the heating zone of the twin-screw extruder, preheating to a temperature of 50-80 ° C, and then feeding the mixture into a twin-screw extruder to adjust the twin-screw extrusion
  • the speed of the machine is 1-10r/min, and the mixture is extruded.
  • the extrusion temperature is 150 ° C or higher, preferably 175 to 200 ° C, and further preferably 180 ° C.
  • the dynamic vulcanization and flame retardant TPV composite material of the invention is prepared by using a specific amount of polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, flame retardant, flow modifier, crosslinking agent, heat stabilizer and ultraviolet light absorber.
  • the flame retardant is uniformly dispersed in the obtained dynamic vulcanized flame-retardant TPV composite material, and the obtained dynamic vulcanized flame-retardant TPV composite material has excellent antibacterial property, good processing property and easy processing and molding.
  • the preparation method of the dynamic vulcanization flame retardant TPV composite material of the invention has the advantages of simple process, convenient operation and high benefit, and is suitable for industrial production.
  • the invention provides a dynamic vulcanization flame retardant TPV composite material, which is mainly prepared from the following parts by mass:
  • PP polypropylene
  • EPDM polypropylene
  • TPU thermoplastic polyurethane elastomer
  • flame retardant 0.5-1.5 flow modifier Parts
  • 0.2-0.6 parts of a crosslinking agent 0.2-0.8 parts of a heat stabilizer
  • 0.2-0.8 parts of an ultraviolet light absorber 20-50 parts of polypropylene (PP), 20-60 parts of EPDM, 5-15 parts of thermoplastic polyurethane elastomer (TPU), 15-30 parts of flame retardant, 0.5-1.5 flow modifier Parts, 0.2-0.6 parts of a crosslinking agent, 0.2-0.8 parts of a heat stabilizer, and 0.2-0.8 parts of an ultraviolet light absorber.
  • the dynamic vulcanization and flame retardant TPV composite material of the invention is prepared by using a specific amount of polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, flame retardant, flow modifier, crosslinking agent, heat stabilizer and ultraviolet light absorber.
  • the flame retardant is uniformly dispersed in the obtained dynamic vulcanized flame retardant TPV composite material, and the obtained dynamic vulcanized flame retardant TPV composite material has excellent performance.
  • the antibacterial property, and the processing performance is good, and it is easy to process and shape.
  • the dynamically vulcanized flame retardant TPV composite is mainly prepared from the following parts by mass:
  • polypropylene 30-50 parts of EPDM rubber, 8-12 parts of thermoplastic polyurethane elastomer, 20-25 parts of flame retardant, 0.8-1.2 parts of flow modifier, 0.3-0.5 parts of cross-linking agent , heat stabilizer 0.4-0.6 parts and ultraviolet light absorber 0.4-0.6 parts.
  • the dynamically vulcanized flame retardant TPV composite is mainly prepared from the following parts by mass:
  • the thermoplastic polyurethane elastomer has a melt flow rate of 25-55 g/10 min at 200 ° C and a pressure of 2.16 Kg, and a Rockwell hardness of 45-65;
  • the high flow thermoplastic polyurethane elastomer helps to further improve the fluidity of the resulting dynamically vulcanized flame retardant TPV composite and improve its processability.
  • the flame retardant comprises one or more of a halogen-free flame retardant and an inorganic flame retardant, and preferably the halogen-free flame retardant comprises N,N-bis(2- One or more of diethyl hydroxyethyl)aminomethylenephosphonate and ammonium polyphosphate, further preferably a halogen-free flame retardant comprising N,N-bis(2-hydroxyethyl)aminomethylenephosphine Diethyl acid and ammonium polyphosphate.
  • the flame retardant may further include an inorganic flame retardant, and the inorganic flame retardant has a high decomposition temperature, and in addition to the flame retardant effect, the effect of suppressing the generation of smoke and hydrogen chloride, inorganic
  • the flame retardant includes, for example, one or more of aluminum hydroxide and magnesium hydroxide.
  • the mass ratio of the diethyl N,N-bis(2-hydroxyethyl)aminomethylenephosphonate and the ammonium polyphosphate is 1:0.5-2, preferably 1:0.8-1.2, further preferably It is 1:1.
  • thermoplastic polyurethane elastomer and EPDM rubber are swelled to plasticize, and co-crosslinking with EPDM in dynamic vulcanization by adding a specific flame retardant during the extrusion process It can achieve good dispersion in the fully crosslinked rubber dispersed phase, fully improve the antistatic property of the obtained dynamic vulcanized flame retardant TPV composite, and at the same time avoid degradation of the flame retardant.
  • the flow modifier comprises one or more of an internal lubricant, an external lubricant, and a composite lubricant, and preferably the internal lubricant includes a higher aliphatic alcohol, a fatty acid ester. And one or more of the long chain polyfunctional esters, further preferably the long chain polyfunctional ester comprises an AM-80 flow modifier.
  • the external lubricant includes, for example, higher fatty acids, fatty amides, paraffin wax, and the like.
  • the specific flow modifier used has very small volatility, has good dispersibility as a processing aid, and can be used for extrusion, injection molding, calendering, etc. of the polymer, and can improve the processing fluidity of the melt.
  • the melt index is greatly increased without impairing the impact properties of the article.
  • the crosslinking agent comprises one or more of external crosslinking agents
  • the external crosslinking agent includes, for example, polyisocyanate, polyamine, polypropylene glycol glycidyl ether, orthosilicate Ethyl ester, dimethyl propylene Acidic acid glycol ester, di-(tert-butylperoxyisopropyl)benzene (odorless DCP) and triallyl isocyanurate (TAIC), etc.
  • the crosslinking agent preferably comprises two One or more of -(t-butylperoxyisopropyl)benzene (odorless DCP) and triallyl isocyanurate (TAIC), the further crosslinking agent preferably comprising di-(tert-butyl Isopropyl)benzene and triallyl isocyanurate are oxidized.
  • the mass ratio of the di-(tert-butylperoxyisopropyl)benzene and the triallyl isocyanurate is 1:0.5-2, preferably 1:0.8-1.2, further preferably 1 :1.
  • crosslinking agent helps to promote the crosslinking reaction and improve the mechanical properties of the resulting dynamically vulcanized flame retardant TPV composite.
  • the heat stabilizer comprises one or more of antioxidants, preferably the antioxidant comprises 2,6-tert-butyl-4-methylphenol (antioxidant) -264), tetrakis(4-hydroxy-3,5-di-tert-butylphenylpropionic acid) pentaerythritol ester (antioxidant-1010), 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid
  • antioxidants comprises 2,6-tert-butyl-4-methylphenol (antioxidant) -264), tetrakis(4-hydroxy-3,5-di-tert-butylphenylpropionic acid) pentaerythritol ester (antioxidant-1010), 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid
  • an ester antioxidant-1076
  • TPP triphenyl phosphite
  • TNP tridecyl phenyl phosphite
  • the use of a specific heat stabilizer can effectively delay or inhibit the oxidation process of the obtained dynamically vulcanized flame-retardant TPV composite, thereby preventing the aging of the obtained dynamically vulcanized flame-retardant TPV composite and prolonging its service life.
  • the ultraviolet light absorber comprises one of a benzophenone ultraviolet light absorber, a benzotriazole ultraviolet light absorber, and a piperidine ultraviolet light absorber.
  • a benzophenone ultraviolet light absorber preferably one of a benzophenone ultraviolet light absorber, a benzotriazole ultraviolet light absorber, and a piperidine ultraviolet light absorber.
  • a variety preferably including 2-hydroxy-4-methoxybenzophenone (UV-9), 2,2'-dihydroxy-4-methoxybenzophenone (UV-24), 2 (2 -hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole (UV-328) and bis(2,2,6,6-tetramethylpiperidine) sebacic acid
  • One or more of the esters further preferably include 2-hydroxy-4-methoxybenzophenone.
  • Polypropylene is very sensitive to ultraviolet light.
