WO2018192173A1 - Dynamically-vulcanized antistatic tpv composite material and preparation method therefor - Google Patents

Abstract

A dynamically-vulcanized antistatic TPV composite material and a preparation method therefor. The dynamically-vulcanized antistatic TPV composite material of the present invention is prepared from specific amounts of polypropylene, ethylene propylene diene monomer rubber, a thermoplastic polyurethane elastomer, an antibacterial agent, a flow modifier, a crosslinking agent, a heat stabilizer and an ultraviolet absorber. The antibacterial agent is evenly dispersed in the obtained dynamically-vulcanized antistatic TPV composite material, and the obtained dynamically-vulcanized antistatic TPV composite material has excellent antibacterial properties and good processing performance, and is easy to process and mold. The preparation method for the dynamically-vulcanized antistatic TPV composite material of the present invention is simple in process, convenient to operate, high in benefits and suitable for industrial production.

Description

Dynamic vulcanization antistatic TPV composite material and preparation method thereof

Cross-reference to related applications

This application claims priority to Chinese Patent Application No. CN201710261279.2, entitled "Dynamic Vulcanization Antistatic TPV Composite Material and Its Preparation Method", filed on April 20, 2017, the entire contents of which is hereby incorporated by reference. This is incorporated herein by reference.

Technical field

The invention relates to the technical field of materials science, in particular to a dynamic vulcanization antistatic TPV composite material and a preparation method thereof.

Background technique

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. In the middle of the 20th century, with the rapid development of industrial production and the rapid application and application of polymer materials, on the one hand, the wide application of some high-density polymer materials such as plastics and rubber, and the high speed of modern production processes. The electrostatic energy can be accumulated to a high degree. On the other hand, the production and use of static sensitive materials, such as light oil, gunpowder, solid electronic devices, etc., the industrial and mining enterprises are also increasingly exposed to static electricity. Electrostatic hazards have caused considerable consequences and losses. Therefore, antistatic materials have attracted more and more people's attention. It is particularly important to develop a vulcanized TPV composite with excellent mechanical properties and antistatic effect, which has a huge market space.

In the related art, the dynamic vulcanized TPV material has poor antistatic property, poor processing property, and difficult molding process, which affects material properties.

In view of this, the present invention has been specifically proposed.

Summary of the invention

A first object of the present invention is to provide a dynamic vulcanization antistatic TPV composite material. The antistatic agent in the dynamic vulcanization antistatic TPV composite material has uniform dispersion, excellent antistatic property, good processing performance and easy processing and molding.

A second object of the present invention is to provide a method for preparing the dynamic vulcanization antistatic TPV composite material, which is simple in process, convenient in operation, high in efficiency, and suitable for industrial production.

In order to achieve the above object of the present invention, the following technical solutions are adopted:

A dynamically vulcanized antistatic TPV composite material prepared by the following parts by mass:

20-50 parts of polypropylene, 20-60 parts of ethylene propylene diene monomer, 5-15 parts of thermoplastic polyurethane elastomer, 2-6 parts of antistatic agent, 0.5-1.5 parts of flow modifier, 0.2-0.6 parts of crosslinking agent , heat stabilizer 0.2-0.8 parts and ultraviolet light absorber 0.2-0.8 parts.

The dynamic vulcanization antistatic TPV composite material of the invention is prepared by using a specific amount of polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, antistatic agent, flow modifier, crosslinking agent, heat stabilizer and ultraviolet light absorber. The antistatic agent is uniformly dispersed in the obtained dynamic vulcanized antistatic TPV composite material, and the obtained dynamic vulcanized antistatic TPV composite material has excellent antistatic property, good processing property and easy processing and molding.

Preferably, the dynamically vulcanized antistatic TPV composite is prepared mainly from the following parts by mass:

30-40 parts of polypropylene, 30-50 parts of ethylene propylene diene monomer, 8-12 parts of thermoplastic polyurethane elastomer, 3-5 parts of antistatic agent, 0.8-1.2 parts of flow modifier, 0.3-0.5 parts of crosslinking agent , heat stabilizer 0.4-0.6 parts and ultraviolet light absorber 0.4-0.6 parts.

Further preferably, the dynamically vulcanized antistatic TPV composite is prepared mainly from the following parts by mass:

35 parts of polypropylene, 40 parts of ethylene propylene diene monomer, 10 parts of thermoplastic polyurethane elastomer, 4 parts of antistatic agent, 1 part of flow modifier, 0.4 part of crosslinking agent, 0.5 part of heat stabilizer and 0.5 part of ultraviolet light absorber Share.

Alternatively, the 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.

Optionally, the antistatic agent comprises one or more of an internal mixed antistatic agent, preferably one or more of castor oil alkanolamide borate and methyl ricinoleate ammonium sulfate, Further preferably including castor oil alkanolamide boron Acid ester and ammonium ricinoleate ammonium sulfate. In other words, the antistatic agent may be castor oil alkanolamide borate, or may be ammonium ricinoleate ammonium sulfate, or may be ricinoleic alkanolamide borate and methyl ricinoleate ammonium sulfate. mixture. The antistatic agent may contain a small amount of impurities that do not participate in the reaction.

