CN114806011B - A kind of propylene polymer composition and preparation method thereof - Google Patents

Abstract

The invention belongs to the field of high polymer materials, and particularly relates to a propylene polymer composition and a preparation method thereof. The propylene polymer composition provided by the invention comprises the following raw material components: 100 parts by weight of a propylene polymer; 0.1 to 1 weight portion of reactive hindered phenol grafted propylene polymer; 0.1 to 1 weight portion of reactive hindered amine grafted propylene polymer; the reactive hindered phenol grafted propylene polymer is prepared by mixing propylene polymer with reactive hindered phenol after plasma treatment; the reactive hindered amine grafted propylene polymer is prepared by mixing and reacting a propylene polymer with reactive hindered amine after plasma treatment. According to the invention, after the propylene polymer is subjected to plasma treatment, the hindered amine and the hindered phenol are respectively grafted, and then the grafted modification is added into the propylene polymer base material, so that the propylene polymer composition with excellent electron beam irradiation resistance is finally obtained.

Description

A kind of propylene polymer composition and preparation method thereof

Technical field

The invention belongs to the field of polymer materials, and in particular relates to a propylene polymer composition and a preparation method thereof.

Background technique

Polypropylene (PP) is a thermoplastic synthetic resin with excellent properties. It is a colorless, translucent thermoplastic lightweight general-purpose plastic. PP materials have good chemical resistance, heat resistance, electrical insulation, high-strength mechanical properties and high wear-resistant processing properties. Since their inception, PP materials have rapidly been used in machinery, automobiles, electronic appliances, construction, textiles, packaging, It has been widely developed and applied in many fields such as agriculture, forestry, fishery and food industry.

In recent years, PP materials have been increasingly used in the field of medical devices. However, the radiation stability of ordinary medical PP is poor. PP will degrade after radiation disinfection, resulting in deterioration of physical and mechanical properties and yellowing in color. In addition, the degradation problem of ordinary medical PP after irradiation, sterilization, sterilization and storage for a period of time becomes more serious, and may even lose performance. This phenomenon is called the "post-irradiation effect". The reduction of mechanical properties and yellowing problems caused by radiation degradation, as well as the "post-irradiation effect", seriously limit the application of PP materials in medical devices and other radiation processing fields. How to solve the above problems is an urgent need to be solved in this field. technical challenge.

Contents of the invention

In view of this, the object of the present invention is to provide a propylene polymer composition and a preparation method thereof. The propylene polymer composition provided by the present invention has very excellent resistance to electron beam irradiation.

The invention provides a propylene polymer composition, whose raw material components include:

Propylene polymer 100 parts;

Reactive hindered phenol grafted propylene polymer 0.1 to 1 part;

Reactive hindered amine grafted propylene polymer 0.1 to 1 part;

The reactive hindered phenol-grafted propylene polymer is made by mixing a propylene polymer with a reactive hindered phenol after plasma treatment; the reactive hindered phenol is 2,6-bis-tert-butyl-4-[2 -(2-oxiranyl)ethyl]phenol and/or 2,6-di-tert-butyl-4-[(2-oxiranyl)methyl]phenol;

The reactive hindered amine-grafted propylene polymer is made by mixing a propylene polymer with a reactive hindered amine after plasma treatment; the reactive hindered amine is 1-acetyl-2,2,6,6- Tetramethyl-4-[(2-oxiranyl)methoxy]piperidine and/or 1,2,2,6,6-pentamethyl-4-[(2-oxiranyl) )methoxy]piperidine.

Preferably, the mass ratio of the propylene polymer and the reactive hindered phenol used in preparing the reactive hindered phenol-grafted propylene polymer is 1: (0.05-0.5).

Preferably, the reactive hindered phenol grafted propylene polymer is prepared according to the following steps:

A) Plasma treatment is performed on the propylene polymer under an oxygen atmosphere to obtain a pretreated propylene polymer; under acidic conditions, the pretreated propylene polymer and the reactive hindered phenol are mixed and reacted in a solvent to obtain a reactive hindered phenol polymer. propylene polymer;

or,

A') Plasma treatment of the propylene polymer in an ammonia atmosphere to obtain a pretreated propylene polymer; mix and react the pretreated propylene polymer with a reactive hindered phenol in a solvent to obtain a reactive hindered phenol grafted propylene polymer things.