  • the addition of an ultraviolet light absorber can improve the aging resistance of polypropylene.
  • the specific ultraviolet light absorber can effectively absorb the ultraviolet light in the sunlight and the fluorescent light source, prevent the ultraviolet ray from damaging the obtained dynamic vulcanized flame retardant TPV composite material, and improve the stability of the obtained dynamic vulcanized flame retardant TPV composite material under long-time illumination. .
  • a dynamic vulcanized flame-retardant TPV composite material which comprises polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, flame retardant, flow modifier, crosslinking agent, heat stabilizer and ultraviolet
  • the light absorbing agent is thoroughly mixed to obtain a mixture, and the mixture is extruded to obtain a dynamic vulcanized flame retardant TPV composite material.
  • the preparation method of the dynamic vulcanization flame retardant TPV composite material of the invention has the advantages of simple process, convenient operation and high benefit, and is suitable for industrial production.
  • the preparation method of the dynamic vulcanized flame retardant TPV composite material comprises:
  • the ethylene propylene diene monomer, the thermoplastic polyurethane elastomer and the flame retardant are kneaded proportionally, and then polypropylene, a flow modifier, a crosslinking agent, a heat stabilizer and an ultraviolet light absorber are added, and the mixture is sufficiently mixed to obtain a mixture. , extruding the mixture, A dynamic vulcanized flame retardant TPV composite was obtained.
  • the specific feeding mixing sequence is adopted to facilitate further uniform and uniform mixing of the raw materials, and a dynamic vulcanized flame-retardant TPV composite material with uniform properties and uniformity is obtained by extrusion.
  • the crosslinking agent, the polypropylene, the flow modifier, and the heat stabilizer are sequentially added by means of sequential addition. It is sufficiently mixed with the ultraviolet light absorber, wherein the interval time is 1 min or more, preferably 2-5 min, further preferably 3 min; the mixing time is 10 min or more, preferably 20-30 min, and further preferably 25 min.
  • each raw material it is sequentially added in order and in order, wherein the addition of the crosslinking agent enables the pre-mixed raw materials (for example: ethylene propylene diene monomer, thermoplastic polyurethane elastomer and flame retardant) Forming a chemical bond with other materials added later (for example, polypropylene, flow modifier, heat stabilizer, and ultraviolet light absorber), and forming a network structure, which is beneficial to improve the overall strength and elasticity, while heat
  • the stabilizer and the ultraviolet light absorber are added later, and can directly act on the unstable portion of the raw material to enhance the stability of the dynamically vulcanized flame-retardant TPV composite material, and the sequential addition can also ensure the respective raw materials.
  • Mix uniformity for example: ethylene propylene diene monomer, thermoplastic polyurethane elastomer and flame retardant
  • the flame retardant is divided into three parts, the ethylene propylene diene rubber is added to the first flame retardant, and after mixing uniformly, the second flame retardant is added by stirring, and then the thermoplastic polyurethane elastomer is added, and after being uniformly mixed, , the remaining third flame retardant is added again, and the mass ratio of the three flame retardants is 1:1-2:1-2; preferably 1:1:2.
  • the flame retardant is added in three parts and added separately to ensure the mixing uniformity of the flame retardant, the EPDM rubber and the thermoplastic polyurethane elastomer, which is beneficial to improving the dynamic vulcanization flame retardant.
  • the mixing of the ethylene propylene diene monomer, the thermoplastic polyurethane elastomer and the flame retardant is carried out using an internal mixer.
  • the ethylene propylene diene monomer, the thermoplastic polyurethane elastomer and the flame retardant are kneaded by an internal mixer, and after the kneading, the rubber is discharged, cooled for 20-24 hours, and then the polypropylene and the flow modifier are mixed with an internal mixer.
  • the crosslinking agent, the heat stabilizer and the ultraviolet light absorber are mixed, wherein the first internal mixer has a rotation speed of 40-50 r/min, and the second internal mixer has a rotation speed of 10-20 r/min.
  • the long-term cooling of the previously added raw materials ensures the mixing uniformity of the previously added raw materials and is added at a higher rotational speed.
  • the raw materials are mixed and the later added raw materials (for example, polypropylene, flow modifier, crosslinking agent, heat stabilizer and ultraviolet light absorber) are mixed at a lower rotation speed, and the mixing is more uniform.
  • the cooling debinding comprises cooling at a cooling rate of 5-6 ° C / h, after cooling for 6-8 h, cooling at a cooling rate of 1-2 ° C / h for 14-16 h.
  • Cooling the rubber with different cooling rates is beneficial to promote the production of the rubber molecules during the mixing process. Reorientation of the residual stress is beneficial to enhance the uniformity and plasticity of the finally produced dynamically vulcanized flame retardant TPV composite.
  • the kneading temperature is 50-80 ° C, preferably 60-70 ° C, and further preferably 60 ° C.
  • the kneading time is 20 min or more, preferably 20-40 min, and further preferably 30 min.
  • the specific mixing temperature and time are used to promote the uniform mixing of the EPDM rubber, the thermoplastic polyurethane elastomer and the flame retardant, improve the antibacterial property of the obtained dynamic vulcanized flame retardant TPV composite, and improve the processing energy.
  • the extrusion is carried out using a twin screw extruder.
  • the heating zone of the twin-screw extruder is preheated, preheated to a temperature of 50-80 ° C, and then the mixture is fed into a twin-screw extruder to adjust the rotation speed of the twin-screw extruder to be 1- 10r/min, mixed extrusion.
  • Preheating the twin-screw extruder ensures that the temperature of the material discharged through the mixer when entering the twin-screw extruder is not too large, which is beneficial to maintain the structural stability of the material.
  • the temperature of the extrusion is 150 ° C or higher, preferably 175 to 200 ° C, and more preferably 180 ° C.
  • the use of a specific extrusion temperature can promote rapid material formation, ensure the fluidity of the material, reduce the expansion rate of the extrudate, and improve the yield.
  • a preparation method of dynamic vulcanized flame retardant TPV composite material comprising:
  • EPDM rubber thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester, ammonium polyphosphate Mixing at 50 ° C for 60 min in an internal mixer;
  • a preparation method of dynamic vulcanized flame retardant TPV composite material comprising:
  • EPDM rubber thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester, ammonium polyphosphate Mixing at 80 ° C for 20 min in an internal mixer;
  • a preparation method of dynamic vulcanized flame retardant TPV composite material comprising:
  • EPDM rubber thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester, ammonium polyphosphate Mixing at 60 ° C for 20 min in an internal mixer;
  • a preparation method of dynamic vulcanized flame retardant TPV composite material comprising:
  • EPDM rubber thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester, ammonium polyphosphate Mixing at 70 ° C for 40 min in an internal mixer;
  • a preparation method of dynamic vulcanized flame retardant TPV composite material comprising:
  • EPDM rubber thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), N,N-bis(2-hydroxyethyl)aminomethylenephosphonic acid diethyl ester, ammonium polyphosphate Mixing at 60 ° C for 30 min in an internal mixer;
  • a preparation method of dynamic vulcanized flame retardant TPV composite material comprising:
  • Body (TPU, commercially available grade 87I85), after mixing evenly, add a third flame retardant again, mix in a mixer at 40r/min for 60min at 60°C, then drain the glue to 5°C
  • the cooling rate of /h was cooled, and after cooling for 6 hours, it was cooled at a cooling rate of 2 ° C / h for 14 h.
  • the mixture was fed into a twin-screw extruder, and the speed of the twin-screw extruder was adjusted to 1 r/min, and the mixture was extruded.
  • the screw processing extrusion temperature of the twin-screw extruder was 180 ° C, and a dynamic vulcanized flame retardant TPV composite material was obtained.
  • a preparation method of dynamic vulcanized flame retardant TPV composite material comprising:
  • Machine blending extrusion preheating the heating zone of the twin-screw extruder, preheating to a temperature of 80 ° C, then feeding the mixture into a twin-screw extruder, adjusting the speed of the twin-screw extruder to 10 r /min, mixed extrusion.