Alternatively, the antistatic agent is used in an amount of from 0.2 to 0.6% by weight of the sum of the mass of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer.

Alternatively, the antistatic agent is used in an amount of from 0.3 to 0.5% by weight of the sum of the mass of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer.

Alternatively, the antistatic agent is used in an amount of from 0.4 to 0.5% by weight of the sum of the mass of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer.

Preferably, the mass ratio of the castor oil alkanolamide borate and the methyl ricinoleate ammonium sulfate is 1:0.5-2, preferably 1:0.8-1.2, further preferably 1:1.

Optionally, the flow modifier comprises one or more of an internal lubricant, an external lubricant, and a composite lubricant. The internal lubricant preferably comprises one or more of a higher aliphatic alcohol, a fatty acid ester and a long chain polyfunctional ester, and further preferably the long chain polyfunctional ester comprises an AM-80 flow modifier. It should be understood that the external lubricant includes, for example, higher fatty acids, fatty amides, paraffin wax, and the like.

Optionally, the crosslinking agent comprises one or more of an external crosslinking agent, and the external crosslinking agent includes, for example, polyisocyanate, polyamine, polypropylene glycol glycidyl ether, ethyl orthosilicate, dimethacrylic acid. Ethylene glycol ester, di-(tert-butylperoxyisopropyl)benzene (odorless DCP) and triallyl isocyanurate (TAIC), etc., in this embodiment, the crosslinking agent preferably comprises two- One or more of (tert-butylperoxyisopropyl)benzene and triallyl isocyanurate, the further crosslinking agent preferably comprises bis-(tert-butylperoxyisopropyl)benzene and three Allyl isocyanurate (TAIC).

Preferably, 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.

Preferably, the crosslinking agent is used in an amount of from 5 to 20% of the antistatic agent. Preferably, the crosslinking agent is used in an amount of from 8 to 12% of the antistatic agent. Preferably, the crosslinking agent is used in an amount of 10% of the antistatic agent.

Optionally, the heat stabilizer comprises one or more of antioxidants, preferably antioxidants include 2,6-tert-butyl-4-methylphenol, tetrakis(4-hydroxy-3,5- Di-tert-butylphenylpropionic acid pentaerythritol ester, 3,5-di-tert-butyl-4-hydroxybenzene One or more of octadecyl propionate, triphenyl phosphite and tridecyl phenyl phosphite (TNP), further preferably including 2,6-tert-butyl-4-methylphenol (antioxidant) -264). Optionally, the amount of the heat stabilizer is 0.3-0.7% of the sum of the masses of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer; preferably, the heat stabilizer is used in the amount of polypropylene or ethylene propylene diene monomer. The sum of the masses of the thermoplastic polyurethane elastomer is 0.4-0.6%.

Optionally, 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 (UV-9), 2,2'-dihydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-3',5'-di One or more of tert-butylphenyl)-5-chlorobenzotriazole and bis(2,2,6,6-tetramethylpiperidine) sebacate, further preferably including 2-hydroxyl 4-methoxybenzophenone.

Optionally, the amount of the ultraviolet light absorber is 0.3-0.7% of the sum of the masses of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer; preferably, the ultraviolet light absorber is used in the amount of polypropylene, three The sum of the mass of the ethylene propylene rubber and the thermoplastic polyurethane elastomer is 0.4-0.6%.

Polypropylene is very sensitive to ultraviolet light. In this embodiment, 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. .

The above preparation method of a dynamic vulcanization antistatic TPV composite material, which comprises polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, antistatic agent, flow modifier, crosslinking agent, heat stabilizer and ultraviolet The light absorber is thoroughly mixed and extruded to obtain a dynamically vulcanized antistatic TPV composite.

The preparation method of the dynamic vulcanization antistatic TPV composite material of the invention has the advantages of simple process, convenient operation and high benefit, and is suitable for industrial production.

Preferably, the preparation method of the dynamic vulcanization antistatic TPV composite material comprises:

The ethylene propylene diene monomer, the thermoplastic polyurethane elastomer and the antistatic agent 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 dynamically vulcanized antistatic TPV composite was obtained.

Alternatively, the kneading temperature is 50-80 ° C, preferably 60-70 ° C, and further preferably 60 ° C.

Alternatively, the kneading time is 20 min or more, preferably 20-40 min, further preferably 30 min.

Alternatively, the extrusion temperature is 150 ° C or higher, preferably 175 to 200 ° C, and further preferably 180 ° C.