  • the screw processing extrusion temperature of the twin-screw extruder was 180 ° C, and a dynamic vulcanized flame retardant TPV composite material was obtained.
  • a preparation method of dynamic vulcanized flame retardant TPV composite material comprising:
  • the heating zone of the twin-screw extruder is preheated, preheated to a temperature of 70 ° C, and then the mixture is fed into a twin-screw extruder to adjust the rotation speed of the twin-screw extruder to 5 r / min, and the mixture is extruded. .
  • the screw processing extrusion temperature of the twin-screw extruder was 180 ° C, and a dynamic vulcanized flame retardant TPV composite material was obtained.
  • the performance test of the dynamic vulcanized flame-retardant TPV composite obtained in Examples 1-5 of the present invention was carried out, and the obtained dynamic vulcanized flame-retardant TPV composite materials were respectively subjected to corresponding standards (tensile strength GB/T1040.2-2006/1A/50, cantilever
  • the beam notched impact strength GB/T1843-2008/A, the limiting oxygen index GB/T2406.1-2008, the burning grade GB/T 2408-2008) were prepared into standard test splines, and the comparative examples 1-5 were respectively implemented by the present invention.
  • Test Example 1 Ethylene propylene diene monomer, thermoplastic polyurethane elastomer and flame retardant were mixed in the manner provided in Example 6 to obtain a mixture 1, and the mixture 1 was subjected to subsequent operations to prepare a dynamically vulcanized flame-retardant TPV composite material 1.
  • Comparative Example 6 was substantially the same as Example 6, except that ethylene propylene diene monomer, a thermoplastic polyurethane elastomer and a flame retardant were added together and mixed to obtain a mixture 2, and the mixture 2 was subsequently subjected to Operation to prepare a dynamically vulcanized flame retardant TPV composite 2 .
  • the mixing uniformity of the mixture 1 and the mixture 2 was tested.
  • the detection method of the mixing uniformity was as follows: X and Y were respectively sampled from the mixture 1 and the mixture 2, and the number of samples was 5, respectively, and the content of the flame retardant in the sample was measured, respectively. The average value and the mean square error were calculated, and the experimental results are shown in Table 2.
  • the dynamic vulcanization and flame retardant TPV composite material of the invention is prepared by using a specific amount of polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, flame retardant, flow modifier, crosslinking agent, heat stabilizer and ultraviolet light absorber.
  • the flame retardant is uniformly dispersed in the obtained dynamic vulcanized flame-retardant TPV composite material, and the obtained dynamic vulcanized flame-retardant TPV composite material has excellent antibacterial property, good processing property and easy processing and molding.
  • the preparation method of the dynamic vulcanization flame retardant TPV composite material of the invention has the advantages of simple process, convenient operation and high benefit, and is suitable for industrial production.

Abstract

一种动态硫化阻燃TPV复合材料及其制备方法和应用，该动态硫化阻燃TPV复合材料采用特定用量的聚丙烯、三元乙丙橡胶、热塑性聚氨酯弹性体、阻燃剂、流动改性剂、交联剂、热稳定剂和紫外光吸收剂制备得到，阻燃剂在所得动态硫化阻燃TPV复合材料中分散均匀，所得动态硫化阻燃TPV复合材料具有优异的阻燃性能，且加工性能好，易于加工成型。该动态硫化阻燃TPV复合材料的制备方法工艺简单，操作方便，效益高，适合于进行工业化生产。

Description

一种动态硫化阻燃TPV复合材料及其制备方法
相关申请的交叉引用
本申请要求于2017年04月20日提交中国专利局的申请号为2017102618337、名称为“一种动态硫化阻燃TPV复合材料及其制备方法”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
本发明涉及材料科学技术领域，具体而言，涉及一种动态硫化阻燃TPV复合材料及其制备方法。
背景技术
TPV是Thermoplastic Vulcanizate的简称，中文名称为热塑性三元乙丙动态硫化弹性体或热塑性三元乙丙动态硫化橡胶，是高度硫化的三元乙丙橡胶EPDM微粒分散在连续聚丙烯PP相中组成的高分子弹性体材料。TPV常温下的物理性能和功能类似于热固性橡胶，在高温下表现为热塑性塑料的特性，可以快速经济和方便地加工成型。在汽车、电线电缆、室内装修和绝缘材料等领域得到广泛应用。但是其致命的缺点是容易燃烧，氧指数仅有17.5％，限制了该材料的应用领域，因此提高其阻燃性能有很大的必要性。随着环保意识的不断增强，阻燃剂的研究越来越受到人们的关注，其中膨胀型阻燃剂是阻燃剂重要的一类。EPDM/PP体系由于两者的热分解温度相差太大，PP的热分解温度为328-410℃，而EPDM的热分解温度为507-900℃，因此很难选择到与二者同时匹配的阻燃剂，且其特殊的结构特点，阻燃剂很难进入到完全交联的橡胶分散相；由于在挤出过程中EPDM发生动态交联，粘度增加，螺杆剪切产生大量热量会使得一部分的阻燃剂分解，给阻燃带来难度，这是国内外至今仍未对其进行较好阻燃的主要原因。
相关技术中，动态硫化TPV材料阻燃性能差，并且加工性能差，成型加工困难，影响材料性能。
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种动态硫化阻燃TPV复合材料，所述的动态硫化阻燃TPV复合材料中阻燃剂分散均匀，阻燃性能优异，加工性能好，易于加工成型。
本发明的第二目的在于提供一种所述的动态硫化阻燃TPV复合材料的制备方法，该方法工艺简单，操作方便，效益高，适合于进行工业化生产。
为了实现本发明的上述目的，特采用以下技术方案：
一种动态硫化阻燃TPV复合材料，所述动态硫化阻燃TPV复合材料主要由以下质量份数的成分制备得到：
聚丙烯20-50份、三元乙丙橡胶20-60份、热塑性聚氨酯弹性体5-15份、阻燃剂15-30份、流动改性剂0.5-1.5份、交联剂0.2-0.6份、热稳定剂0.2-0.8份和紫外光吸收剂0.2-0.8份。
本发明动态硫化阻燃TPV复合材料采用特定用量的聚丙烯、三元乙丙橡胶、热塑性聚氨酯弹性体、阻燃剂、流动改性剂、交联剂、热稳定剂和紫外光吸收剂制备得到，阻燃剂在所得动态硫化阻燃TPV复合材料中分散均匀，所得动态硫化阻燃TPV复合材料具有优异的抗菌性能，且加工性能好，易于加工成型。
优选地，所述动态硫化阻燃TPV复合材料主要由以下质量份数的成分制备得到：
聚丙烯30-40份、三元乙丙橡胶30-50份、热塑性聚氨酯弹性体8-12份、阻燃剂20-25份、流动改性剂0.8-1.2份、交联剂0.3-0.5份、热稳定剂0.4-0.6份和紫外光吸收剂0.4-0.6份。
进一步优选地，所述动态硫化阻燃TPV复合材料主要由以下质量份数的成分制备得到：
聚丙烯35份、三元乙丙橡胶40份、热塑性聚氨酯弹性体10份、阻燃剂22份、流动改性剂1份、交联剂0.4份、热稳定剂0.5份和紫外光吸收剂0.5份。
可选地，所述热塑性聚氨酯弹性体在200℃，压力2.16Kg条件下的熔融流动速率为25-55g/10min，且洛氏硬度为45-65。
可选地，所述阻燃剂包括无卤阻燃剂和无机阻燃剂中的一种或多种，优选无卤阻燃剂包括N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和聚磷酸铵中的一种或多种，进一步优选无卤阻燃剂包括N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和聚磷酸铵。
优选地，所述N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和聚磷酸铵的质量比为1：0.5-2，优选为1：0.8-1.2，进一步优选为1：1。
可选地，所述流动改性剂包括内润滑剂、外润滑剂以及复合型润滑剂中的一种或多种，优选地，内润滑剂包括高级脂肪醇、脂肪酸酯和长链多官能团酯中的一种或多种，进一步优选长链多官能团酯包括AM-80流动改性剂。
可选地，所述交联剂包括外交联剂中的一种或多种，优选包括二-(叔丁基过氧化异丙基)苯和三烯丙基异氰脲酸酯、二丙烯酸-1,4-丁二醇酯、过氧化二异丙苯中的一种或多 种，进一步优选包括二-(叔丁基过氧化异丙基)苯和三烯丙基异氰脲酸酯。
优选地，所述二-(叔丁基过氧化异丙基)苯和三烯丙基异氰脲酸酯的质量比为1：0.5-2，优选为1：0.8-1.2，进一步优选为1：1。
可选地，所述热稳定剂包括抗氧剂中的一种或多种，优选包括2,6-叔丁基-4-甲基苯酚、四(4-羟基-3,5-二叔丁基苯基丙酸)季戊四醇酯、3,5-二叔丁基-4-羟基苯丙酸十八酯、亚磷酸三苯酯和亚磷酸三壬基苯酯中的一种或多种，进一步优选包括2,6-叔丁基-4-甲基苯酚。
可选地，所述紫外光吸收剂包括二苯甲酮类紫外光吸收剂、苯并三唑类紫外光吸收剂和哌啶类紫外光吸收剂中的一种或多种，优选包括2-羟基-4-甲氧基二苯甲酮、2,2’-二羟基-4-甲氧基二苯甲酮、2(2-羟基-3’,5’-二叔丁基苯基)-5-氯代苯并三唑和双(2,2,6,6-四甲基哌啶)癸二酸酯中的一种或多种，进一步优选包括2-羟基-4-甲氧基二苯甲酮。
上述的一种动态硫化阻燃TPV复合材料的制备方法，按比例将聚丙烯、三元乙丙橡胶、热塑性聚氨酯弹性体、阻燃剂、流动改性剂、交联剂、热稳定剂和紫外光吸收剂充分混合后挤出，得到一种动态硫化阻燃TPV复合材料。
本发明动态硫化阻燃TPV复合材料的制备方法工艺简单，操作方便，效益高，适合于进行工业化生产。
优选地，所述一种动态硫化阻燃TPV复合材料的制备方法包括：
按比例将三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂进行混炼，之后加入聚丙烯、流动改性剂、交联剂、热稳定剂和紫外光吸收剂，充分混合后挤出，得到一种动态硫化阻燃TPV复合材料。
优选地，在按比例将三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂进行混炼之后，依次间隔加入交联剂、聚丙烯、流动改性剂、热稳定剂和紫外光吸收剂，充分混合，其中，间隔时间为1min以上，优选为2-5min，进一步优选为3min；混合时间为10min以上，优选为20-30min，进一步优选为25min。
按比例并按顺序依次加入，确保了各个原料的混合均匀度，制得的动态硫化阻燃TPV复合材料的均匀性佳，加工性能好，易于加工成型。
优选地，将阻燃剂分为三份，向第一份阻燃剂中加入三元乙丙橡胶，混合均匀后，搅拌加入第二份阻燃剂，接着加入热塑性聚氨酯弹性体，混合均匀后，再次加入剩余的第三份阻燃剂，三份阻燃剂的质量比为1:1-2:1-2；优选为1:1:2。
优选地，将三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂采用密炼机进行混炼，混炼后排胶，冷却20-24h，再以密炼机对聚丙烯、流动改性剂、交联剂、热稳定剂和紫外光吸收剂进行混合，其中，第一密炼机的转速为40-50r/min，第二密炼机的转速为 10-20r/min。
优选地，冷却排胶包括以5-6℃/h的冷却速度进行冷却，冷却6-8h后，以1-2℃/h的冷却速度冷却14-16h。
可选地，所述混炼的温度为50-80℃，优选为60-70℃，进一步优选为60℃。
可选地，所述混炼的时间为20min以上，优选为20-40min，进一步优选为30min。
优选地，挤出混合料包括：先将双螺杆挤出机的加热区进行预热，预热至温度为50-80℃，然后将混合料喂入双螺杆挤出机，调节双螺杆挤出机的转速为1-10r/min，混合挤出。
可选地，所述挤出的温度为150℃以上，优选为175-200℃，进一步优选为180℃。
与现有技术相比，本发明的有益效果例如包括：
本发明动态硫化阻燃TPV复合材料采用特定用量的聚丙烯、三元乙丙橡胶、热塑性聚氨酯弹性体、阻燃剂、流动改性剂、交联剂、热稳定剂和紫外光吸收剂制备得到，阻燃剂在所得动态硫化阻燃TPV复合材料中分散均匀，所得动态硫化阻燃TPV复合材料具有优异的抗菌性能，且加工性能好，易于加工成型。本发明动态硫化阻燃TPV复合材料的制备方法工艺简单，操作方便，效益高，适合于进行工业化生产。
具体实施方式