Compared with the prior art, the beneficial effects of the present invention are:

The dynamic vulcanization antistatic TPV composite material of the invention is prepared by using a specific amount of polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, antistatic agent, flow modifier, crosslinking agent, heat stabilizer and ultraviolet light absorber. The antistatic agent is uniformly dispersed in the obtained dynamic vulcanized antistatic TPV composite material, and the obtained dynamic vulcanized antistatic TPV composite material has excellent antistatic property, good processing property and easy processing and molding. The preparation method of the dynamic vulcanization antistatic TPV composite material of the invention has the advantages of simple process, convenient operation and high benefit, and is suitable for industrial production.

detailed description

The technical solutions of the present invention will be clearly and completely described below in conjunction with the specific embodiments, but those skilled in the art will understand that the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments, only The invention is illustrated and should not be construed as limiting the scope of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention. Those who do not specify the specific conditions in the examples are carried out according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are conventional products that can be obtained by commercially available purchase.

The invention provides a dynamic vulcanization antistatic TPV composite material, which is prepared mainly from the following parts by mass:

20-50 parts of polypropylene (PP), 20-60 parts of EPDM, 5-15 parts of thermoplastic polyurethane elastomer (TPU), 2-6 parts of antistatic agent, 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 antistatic TPV composite material of the invention is prepared by using a specific amount of polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, antistatic agent, flow modifier, crosslinking agent, heat stabilizer and ultraviolet light absorber. The antistatic agent is uniformly dispersed in the obtained dynamic vulcanized antistatic TPV composite material, and the obtained dynamic vulcanized antistatic TPV composite material has excellent antistatic property, good processing property and easy processing and molding.

Preferably, the dynamically vulcanized antistatic TPV composite is prepared mainly from the following parts by mass:

30-40 parts of polypropylene, 30-50 parts of ethylene propylene diene monomer, 8-12 parts of thermoplastic polyurethane elastomer, antistatic agent 3-5 parts, flow modifier 0.8-1.2 parts, cross-linking agent 0.3-0.5 parts, heat stabilizer 0.4-0.6 parts, and ultraviolet light absorber 0.4-0.6 parts.

Further preferably, the dynamically vulcanized antistatic TPV composite is prepared mainly from the following parts by mass:

35 parts of polypropylene, 40 parts of ethylene propylene diene monomer, 10 parts of thermoplastic polyurethane elastomer, 4 parts of antistatic agent, 1 part of flow modifier, 0.4 part of crosslinking agent, 0.5 part of heat stabilizer and 0.5 part of ultraviolet light absorber Share.

In a preferred embodiment of the present invention, 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 antistatic TPV composite and improve its processing properties.

In a preferred embodiment of the present invention, the antistatic agent comprises one or more of an internal mixed type antistatic agent, preferably including castor oil alkanolamide borate and methyl ricinoleate ammonium sulfate. One or more of them further preferably include castor oil alkanolamide borate and methyl ricinoleate ammonium sulfate. In other words, the antistatic agent may be castor oil alkanolamide borate, or may be ammonium ricinoleate ammonium sulfate, or may be ricinoleic alkanolamide borate and methyl ricinoleate ammonium sulfate. mixture. The antistatic agent may contain a small amount of impurities that do not participate in the reaction.

Alternatively, the antistatic agent is used in an amount of from 0.2 to 0.6% by weight of the sum of the mass of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer.

Alternatively, the antistatic agent is used in an amount of from 0.3 to 0.5% by weight of the sum of the mass of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer.

Alternatively, the antistatic agent is used in an amount of from 0.4 to 0.5% by weight of the sum of the mass of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer.

Preferably, the mass ratio of the castor oil alkanolamide borate and the methyl ricinoleate ammonium sulfate is 1:0.5-2, preferably 1:0.8-1.2, further preferably 1:1.

Using a specific antistatic agent, the thermoplastic polyurethane elastomer and EPDM rubber are swelled to plasticize, and co-crosslinking with EPDM in dynamic vulcanization by adding a specific antistatic agent during the extrusion process It can achieve good dispersion in the fully crosslinked rubber dispersed phase and fully improve the obtained dynamic vulcanized antistatic TPV composite. Antistatic properties.

In a preferred embodiment of the invention, the flow modifier comprises one or more of an internal lubricant, an external lubricant, and a composite lubricant. The internal lubricant preferably comprises one or more of a higher aliphatic alcohol, a fatty acid ester and a long chain polyfunctional ester, and further preferably the long chain polyfunctional ester comprises an AM-80 flow modifier. It should be understood that 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.

In a preferred embodiment of the present invention, the crosslinking agent comprises one or more of external crosslinking agents, and the external crosslinking agent includes, for example, polyisocyanate, polyamine, polypropylene glycol glycidyl ether, orthosilicate Ethyl ester, ethylene glycol dimethacrylate, di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), etc., in this embodiment, The crosslinking agent preferably comprises one or more of bis-(tert-butylperoxyisopropyl)benzene (odorless DCP) and triallyl isocyanurate (TAIC), further preferably the external crosslinking agent comprises two -(tert-butylperoxyisopropyl)benzene and triallyl isocyanurate (TAIC).