下面将结合具体实施方式对本发明的技术方案进行清楚、完整地描述，但是本领域技术人员将会理解，下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
本发明提供了一种动态硫化阻燃TPV复合材料，所述动态硫化阻燃TPV复合材料主要由以下质量份数的成分制备得到：
聚丙烯(PP)20-50份、三元乙丙橡胶(EPDM)20-60份、热塑性聚氨酯弹性体(TPU)5-15份、阻燃剂15-30份、流动改性剂0.5-1.5份、交联剂0.2-0.6份、热稳定剂0.2-0.8份和紫外光吸收剂0.2-0.8份。
本发明动态硫化阻燃TPV复合材料采用特定用量的聚丙烯、三元乙丙橡胶、热塑性聚氨酯弹性体、阻燃剂、流动改性剂、交联剂、热稳定剂和紫外光吸收剂制备得到，阻燃剂在所得动态硫化阻燃TPV复合材料中分散均匀，所得动态硫化阻燃TPV复合材料具有优异 的抗菌性能，且加工性能好，易于加工成型。优选地，所述动态硫化阻燃TPV复合材料主要由以下质量份数的成分制备得到：
聚丙烯30-40份、三元乙丙橡胶30-50份、热塑性聚氨酯弹性体8-12份、阻燃剂20-25份、流动改性剂0.8-1.2份、交联剂0.3-0.5份、热稳定剂0.4-0.6份和紫外光吸收剂0.4-0.6份。
进一步优选地，所述动态硫化阻燃TPV复合材料主要由以下质量份数的成分制备得到：
聚丙烯35份、三元乙丙橡胶40份、热塑性聚氨酯弹性体10份、阻燃剂22份、流动改性剂1份、交联剂0.4份、热稳定剂0.5份和紫外光吸收剂0.5份。
本发明一种优选的具体实施方式中，所述热塑性聚氨酯弹性体在200℃，压力2.16Kg条件下的熔融流动速率为25-55g/10min，且洛氏硬度为45-65；采用这种具有高流动性的热塑性聚氨酯弹性体，有助于进一步改善所得动态硫化阻燃TPV复合材料的流动性，改善其加工性能。本发明一种优选的具体实施方式中，所述阻燃剂包括无卤阻燃剂和无机阻燃剂中的一种或多种，优选无卤阻燃剂包括N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和聚磷酸铵中的一种或多种，进一步优选无卤阻燃剂包括N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和聚磷酸铵。应理解，在本发明的其他实施例中，阻燃剂还可以包括无机阻燃剂，无机阻燃剂分解温度高，除了有阻燃效果外，还有抑制发烟和氯化氢生成的作用，无机阻燃剂例如包括氢氧化铝和氢氧化镁中的一种或多种。
优选地，所述N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和聚磷酸铵的质量比为1：0.5-2，优选为1：0.8-1.2，进一步优选为1：1。
采用特定阻燃剂，使得热塑性聚氨酯弹性体和三元乙丙橡胶产生溶胀起增塑作用，并通过加入特定阻燃剂在动态硫化中与三元乙丙橡胶实现共交联，在挤出过程中可以在完全交联的橡胶分散相实现良好分散，充分提高所得动态硫化阻燃TPV复合材料的抗静电性能，同时能够避免阻燃剂发生降解。
本发明一种优选的具体实施方式中，所述流动改性剂包括内润滑剂、外润滑剂以及复合型润滑剂中的一种或多种，优选内润滑剂包括高级脂肪醇、脂肪酸酯和长链多官能团酯中的一种或多种，进一步优选长链多官能团酯包括AM-80流动改性剂。应理解，外润滑剂例如包括高级脂肪酸、脂肪酰胺、石蜡等。
所采用的特定流动改性剂，具有非常小的挥发性，作为加工助剂，具有良好的分散性，能够用于聚合物的挤出，注塑，压延等，可以提高熔体的加工流动性，大幅度提高熔融指数，且不降低制品的冲击性能。
本发明一种优选的具体实施方式中，所述交联剂包括外交联剂中的一种或多种，外交联剂例如包括：多异氰酸酯、多元胺类、聚丙二醇缩水甘油醚、正硅酸乙酯、二甲基丙烯 酸乙二醇酯、二-(叔丁基过氧化异丙基)苯(无味DCP)和三烯丙基异氰脲酸酯(TAIC)等等，本实施例中，交联剂优选包括二-(叔丁基过氧化异丙基)苯(无味DCP)和三烯丙基异氰脲酸酯(TAIC)中的一种或多种，进一步交联剂优选包括二-(叔丁基过氧化异丙基)苯和三烯丙基异氰脲酸酯。
优选地，所述二-(叔丁基过氧化异丙基)苯和三烯丙基异氰脲酸酯的质量比为1：0.5-2，优选为1：0.8-1.2，进一步优选为1：1。
采用特定的交联剂，有助于促进交联反应的进行，提高所得动态硫化阻燃TPV复合材料的机械性能。
本发明一种优选的具体实施方式中，所述热稳定剂包括抗氧剂中的一种或多种，优选抗氧剂包括2,6-叔丁基-4-甲基苯酚(抗氧剂-264)、四(4-羟基-3，5-二叔丁基苯基丙酸)季戊四醇酯(抗氧剂-1010)、3，5-二叔丁基-4-羟基苯丙酸十八酯(抗氧剂-1076)、亚磷酸三苯酯(TPP)和亚磷酸三壬基苯酯(TNP)中的一种或多种，进一步优选包括2,6-叔丁基-4-甲基苯酚。
采用特定热稳定剂，能够有效延缓或抑制所得动态硫化阻燃TPV复合材料的氧化过程的进行，从而阻止所得动态硫化阻燃TPV复合材料的老化并延长其使用寿命。
本发明一种优选的具体实施方式中，所述紫外光吸收剂包括二苯甲酮类紫外光吸收剂、苯并三唑类紫外光吸收剂和哌啶类紫外光吸收剂中的一种或多种，优选包括2-羟基-4-甲氧基二苯甲酮(UV-9)、2,2’-二羟基-4-甲氧基二苯甲酮(UV-24)、2(2-羟基-3’,5’-二叔丁基苯基)-5-氯代苯并三唑(UV-328)和双(2,2,6,6-四甲基哌啶)癸二酸酯中的一种或多种，进一步优选包括2-羟基-4-甲氧基二苯甲酮。
聚丙烯对紫外线很敏感，在本实施例中，紫外光吸收剂的加入能够改善聚丙烯的耐老化性能。采用特定紫外光吸收剂，能够有效吸收阳光及荧光光源中的紫外线部分，防止紫外线对所得动态硫化阻燃TPV复合材料产生破坏，提高所得动态硫化阻燃TPV复合材料在长时间光照下的稳定性。
上述的一种动态硫化阻燃TPV复合材料的制备方法，按比例将聚丙烯、三元乙丙橡胶、热塑性聚氨酯弹性体、阻燃剂、流动改性剂、交联剂、热稳定剂和紫外光吸收剂充分混合后得到混合料，挤出混合料，得到一种动态硫化阻燃TPV复合材料。
本发明动态硫化阻燃TPV复合材料的制备方法工艺简单，操作方便，效益高，适合于进行工业化生产。
优选地，所述一种动态硫化阻燃TPV复合材料的制备方法包括：
按比例将三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂进行混炼，之后加入聚丙烯、流动改性剂、交联剂、热稳定剂和紫外光吸收剂，充分混合后得到混合料，挤出混合料， 得到一种动态硫化阻燃TPV复合材料。
采用特定加料混合顺序，有助于各原料进一步充分均匀混合，通过挤出得到性质均匀稳定的动态硫化阻燃TPV复合材料。
进一步地，在按比例将三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂进行混炼之后，采用依次间隔加入的方式，依次加入交联剂、聚丙烯、流动改性剂、热稳定剂和紫外光吸收剂，充分混合，其中，间隔时间为1min以上，优选为2-5min，进一步优选为3min；混合时间为10min以上，优选为20-30min，进一步优选为25min。
本实施例中，依据各个原料的性质，按比例并按顺序依次加入，其中交联剂的加入能够使预先混炼原料(例如：三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂)能够与在后加入的其他原料(例如：聚丙烯、流动改性剂、热稳定剂和紫外光吸收剂)之间形成化学键，并形成网状结构，这样有利于提升整体的强度和弹性，而热稳定剂和紫外光吸收剂的在后加入，能够直接作用于原料中的不稳定部位，加强制得的动态硫化阻燃TPV复合材料的稳定性，同时按顺序依次加入还能够确保了各个原料的混合均匀度。
优选地，将阻燃剂分为三份，向第一份阻燃剂中加入三元乙丙橡胶，混合均匀后，搅拌加入第二份阻燃剂，接着加入热塑性聚氨酯弹性体，混合均匀后，再次加入剩余的第三份阻燃剂，三份阻燃剂的质量比为1:1-2:1-2；优选为1:1:2。
本实施例中，采用将阻燃剂分为三份依次加入分别加入，确保了阻燃剂、三元乙丙橡胶以及热塑性聚氨酯弹性体的混合均匀度，有利于提升制得的动态硫化阻燃TPV复合材料的品质。
可选地，所述将三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂进行混炼采用密炼机完成。
优选地，将三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂采用密炼机进行混炼，混炼后排胶，冷却20-24h，再以密炼机对聚丙烯、流动改性剂、交联剂、热稳定剂和紫外光吸收剂进行混合，其中，第一密炼机的转速为40-50r/min，第二密炼机的转速为10-20r/min。
在先加入的原料(例如：三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂)进行长时间的冷却，能够保证在先加入的原料的混合均一性，并且以较高转速对在先加入的原料进行混合，以较低的转速对在后加入的原料(例如：聚丙烯、流动改性剂、交联剂、热稳定剂和紫外光吸收剂)进行混合，混合更均匀。
优选地，冷却排胶包括以5-6℃/h的冷却速度进行冷却，冷却6-8h后，以1-2℃/h的冷却速度冷却14-16h。
采用不同的冷却速度对排胶进行冷却，有利于促使排胶分子在混炼过程中产生的 剩余应力进行重新定向，有利于增强最终制得的动态硫化阻燃TPV复合材料的均匀性和可塑性。
本发明一种优选的具体实施方式中，所述混炼的温度为50-80℃，优选为60-70℃，进一步优选为60℃。
本发明一种优选的具体实施方式中，所述混炼的时间为20min以上，优选为20-40min，进一步优选为30min。
采用特定混炼温度和时间，有助于三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂充分混合均匀，提高所得动态硫化阻燃TPV复合材料的抗菌性能，并改善其加工新能。
可选地，所述挤出采用双螺杆挤出机进行。
具体地，先将双螺杆挤出机的加热区进行预热，预热至温度为50-80℃，然后将混合料喂入双螺杆挤出机，调节双螺杆挤出机的转速为1-10r/min，混合挤出。
对双螺杆挤出机进行预热，能够保证经密炼机排出的物料在进入双螺旋挤出机时，温差不会太大，有利于保持物料的结构稳定性。
本发明一种优选的具体实施方式中，所述挤出的温度为150℃以上，优选为175-200℃，进一步优选为180℃。
采用特定挤出温度，能够促进物料快速成型，保证物料的流动性，减少挤出物膨胀率，提高产率。
实施例1
一种动态硫化阻燃TPV复合材料的制备方法，包括：
(1)分别称量聚丙烯(T30S)20kg、三元乙丙橡胶20kg、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)5kg、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯10kg、聚磷酸铵5kg、AM-80流动改性剂0.5kg、二-(叔丁基过氧化异丙基)苯(无味DCP)0.133kg、三烯丙基异氰脲酸酯(TAIC)0.067kg、亚磷酸三壬基苯酯(TNP)0.2kg和2-羟基-4-甲氧基二苯甲酮(UV-9)0.2kg；
(2)将三元乙丙橡胶、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、聚磷酸铵在密炼机中，在50℃下混炼60min；
(3)再加入聚丙烯(T30S)、AM-80流动改性剂、二-(叔丁基过氧化异丙基)苯(无味DCP)、三烯丙基异氰脲酸酯(TAIC)、亚磷酸三壬基苯酯(TNP)和2-羟基-4-甲氧基二苯甲酮(UV-9)，充分混合后，采用双螺杆挤出机共混挤出，双螺杆挤出机的螺杆加工挤出温度为150℃，得到一种动态硫化阻燃TPV复合材料。
实施例2
一种动态硫化阻燃TPV复合材料的制备方法，包括：
(1)分别称量聚丙烯(T30S)50kg、三元乙丙橡胶60kg、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)15kg、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯10kg、聚磷酸铵20kg、AM-80流动改性剂1.5kg、二-(叔丁基过氧化异丙基)苯(无味DCP)0.2kg、三烯丙基异氰脲酸酯(TAIC)0.4kg、四(4-羟基-3，5-二叔丁基苯基丙酸)季戊四醇酯(抗氧剂-1010)0.8kg和2,2’-二羟基-4-甲氧基二苯甲酮(UV-24)0.8kg；
(2)将三元乙丙橡胶、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、聚磷酸铵在密炼机中，在80℃下混炼20min；
(3)再加入聚丙烯(T30S)、AM-80流动改性剂、二-(叔丁基过氧化异丙基)苯(无味DCP)、三烯丙基异氰脲酸酯(TAIC)、四(4-羟基-3，5-二叔丁基苯基丙酸)季戊四醇酯(抗氧剂-1010)和2,2’-二羟基-4-甲氧基二苯甲酮(UV-24)，充分混合后，采用双螺杆挤出机共混挤出，双螺杆挤出机的螺杆加工挤出温度为175℃，得到一种动态硫化阻燃TPV复合材料。
实施例3
一种动态硫化阻燃TPV复合材料的制备方法，包括：
(1)分别称量聚丙烯(T30S)30kg、三元乙丙橡胶30kg、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)8kg、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯11.11kg、聚磷酸铵8.89kg、AM-80流动改性剂0.8kg、二-(叔丁基过氧化异丙基)苯(无味DCP)0.167kg、三烯丙基异氰脲酸酯(TAIC)0.133kg、3,5-二叔丁基-4-羟基苯丙酸十八酯(抗氧剂-1076)0.4kg和2(2-羟基-3’,5’-二叔丁基苯基)-5-氯代苯并三唑(UV-328)0.4kg；
(2)将三元乙丙橡胶、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、聚磷酸铵在密炼机中，在60℃下混炼20min；
(3)再加入聚丙烯(T30S)、AM-80流动改性剂、二-(叔丁基过氧化异丙基)苯(无味DCP)、三烯丙基异氰脲酸酯(TAIC)、3，5-二叔丁基-4-羟基苯丙酸十八酯(抗氧剂-1076)和2(2-羟基-3’，5’-二叔丁基苯基)-5-氯代苯并三唑(UV-328)，充分混合后，采用双螺杆挤出机共混挤出，所述双螺杆挤出机的螺杆加工挤出温度为200℃，得到一种动态硫化阻燃TPV复合材料。
实施例4
一种动态硫化阻燃TPV复合材料的制备方法，包括：
(1)分别称量聚丙烯(T30S)40kg、三元乙丙橡胶50kg、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)12kg、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯11.36kg、聚磷酸铵13.64kg、AM-80流动改性剂1.2kg、二-(叔丁基过氧化异丙基)苯(无味DCP)0.227kg、三烯丙基异氰脲酸酯(TAIC)0.273kg、亚磷酸三苯酯(TPP)0.6kg和双(2,2,6,6-四甲基哌啶)癸二酸酯0.6kg；
(2)将三元乙丙橡胶、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、聚磷酸铵在密炼机中，在70℃下混炼40min；
(3)再加入聚丙烯(T30S)、AM-80流动改性剂、二-(叔丁基过氧化异丙基)苯(无味DCP)、三烯丙基异氰脲酸酯(TAIC)、亚磷酸三苯酯(TPP)和双(2,2,6,6-四甲基哌啶)癸二酸酯，充分混合后，采用双螺杆挤出机共混挤出，双螺杆挤出机的螺杆加工挤出温度为190℃，得到一种动态硫化阻燃TPV复合材料。
实施例5
一种动态硫化阻燃TPV复合材料的制备方法，包括：
(1)分别称量聚丙烯(T30S)35kg、三元乙丙橡胶40kg、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)10kg、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯11kg、聚磷酸铵11kg、AM-80流动改性剂1kg、二-(叔丁基过氧化异丙基)苯(无味DCP)0.2kg、三烯丙基异氰脲酸酯(TAIC)0.2kg、2,6-叔丁基-4-甲基苯酚(抗氧剂-264)0.5kg和2-羟基-4-甲氧基二苯甲酮(UV-9)0.5kg；
(2)将三元乙丙橡胶、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯、聚磷酸铵在密炼机中，在60℃下混炼30min；