Preferably, 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 use of a specific crosslinking agent helps to promote the crosslinking reaction and improve the mechanical properties of the resulting dynamically vulcanized antistatic TPV composite.

In a preferred embodiment of the invention, 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 One or more of an ester (antioxidant-1076), triphenyl phosphite (TPP) and tridecyl phenyl phosphite (TNP), further preferably including 2,6-tert-butyl-4-methyl Phenolic. Optionally, the amount of the heat stabilizer is 0.3-0.7% of the sum of the masses of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer; preferably, the heat stabilizer is used in the amount of polypropylene or ethylene propylene diene monomer. The sum of the masses of the thermoplastic polyurethane elastomer is 0.4-0.6%.

The use of specific heat stabilizers can effectively retard or inhibit the oxidation of the obtained dynamically vulcanized antistatic TPV composites. The process proceeds to prevent aging of the resulting dynamically vulcanized antistatic TPV composite and prolong its useful life.

In a preferred embodiment of the present invention, the ultraviolet light absorber comprises 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) One or more of the diesters further preferably include 2-hydroxy-4-methoxybenzophenone.

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 antistatic TPV composite material, and improve the stability of the obtained dynamic vulcanized antistatic TPV composite material under long-time illumination. .

Optionally, the amount of the ultraviolet light absorber is 0.3-0.7% of the sum of the masses of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer; preferably, the ultraviolet light absorber is used in the amount of polypropylene, three The sum of the mass of the ethylene propylene rubber and the thermoplastic polyurethane elastomer is 0.4-0.6%.

Polypropylene is very sensitive to ultraviolet light. In this embodiment, 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. .

The above preparation method of a dynamic vulcanization antistatic TPV composite material, which comprises polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, antistatic agent, flow modifier, crosslinking agent, heat stabilizer and ultraviolet The light absorber is thoroughly mixed and extruded to obtain a dynamically vulcanized antistatic TPV composite.

The preparation method of the dynamic vulcanization antistatic TPV composite material of the invention has the advantages of simple process, convenient operation and high benefit, and is suitable for industrial production.

Preferably, the preparation method of the dynamic vulcanization antistatic TPV composite material comprises:

The ethylene propylene diene monomer, the thermoplastic polyurethane elastomer and the antistatic agent 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 dynamically vulcanized antistatic TPV composite was obtained.

Using a specific feeding mixing sequence, the raw materials are further uniformly mixed uniformly, and the properties are obtained by extrusion. Uniformly stable, dynamically vulcanized antistatic TPV composite.

Optionally, the mixing of the ethylene propylene diene monomer, the thermoplastic polyurethane elastomer and the antistatic agent is carried out using an internal mixer.

Alternatively, the extrusion is carried out using a twin screw extruder.

In a preferred embodiment of the present invention, the kneading temperature is 50-80 ° C, preferably 60-70 ° C, and further preferably 60 ° C.

In a preferred embodiment of the present invention, the kneading time is 20 min or more, preferably 20-40 min, and further preferably 30 min.

Using a specific mixing temperature and time, the ethylene propylene diene monomer, the thermoplastic polyurethane elastomer and the antistatic agent are well mixed, and the antistatic property of the obtained dynamic vulcanized antistatic TPV composite material is improved, and the processing energy is improved.

In a preferred embodiment of the invention, 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.

Example 1

A method for preparing a dynamic vulcanization antistatic TPV composite material, comprising:

(1) Weigh 20kg of polypropylene (T30S), 20kg of EPDM rubber, 5kg of thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), 1.33kg of castor oil alkanolamide borate, ricinoleic acid 0.67kg of ammonium ester sulfate, 0.5kg of AM-80 flow modifier, 0.133kg of di-(tert-butylperoxyisopropyl)benzene (odorless DCP), and triallyl isocyanurate (TAIC) 0.067kg , 0.2 kg of tridecyl phenyl phosphite (TNP) and 0.2 kg of 2-hydroxy-4-methoxybenzophenone (UV-9);

(2) EPDM, thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), castor oil alkanolamide borate and ammonium ricinoleate ammonium sulfate in an internal mixer at 50 ° C Mixing for 60 minutes;

(3) Further adding polypropylene (T30S), di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), tridecylphenyl phosphite ( TNP) and 2-hydroxy-4-methoxybenzophenone (UV-9), after thorough mixing, blending and extruding using a twin-screw extruder, the screw processing extrusion temperature of the twin-screw extruder At 150 ° C, a dynamically vulcanized antistatic TPV composite was obtained.