(3)再加入聚丙烯(T30S)、AM-80流动改性剂、二-(叔丁基过氧化异丙基)苯(无味DCP)、三烯丙基异氰脲酸酯(TAIC)、2,6-叔丁基-4-甲基苯酚(抗氧剂-264)和2-羟基-4-甲氧基二苯甲酮(UV-9)，充分混合后，采用双螺杆挤出机共混挤出，双螺杆挤出机的螺杆加工挤出温度为180℃，得到一种动态硫化阻燃TPV复合材料。
实施例6
一种动态硫化阻燃TPV复合材料的制备方法，包括：
(1)分别称量聚丙烯(T30S)32kg、三元乙丙橡胶42kg、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)12kg、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯10kg、聚磷酸铵11kg、AM-80流动改性剂1.2kg、二-(叔丁基过氧化异丙基)苯(无味DCP)0.2kg、三烯丙基异氰脲酸酯(TAIC)0.2kg、2,6-叔丁基-4-甲基苯酚(抗氧剂-264)0.4kg和2-羟 基-4-甲氧基二苯甲酮(UV-9)0.4kg；
(2)将N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和聚磷酸铵共同作为阻燃剂，将该阻燃剂分为三份，三份阻燃剂的质量比为1:1:2，将第一份阻燃剂加入密炼机中，开启搅拌，加入三元乙丙橡胶，混合均匀后，加入第二份阻燃剂，接着加入热塑性聚氨酯弹性体(TPU，市售牌号为87I85)，混合均匀后，再次加入第三份阻燃剂，在密炼机中以40r/min的转速于60℃下混炼30min，接着排胶，以5℃/h的冷却速度进行冷却，冷却6h后，以2℃/h的冷却速度冷却14h。
(3)再依次间隔加入作为交联剂的二-(叔丁基过氧化异丙基)苯(无味DCP)和三烯丙基异氰脲酸酯(TAIC)，每间隔3min依次加入聚丙烯(T30S)、AM-80流动改性剂、2,6-叔丁基-4-甲基苯酚(抗氧剂-264)和2-羟基-4-甲氧基二苯甲酮(UV-9)，密炼机以10r/min的转速对上述原料充分混合25min后，采用双螺杆挤出机共混挤出，先对双螺杆挤出机的加热区进行预热，预热至温度为50℃，然后将混合料喂入双螺杆挤出机，调节双螺杆挤出机的转速为1r/min，混合挤出。双螺杆挤出机的螺杆加工挤出温度为180℃，得到一种动态硫化阻燃TPV复合材料。
实施例7
一种动态硫化阻燃TPV复合材料的制备方法，包括：
(1)分别称量聚丙烯(T30S)32kg、三元乙丙橡胶45kg、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)10kg、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯15kg、
脂肪酸酯1kg、二丙烯酸-1，4-丁二醇酯0.2kg、过氧化二异丙苯0.2kg、3,5-二叔丁基-4-羟基苯丙酸十八酯0.2kg、亚磷酸三苯酯0.3kg、2(2-羟基-3’,5’-二叔丁基苯基)-5-氯代苯并三唑0.2kg和双(2,2,6,6-四甲基哌啶)癸二酸酯0.2kg；
(2)将N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯作为阻燃剂，将该阻燃剂分为三份，三份阻燃剂的质量比为1:1:1，将第一份阻燃剂加入密炼机中，开启搅拌，加入三元乙丙橡胶，混合均匀后，加入第二份阻燃剂，接着加入热塑性聚氨酯弹性体(TPU，市售牌号为87I85)，混合均匀后，再次加入第三份阻燃剂，在密炼机中以50r/min的转速于60℃下混炼30min，接着排胶，以6℃/h的冷却速度进行冷却，冷却8h后，以1℃/h的冷却速度冷却16h。
(3)先加入作为交联剂的二丙烯酸-1，4-丁二醇酯和过氧化二异丙苯，每间隔3min依次加入聚丙烯(T30S)、脂肪酸酯、3,5-二叔丁基-4-羟基苯丙酸十八酯、亚磷酸三苯酯、2(2-羟基-3’,5’-二叔丁基苯基)-5-氯代苯并三唑和双(2,2,6,6-四甲基哌啶)癸二酸酯，密炼机以20r/min的转速对上述原料充分混合25min后，采用双螺杆挤出 机共混挤出，先对双螺杆挤出机的加热区进行预热，预热至温度为80℃，然后将混合料喂入双螺杆挤出机，调节双螺杆挤出机的转速为10r/min，混合挤出。双螺杆挤出机的螺杆加工挤出温度为180℃，得到一种动态硫化阻燃TPV复合材料。
实施例8
一种动态硫化阻燃TPV复合材料的制备方法，包括：
(1)分别称量聚丙烯(T30S)38kg、三元乙丙橡胶60kg、热塑性聚氨酯弹性体(TPU，市售牌号为87I85)15kg、N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯20kg、脂肪酸酯1kg、二丙烯酸-1,4-丁二醇酯0.2kg、三烯丙基异氰脲酸酯0.2kg、3,5-二叔丁基-4-羟基苯丙酸十八酯0.2kg、亚磷酸三苯酯0.3kg、2(2-羟基-3’,5’-二叔丁基苯基)-5-氯代苯并三唑0.3kg和双(2,2,6,6-四甲基哌啶)癸二酸酯0.1kg；
(2)将N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯作为阻燃剂，将该阻燃剂分为三份，三份阻燃剂的质量比为1:2:2，将第一份阻燃剂加入密炼机中，开启搅拌，加入三元乙丙橡胶，混合均匀后，加入第二份阻燃剂，接着加入热塑性聚氨酯弹性体(TPU，市售牌号为87I85)，混合均匀后，再次加入第三份阻燃剂，在密炼机中以45r/min的转速于60℃下混炼30min，接着排胶，以5℃/h的冷却速度进行冷却，冷却7h后，以1℃/h的冷却速度冷却15h。
(3)先加入作为交联剂的二丙烯酸-1,4-丁二醇酯和三烯丙基异氰脲酸酯，每间隔3min依次加入聚丙烯(T30S)、脂肪酸酯、3,5-二叔丁基-4-羟基苯丙酸十八酯、亚磷酸三苯酯、2(2-羟基-3’,5’-二叔丁基苯基)-5-氯代苯并三唑和双(2,2,6,6-四甲基哌啶)癸二酸酯，密炼机以15r/min的转速对上述原料充分混合25min后，采用双螺杆挤出机共混挤出，先对双螺杆挤出机的加热区进行预热，预热至温度为70℃，然后将混合料喂入双螺杆挤出机，调节双螺杆挤出机的转速为5r/min，混合挤出。双螺杆挤出机的螺杆加工挤出温度为180℃，得到一种动态硫化阻燃TPV复合材料。
对比实验
一、动态硫化阻燃TPV复合材料性能测试
对本发明实施例1-5所得的动态硫化阻燃TPV复合材料进行性能测试，将所得动态硫化阻燃TPV复合材料分别按照对应标准(拉伸强度GB/T1040.2-2006/1A/50、悬臂梁缺口冲击强度GB/T1843-2008/A、极限氧指数GB/T2406.1-2008、燃烧等级GB/T 2408-2008)制备成标准测试样条，对比例1-5依次分别采用本发明实施例1-5所述方法，但不使用N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯或聚磷酸铵等任何阻燃剂，进行以下各项测试，其性 能结果如表1所示：
表1本发明动态硫化阻燃TPV复合材料性能测试结果
Figure PCTCN2017101939-appb-000001
通过表1可以看出，本发明使用了阻燃剂后，拉伸强度能够达到不使用阻燃剂的水平，悬臂梁缺口冲击强度有轻微的降低，但其阻燃能力大幅提高，并且改善了加工性能，更容易加工成型，有效解决了动态硫化过程中抗静电剂均匀分散及阻燃剂易降解的问题。
二、三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂的混合方式选择
试验例1：以实施例6提供的方式对三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂进行混合得到混合物1，对混合物1进行后续操作以制备动态硫化阻燃TPV复合材料1。
对比例6：对比例6与实施例6大致相同，但采用将三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂一并加入，共同混合的方式进行混合得到混合物2，对混合物2进行后续操作以制备动态硫化阻燃TPV复合材料2。
检测混合物1和混合物2的混合均匀度，混合均匀度的检测方法如下：从混合物1和混合物2中分别取样X和Y，样品个数分别为5个，检测样品中阻燃剂的含量，分别计算平均值和均方差，实验结果如表2所示。
表2.试验例1和对比例6提供的不同混合方式的检测结果
示例 样品X X1(％) X2(％) X3(％) X4(％) X5(％) X平均 均方差
试验例1 阻燃剂 30.2 30.6 31.1 30.9 31.2 30.8 0.41
示例 样品Y Y1(％) Y2(％) Y3(％) Y4(％) Y5(％) X平均 均方差
对比例6 阻燃剂 30.1 31.6 29.4 31.3 31.8 30.84 1.04
从表2可以看出，试验例1提供的混合方法混合制得的混合物1中五个样品中阻燃剂的含量分布相较于对比例6的均方差更小，均匀程度更高，制得的动态硫化阻燃TPV复合材料1的品质相较于动态硫化阻燃TPV复合材料2更优。
尽管已用具体实施例来说明和描述了本发明，然而应意识到，以上各实施例仅用以说明本发明的技术方案，而非对其限制；本领域的普通技术人员应当理解：在不背离本发明的精神和范围的情况下，可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围；因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些替换和修改。
工业实用性
本发明动态硫化阻燃TPV复合材料采用特定用量的聚丙烯、三元乙丙橡胶、热塑性聚氨酯弹性体、阻燃剂、流动改性剂、交联剂、热稳定剂和紫外光吸收剂制备得到，阻燃剂在所得动态硫化阻燃TPV复合材料中分散均匀，所得动态硫化阻燃TPV复合材料具有优异的抗菌性能，且加工性能好，易于加工成型。本发明动态硫化阻燃TPV复合材料的制备方法工艺简单，操作方便，效益高，适合于进行工业化生产。

Claims (15)

  1. 一种动态硫化阻燃TPV复合材料，其特征在于，所述动态硫化阻燃TPV复合材料主要由以下质量份数的成分制备得到：
    聚丙烯20-50份、三元乙丙橡胶20-60份、热塑性聚氨酯弹性体5-15份、阻燃剂15-30份、流动改性剂0.5-1.5份、交联剂0.2-0.6份、热稳定剂0.2-0.8份和紫外光吸收剂0.2-0.8份；
    优选地，所述动态硫化阻燃TPV复合材料主要由以下质量份数的成分制备得到：
    聚丙烯30-40份、三元乙丙橡胶30-50份、热塑性聚氨酯弹性体8-12份、阻燃剂20-25份、流动改性剂0.8-1.2份、交联剂0.3-0.5份、热稳定剂0.4-0.6份和紫外光吸收剂0.4-0.6份；
    进一步优选地，所述动态硫化阻燃TPV复合材料主要由以下质量份数的成分制备得到：
    聚丙烯35份、三元乙丙橡胶40份、热塑性聚氨酯弹性体10份、阻燃剂22份、流动改性剂1份、交联剂0.4份、热稳定剂0.5份和紫外光吸收剂0.5份。
  2. 根据权利要求1所述的动态硫化阻燃TPV复合材料，其特征在于，所述热塑性聚氨酯弹性体在200℃，压力2.16Kg条件下的熔融流动速率为25-55g/10min，且洛氏硬度为45-65。
  3. 根据权利要求1所述的动态硫化阻燃TPV复合材料，其特征在于，所述阻燃剂包括无卤阻燃剂和无机阻燃剂中的一种或多种，优选所述无卤阻燃剂包括N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和聚磷酸铵中的一种或多种，进一步优选所述无卤阻燃剂包括N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和聚磷酸铵；
    优选地，所述N,N-双(2-羟乙基)氨基亚甲基膦酸二乙酯和聚磷酸铵的质量比为1：0.5-2，优选为1：0.8-1.2，进一步优选为1：1。
  4. 根据权利要求1所述的动态硫化阻燃TPV复合材料，其特征在于，所述流动改性剂包括内润滑剂、外润滑剂以及复合型润滑剂中的一种或多种，优选地，所述内润滑剂包括高级脂肪醇、脂肪酸酯和长链多官能团酯中的一种或多种，进一步优选所述长链多官能团酯包括AM-80流动改性剂。
  5. 根据权利要求1所述的动态硫化阻燃TPV复合材料，其特征在于，所述交联剂包括外交联剂中的一种或多种，优选包括二-(叔丁基过氧化异丙基)苯和三烯丙基异氰脲酸酯、二丙烯酸-1，4-丁二醇酯、过氧化二异丙苯中的一种或多种，进一步优选包括二-(叔丁基过氧化异丙基)苯和三烯丙基异氰脲酸酯；
    优选地，所述二-(叔丁基过氧化异丙基)苯和三烯丙基异氰脲酸酯的质量比为1：0.5-2，优选为1：0.8-1.2，进一步优选为1：1。
  6. 根据权利要求1所述的动态硫化阻燃TPV复合材料，其特征在于，所述热稳定剂包括抗氧剂中的一种或多种，优选包括2,6-叔丁基-4-甲基苯酚、四(4-羟基-3，5-二叔丁基苯基丙酸)季戊四醇酯、3，5-二叔丁基-4-羟基苯丙酸十八酯、亚磷酸三苯酯和亚磷酸三壬基苯酯中的一种或多种，进一步优选包括2,6-叔丁基-4-甲基苯酚。
  7. 根据权利要求1所述的动态硫化阻燃TPV复合材料，其特征在于，所述紫外光吸收剂包括二苯甲酮类紫外光吸收剂、苯并三唑类紫外光吸收剂和哌啶类紫外光吸收剂中的一种或多种，优选包括2-羟基-4-甲氧基二苯甲酮、2，2’-二羟基-4-甲氧基二苯甲酮、2(2-羟基-3’，5’-二叔丁基苯基)-5-氯代苯并三唑和双(2，2，6，6-四甲基哌啶)癸二酸酯中的一种或多种，进一步优选包括2-羟基-4-甲氧基二苯甲酮。
  8. 如权利要求1-7任一项所述的动态硫化阻燃TPV复合材料的制备方法，其特征在于，按比例将聚丙烯、三元乙丙橡胶、热塑性聚氨酯弹性体、阻燃剂、流动改性剂、交联剂、热稳定剂和紫外光吸收剂充分混合后得到混合料，挤出所述混合料，得到一种动态硫化阻燃TPV复合材料；
    优选地，所述一种动态硫化阻燃TPV复合材料的制备方法包括：
    按比例将三元乙丙橡胶、热塑性聚氨酯弹性体和阻燃剂进行混炼，之后加入聚丙烯、流动改性剂、交联剂、热稳定剂和紫外光吸收剂，充分混合后得到混合料，挤出所述混合料，得到一种动态硫化阻燃TPV复合材料。
  9. 根据权利要求8所述的动态硫化阻燃TPV复合材料的制备方法，其特征在于，在按比例将所述三元乙丙橡胶、所述热塑性聚氨酯弹性体和所述阻燃剂进行混炼之后，依次间隔加入所述交联剂、所述聚丙烯、所述流动改性剂、所述热稳定剂和所述紫外光吸收剂，充分混合，其中，间隔时间为1min以上，优选为2-5min，进一步优选为3min；混合时间为10min以上，优选为20-30min，进一步优选为25min。
  10. 根据权利要求8所述的动态硫化阻燃TPV复合材料的制备方法，其特征在于，将所述阻燃剂分为三份，向第一份所述阻燃剂中加入所述三元乙丙橡胶，混合均匀后，搅拌加入第二份所述阻燃剂，接着加入所述热塑性聚氨酯弹性体，混合均匀后，再次加入剩余的第三份所述阻燃剂，三份所述阻燃剂的质量比为1:1-2:1-2；优选为1:1:2。
  11. 根据权利要求8所述的动态硫化阻燃TPV复合材料的制备方法，其特征在于，所述将三元乙丙橡胶、所述热塑性聚氨酯弹性体和所述阻燃剂采用密炼机以40-50r/min的转速进行混炼，混炼后排胶，冷却20-24h，再以所述密炼机以10-20r/min的 转速对聚丙烯、所述流动改性剂、所述交联剂、所述热稳定剂和所述紫外光吸收剂进行混合。
  12. 根据权利要求11所述的动态硫化阻燃TPV复合材料的制备方法，其特征在于，冷却所述排胶包括以5-6℃/h的冷却速度进行冷却，冷却6-8h后，以1-2℃/h的冷却速度冷却14-16h。
  13. 根据权利要求8-12任一项所述的动态硫化阻燃TPV复合材料的制备方法，其特征在于，所述混炼的温度为50-80℃，优选为60-70℃，进一步优选为60℃；
    优选地，所述混炼的时间为20min以上，优选为20-40min，进一步优选为30min。
  14. 根据权利要求8所述的动态硫化阻燃TPV复合材料的制备方法，其特征在于，挤出所述混合料包括：先将双螺杆挤出机的加热区进行预热，预热至温度为50-80℃，然后将所述混合料喂入所述双螺杆挤出机，调节所述双螺杆挤出机的转速为1-10r/min，混合挤出。
  15. 根据权利要求8或14所述的动态硫化阻燃TPV复合材料的制备方法，其特征在于，所述挤出的温度为150℃以上，优选为175-200℃，进一步优选为180℃。
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