Example 2

A method for preparing a dynamic vulcanization antistatic TPV composite material, comprising:

(1) Weigh 50kg of polypropylene (T30S), 60kg of EPDM rubber, 15kg of thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), 2kg of castor oil alkanolamide borate, methyl ricinoleate 4kg of ammonium sulfate, 1.5kg of AM-80 flow modifier, 0.2kg of di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC) 0.4kg, four (4-hydroxy-3,5-di-tert-butylphenylpropionic acid) pentaerythritol ester (antioxidant-1010) 0.8 kg and 2,2'-dihydroxy-4-methoxybenzophenone (UV- 24) 0.8kg;

(2) EPDM, thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), castor oil alkanolamide borate and methyl ricinoleate ammonium sulfate in an internal mixer at 80 ° C Mixing for 20 minutes;

(3) Further adding polypropylene (T30S), di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), tetrakis (4-hydroxy-3, 5-di-tert-butylphenylpropionic acid pentaerythritol ester (antioxidant-1010) and 2,2'-dihydroxy-4-methoxybenzophenone (UV-24), fully mixed, using double The screw extruder was blended and extruded, and the screw extrusion extrusion temperature of the twin-screw extruder was 175 ° C to obtain a dynamically vulcanized antistatic TPV composite material.

Example 3

A method for preparing a dynamic vulcanization antistatic TPV composite material, comprising:

(1) Weigh 30kg of polypropylene (T30S), 30kg of EPDM rubber, 8kg of thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), 1.67kg of castor oil alkanolamide borate, ricinoleic acid 1.33kg ammonium ester sulfate, 0.8kg AM-80 flow modifier, 0.167kg di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC) 0.133kg , 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid octadecyl ester (antioxidant-1076) 0.4kg and 2(2- Hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole (UV-328) 0.4 kg;

(2) EPDM rubber, thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), castor oil alkanolamide borate and ammonium ricinoleate ammonium sulfate in an internal mixer at 60 ° C Mixing for 20 minutes;

(3) Further adding polypropylene (T30S), di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), 3,5-di-tert-butyl Octadecyl 4-hydroxyphenylpropionate (antioxidant-1076) and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole (UV -328), after thorough mixing, blending and extruding by a twin-screw extruder, the screw processing extrusion temperature of the twin-screw extruder was 200 ° C, and a dynamic vulcanized antistatic TPV composite material was obtained.

Example 4

A method for preparing a dynamic vulcanization antistatic TPV composite material, comprising:

(1) Weigh 40kg of polypropylene (T30S), 50kg of EPDM rubber, 12kg of thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), 2.27kg of castor oil alkanolamide borate, ricinoleic acid 2.73kg of ammonium ester sulfate, 1.2kg of AM-80 flow modifier, 0.227kg of di-(tert-butylperoxyisopropyl)benzene (odorless DCP), and triallyl isocyanurate (TAIC) 0.273kg , 0.6 kg of triphenyl phosphite (TPP) and 0.6 kg of bis(2,2,6,6-tetramethylpiperidine) sebacate;

(2) EPDM rubber, thermoplastic polyurethane elastomer (TPU, commercially available brand 87I85), castor oil alkanolamide borate and methyl ricinoleate ammonium sulfate in an internal mixer at 70 ° C Mixing for 40 minutes;

(3) Further adding polypropylene (T30S), di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), triphenyl phosphite (TPP) And bis(2,2,6,6-tetramethylpiperidine) sebacate, after thorough mixing, blending and extruding using a twin-screw extruder, the screw processing extrusion temperature of the twin-screw extruder At 190 ° C, a dynamically vulcanized antistatic TPV composite was obtained.

Example 5

A method for preparing a dynamic vulcanization antistatic TPV composite material, comprising:

(1) Weighing 35 kg of polypropylene (T30S), 40 kg of EPDM rubber, 10 kg of thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), 2 kg of castor oil alkanolamide borate, and methyl ricinoleate 2kg of ammonium sulfate, 1kg of AM-80 flow modifier, 0.2kg of di-(tert-butylperoxyisopropyl)benzene (odorless DCP), and 0.2kg of triallyl isocyanurate (TAIC), 2, 6-tert-butyl-4-methylphenol (antioxidant-264) 0.5 kg and 2-hydroxy-4-methoxybenzophenone (UV-9) 0.5 kg;

(2) EPDM rubber, thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), castor oil alkanolamide borate and ammonium ricinoleate ammonium sulfate in an internal mixer at 60 ° C Mixing for 30 minutes;

(3) Further adding polypropylene (T30S), di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), 2,6-tert-butyl- 4-methylphenol (antioxidant-264) and 2-hydroxy-4-methoxybenzophenone (UV-9), after thorough mixing, blending and extruding using a twin-screw extruder, the double The screw extruder extrusion temperature of the screw extruder was 180 ° C, and a dynamic vulcanized antistatic TPV composite material was obtained.

Example 6

A method for preparing a dynamic vulcanization antistatic TPV composite material, comprising:

(1) Weighing 35 kg of polypropylene (T30S), 40 kg of EPDM rubber, 10 kg of thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), 3.2 kg of castor oil alkanolamide borate, and ricinoleic acid 0.8kg of ester ammonium sulfate, 1kg of AM-80 flow modifier, 0.2kg of di-(tert-butylperoxyisopropyl)benzene (odorless DCP), 0.2kg of triallyl isocyanurate (TAIC), 2,6-tert-butyl-4-methylphenol (antioxidant-264) 0.5 kg and 2-hydroxy-4-methoxybenzophenone (UV-9) 0.5 kg;

(2) EPDM rubber, thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), castor oil alkanolamide borate and ammonium ricinoleate ammonium sulfate in an internal mixer at 60 ° C Mixing for 30 minutes;

(3) Further adding polypropylene (T30S), di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), 2,6-tert-butyl- 4-methylphenol (antioxidant-264) and 2-hydroxy-4-methoxybenzophenone (UV-9), after thorough mixing, blending and extruding using a twin-screw extruder, the double The screw extruder extrusion temperature of the screw extruder was 180 ° C, and a dynamic vulcanized antistatic TPV composite material was obtained.

Example 7

A method for preparing a dynamic vulcanization antistatic TPV composite material, comprising:

(1) Weighing 35 kg of polypropylene (T30S), 40 kg of EPDM rubber, 10 kg of thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), 1 kg of castor oil alkanolamide borate, and methyl ricinoleate 3 kg of ammonium sulfate, 1 kg of AM-80 flow modifier, 0.2 kg of di-(tert-butylperoxyisopropyl)benzene (odorless DCP), and 0.2 kg of triallyl isocyanurate (TAIC), 2, 6-tert-butyl-4-methylphenol (antioxidant-264) 0.5 kg and 2-hydroxy-4-methoxybenzophenone (UV-9) 0.5 kg;

(2) EPDM rubber, thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), castor oil alkanolamide borate and ammonium ricinoleate ammonium sulfate in an internal mixer at 60 ° C Mixing for 30 minutes;

(3) Further adding polypropylene (T30S), di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), 2,6-tert-butyl- 4-methylphenol (antioxidant-264) and 2-hydroxy-4-methoxybenzophenone (UV-9), after thorough mixing, blending and extruding using a twin-screw extruder, the double The screw extruder extrusion temperature of the screw extruder was 180 ° C, and a dynamic vulcanized antistatic TPV composite material was obtained.

Example 8

A method for preparing a dynamic vulcanization antistatic TPV composite material, comprising:

(1) Weighing 35 kg of polypropylene (T30S), 40 kg of EPDM rubber, 10 kg of thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), 4 kg of castor oil alkanolamide borate, and methyl ricinoleate 4kg ammonium sulfate, 1kg AM-80 flow modifier, 0.2kg of di-(tert-butylperoxyisopropyl)benzene (odorless DCP), 2,6-tert-butyl-4-methylphenol (antioxidant) -264) 0.5 kg and 2-hydroxy-4-methoxybenzophenone (UV-9) 0.5 kg;

(2) EPDM rubber, thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), castor oil alkanolamide borate and ammonium ricinoleate ammonium sulfate in an internal mixer at 60 ° C Mixing for 30 minutes;

(3) Further adding polypropylene (T30S), di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), 2,6-tert-butyl- 4-methylphenol (antioxidant-264) and 2-hydroxy-4-methoxybenzophenone (UV-9), after thorough mixing, blending and extruding using a twin-screw extruder, the double The screw extruder extrusion temperature of the screw extruder was 180 ° C, and a dynamic vulcanized antistatic TPV composite material was obtained.

Example 9

A method for preparing a dynamic vulcanization antistatic TPV composite material, comprising:

(1) Weigh polypropylene (T30S) 35kg, EPDM 40kg, thermoplastic polyurethane elastomer (TPU, commercially available brand 87I85) 10kg, ricinoleic acid methyl ammonium sulfate 4kg, AM-80 flow modification 1 kg, bis-(tert-butylperoxyisopropyl)benzene (odorless DCP) 0.8 kg, 2,6-tert-butyl-4-methylphenol (antioxidant-264) 0.5 kg and 2-hydroxy- 4-methoxybenzophenone (UV-9) 0.5 kg;

(2) EPDM rubber, thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), castor oil alkanolamide borate and ammonium ricinoleate ammonium sulfate in an internal mixer at 60 ° C Mixing for 30 minutes;

(3) Further adding polypropylene (T30S), di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), 2,6-tert-butyl- 4-methylphenol (antioxidant-264) and 2-hydroxy-4-methoxybenzophenone (UV-9), after thorough mixing, blending and extruding using a twin-screw extruder, the double The screw extruder extrusion temperature of the screw extruder was 180 ° C, and a dynamic vulcanized antistatic TPV composite material was obtained.

Example 10

A method for preparing a dynamic vulcanization antistatic TPV composite material, comprising:

(1) Weigh polypropylene (T30S) 35kg, EPDM 40kg, thermoplastic polyurethane elastomer (TPU, commercially available brand 87I85) 10kg, ricinoleic acid methyl ammonium sulfate 4kg, AM-80 flow modification 1kg, triallyl isocyanurate (TAIC) 0.5kg, 2,6-tert-butyl-4-methylphenol (antioxidant-264) 0.5kg and 2-hydroxy-4-methoxy Benzophenone (UV-9) 0.5kg;

(2) EPDM rubber, thermoplastic polyurethane elastomer (TPU, commercially available grade 87I85), castor oil alkanolamide borate and ammonium ricinoleate ammonium sulfate in an internal mixer at 60 ° C Mixing for 30 minutes;

(3) Further adding polypropylene (T30S), di-(tert-butylperoxyisopropyl)benzene (odorless DCP), triallyl isocyanurate (TAIC), 2,6-tert-butyl- 4-methylphenol (antioxidant-264) and 2-hydroxy-4-methoxybenzophenone (UV-9), after thorough mixing, blending and extruding using a twin-screw extruder, the double The screw extruder extrusion temperature of the screw extruder was 180 ° C, and a dynamic vulcanized antistatic TPV composite material was obtained.

The dynamic vulcanization antistatic TPV composite materials obtained in Examples 1-10 of the present invention were tested for performance, and the obtained dynamically vulcanized antistatic TPV composite materials were respectively subjected to corresponding standards (tensile strength GB/T1040.2-2006/1A/50, cantilever Beam notched impact strength GB/T1843-2008/A, surface resistance GB/T1410-2006) prepared into standard test splines, The ratios 1-5 are respectively subjected to the methods described in Examples 1-5 of the present invention, but without using any antistatic agent such as castor oil alkanolamide borate or ammonium ricinoleate ammonium sulfate, the following tests are carried out. The performance results are shown in Table 1:

Table 1 Performance test results of the dynamic vulcanization antistatic TPV composite of the present invention

It can be seen from Table 1 that after using the antistatic agent, the tensile strength can reach the level without using the antistatic agent, and the notched impact strength of the cantilever beam is slightly reduced, but the antistatic ability is greatly improved, and the surface resistance can be improved. It has been improved from 10 ¹² Ω to 10 ⁸ Ω, and has improved processing properties and easier processing. It effectively solves the problem of uniform dispersion of antistatic agents during dynamic vulcanization.

Further, it can be seen from Table 1 that when ricinoleic alkanolamide borate or methyl ricinoleate ammonium sulfate is used alone as an antistatic agent, the surface resistance is remarkably improved compared to when no antistatic agent is used. . However, the surface resistance is not as good as that of the mixture of the two. Further, when the mass ratio of the castor oil alkanolamide borate and the methyl ricinoleate ammonium sulfate is in the range of 1:0.5-2, the surface resistance is remarkable. improve.

Although the present invention has been illustrated and described with respect to the specific embodiments thereof, it should be understood that The technical solutions described in the foregoing embodiments may be modified, or some or all of the technical features may be equivalently replaced, without departing from the spirit and scope of the present invention. All such alternatives and modifications are intended to be included within the scope of the present invention.

Industrial applicability

The dynamic vulcanized flame retardant TPV composite material of the invention is prepared by using a specific amount of polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, antistatic agent, flow modifier, crosslinking agent, heat stabilizer and ultraviolet light absorber. The antistatic agent 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.

Claims (17)

A dynamic vulcanization antistatic TPV composite material, characterized in that the dynamic vulcanization antistatic TPV composite material is mainly prepared from the following parts by mass: 20-50 parts of polypropylene, 20-60 parts of ethylene propylene diene monomer, 5-15 parts of thermoplastic polyurethane elastomer, 2-6 parts of antistatic agent, 0.5-1.5 parts of flow modifier, 0.2-0.6 parts of crosslinking agent , heat stabilizer 0.2-0.8 parts and ultraviolet light absorber 0.2-0.8 parts; Preferably, the dynamically vulcanized antistatic TPV composite is prepared mainly from the following parts by mass: 30-40 parts of polypropylene, 30-50 parts of ethylene propylene diene monomer, 8-12 parts of thermoplastic polyurethane elastomer, 3-5 parts of antistatic agent, 0.8-1.2 parts of flow modifier, 0.3-0.5 parts of crosslinking agent , heat stabilizer 0.4-0.6 parts and ultraviolet light absorber 0.4-0.6 parts; Further preferably, the dynamically vulcanized antistatic TPV composite is prepared mainly from the following parts by mass: 35 parts of polypropylene, 40 parts of ethylene propylene diene monomer, 10 parts of thermoplastic polyurethane elastomer, 4 parts of antistatic agent, 1 part of flow modifier, 0.4 part of crosslinking agent, 0.5 part of heat stabilizer and 0.5 part of ultraviolet light absorber Share. The dynamic vulcanization antistatic TPV composite according to claim 1, wherein 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 Rockwell The hardness is 45-65. The dynamic vulcanization antistatic TPV composite according to claim 1 or 2, wherein the antistatic agent comprises one or more of an internally mixed antistatic agent, preferably comprising castor oil alkanolamide. One or more of borate and ammonium ricinoleate ammonium sulfate, further preferably including castor oil alkanolamide borate and methyl ricinoleate ammonium sulfate; Preferably, the mass ratio of the castor oil alkanolamide borate and the methyl ricinoleate ammonium sulfate is 1:0.5-2, preferably 1:0.8-1.2, further preferably 1:1. The dynamic vulcanization antistatic TPV composite according to any one of claims 1 to 3, wherein the antistatic agent is used in an amount of the polypropylene, the ethylene propylene diene monomer and the thermoplastic Quality of polyurethane elastomer The sum of the amounts is 0.2-0.6%. The dynamic vulcanization antistatic TPV composite according to any one of claims 1 to 4, wherein the antistatic agent is used in an amount of the polypropylene, the ethylene propylene diene monomer and the thermoplastic The sum of the masses of the polyurethane elastomer is 0.3-0.5%. A dynamically vulcanized antistatic TPV composite according to any one of claims 1 to 5, wherein the antistatic agent is used in an amount of the polypropylene, the ethylene propylene diene monomer and the thermoplastic The sum of the masses of the polyurethane elastomer is 0.4-0.5%. A dynamically vulcanized antistatic TPV composite according to any one of claims 1 to 6, wherein the flow modifier comprises one or more of internal lubricants, preferably including long chain polyfunctional groups. The ester further preferably comprises an AM-80 flow modifier. A dynamically vulcanized antistatic TPV composite according to any one of claims 1 to 7, wherein the crosslinking agent comprises one or more of external crosslinking agents, preferably including di-(tert-butyl) One or more of isopropyl oxy) benzene and triallyl isocyanurate, further preferably including bis-(tert-butylperoxyisopropyl)benzene and triallyl isocyanurate Acid ester Preferably, 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. A dynamically vulcanized antistatic TPV composite according to any one of claims 1-8, wherein the crosslinking agent is used in an amount of 5-20% of the antistatic agent. The dynamic vulcanization antistatic TPV composite according to any one of claims 1 to 9, wherein the crosslinking agent is used in an amount of 8-12% of the antistatic agent; preferably, the The crosslinking agent is used in an amount of 10% of the antistatic agent. A dynamically vulcanized antistatic TPV composite according to any one of claims 1 to 10, wherein the heat stabilizer comprises one or more of antioxidants, preferably including 2,6-un Butyl-4-methylphenol, tetrakis(4-hydroxy-3,5-di-tert-butylphenylpropionic acid) pentaerythritol ester, octadecyl 3,5-di-tert-butyl-4-hydroxyphenylpropionate, One or more of triphenyl phosphite and tridecyl phenyl phosphite further preferably include 2,6-tert-butyl-4-methylphenol. A dynamically vulcanized antistatic TPV composite material according to any one of claims 1-11, characterized in that The heat stabilizer is used in an amount of 0.3-0.7% of the sum of the masses of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer; preferably, the heat stabilizer is used in an amount of The sum of the masses of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer is from 0.4 to 0.6%. The dynamic vulcanization antistatic TPV composite material according to any one of claims 1 to 12, wherein the ultraviolet light absorber is used in an amount of the polypropylene, the ethylene propylene diene monomer, and the The sum of the masses of the thermoplastic polyurethane elastomer is 0.3-0.7%; preferably, the ultraviolet light absorber is used in an amount of the sum of the masses of the polypropylene, the ethylene propylene diene monomer and the thermoplastic polyurethane elastomer 0.4-0.6%. The dynamic vulcanization antistatic TPV composite material according to any one of claims 1 to 13, wherein the ultraviolet light absorber comprises a benzophenone ultraviolet light absorber and a benzotriazole ultraviolet light. One or more of an absorbent and a piperidine-based ultraviolet light absorber, preferably comprising 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzol Ketone, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole and bis(2,2,6,6-tetramethylpiperidine) One or more of the diesters further preferably include 2-hydroxy-4-methoxybenzophenone. The method for preparing a dynamic vulcanization antistatic TPV composite according to any one of claims 1 to 14, characterized in that polypropylene, ethylene propylene diene monomer, thermoplastic polyurethane elastomer, antistatic agent, and flow are proportionally The modifier, the crosslinking agent, the heat stabilizer and the ultraviolet light absorber are thoroughly mixed and extruded to obtain a dynamic vulcanization antistatic TPV composite material; Preferably, the preparation method of the dynamic vulcanization antistatic TPV composite material comprises: The ethylene propylene diene monomer, the thermoplastic polyurethane elastomer and the antistatic agent 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 dynamically vulcanized antistatic TPV composite was obtained. The method for preparing a dynamic vulcanization antistatic TPV composite according to claim 15, wherein the kneading temperature is 50-80 ° C, preferably 60-70 ° C, further preferably 60 ° C; Preferably, the kneading time is 20 min or more, preferably 20-40 min, and further preferably 30 min. The method for producing a dynamically vulcanized antistatic TPV composite according to claim 15 or 16, wherein the extrusion temperature is 150 ° C or higher, preferably 175 to 200 ° C, and more preferably 180 ° C.