Preferably, the mass ratio of the propylene polymer and the reactive hindered amine used in preparing the reactive hindered amine-grafted propylene polymer is 1: (0.05-0.5).

Preferably, the reactive hindered amine grafted propylene polymer is prepared according to the following steps:

B) Plasma treatment of the propylene polymer under an oxygen atmosphere to obtain a pretreated propylene polymer; under alkaline conditions, the pretreated propylene polymer and the reactive hindered amine are mixed and reacted in a solvent to obtain the reactive hindered amine. Grafted propylene polymer;

or,

B') Plasma treatment of the propylene polymer in an ammonia atmosphere to obtain a pre-treated propylene polymer; mix and react the pre-treated propylene polymer with a reactive hindered amine in a solvent to obtain a reactive hindered amine grafted propylene polymer things.

Preferably, the raw material components also include a toughening agent; the toughening agent is star structure SEBS.

Preferably, the propylene polymer includes homopolymer polypropylene and/or ethylene-propylene random copolymer.

Preferably, the raw material components also include one or more of nucleating agents, halogen absorbers and lubricants.

Preferably, the nucleating agent is an organic phosphate nucleating agent;

The halogen absorbent includes one or more of calcium stearate, zinc stearate and hydrotalcite;

The lubricant includes one or more of Montan E wax, oleic acid amide and erucic acid amide.

The invention provides a method for preparing the propylene polymer composition described in the above technical solution, which includes the following steps:

The raw materials used to prepare the propylene polymer composition are melt-blended and extruded to obtain the propylene polymer composition.

Compared with the prior art, the present invention provides a propylene polymer composition and a preparation method thereof. The raw material components of the propylene polymer composition provided by the invention include: 100 parts by weight of propylene polymer; 0.1-1 part by weight of reactive hindered phenol-grafted propylene polymer; 0.1-1 part by weight of reactive hindered amine-grafted propylene polymer parts; the reactive hindered phenol grafted propylene polymer is made by mixing and reacting a propylene polymer with a reactive hindered phenol after plasma treatment; the reactive hindered phenol is 2,6-bis-tert-butyl-4- [2-(2-oxiranyl)ethyl]phenol and/or 2,6-di-tert-butyl-4-[(2-oxiranyl)methyl]phenol; the reaction type is hindered Amine-grafted propylene polymer is made by mixing a propylene polymer with a reactive hindered amine after plasma treatment; the reactive hindered amine is 1-acetyl-2,2,6,6-tetramethyl-4 -[(2-oxiranyl)methoxy]piperidine and/or 1,2,2,6,6-pentamethyl-4-[(2-oxiranyl)methoxy] Piperidine. In the present invention, a propylene polymer is subjected to plasma treatment and then a hindered amine and a hindered phenol are respectively grafted, and then the graft modification is added to the propylene polymer base material, and finally a polymer with excellent electron beam irradiation resistance is obtained. The propylene polymer composition solves the problems of existing polypropylene resin materials that are easily degraded by radiation and have obvious "post-irradiation effects". In the preferred technical solution provided by the present invention, by adding star-structured SEBS as a toughening agent in the composition, the toughness of the material can be greatly improved while achieving good heat resistance, stiffness-toughness balance and welding performance, thereby further broadening the Application fields of materials.

Detailed ways

The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only some of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.

The invention provides a propylene polymer composition, whose raw material components include:

Propylene polymer 100 parts;

Reactive hindered phenol grafted propylene polymer 0.1 to 1 part;

Reactive hindered amine grafted propylene polymer 0.1 to 1 part.

In the compositions provided by the present invention, the propylene polymer preferably includes homopolypropylene and/or ethylene-propylene random copolymer. Among them, the isotacticity of the homopolymerized polypropylene is preferably ≥97%; the melt flow rate (230°C, 2.16kg) of the homopolymerized polypropylene is preferably 5 to 30g/10min, and more preferably 12 to 18g/ 10min, specifically it can be 5g/10min, 6g/10min, 7g/10min, 8g/10min, 9g/10min, 10g/10min, 11g/10min, 12g/10min, 13g/10min, 14g/10min, 15g/10min, 16g /10min, 17g/10min, 18g/10min, 19g/10min, 20g/10min, 21g/10min, 22g/10min, 23g/10min, 24g/10min, 25g/10min, 26g/10min, 27g/10min, 28g/10min , 29g/10min or 30g/10min; the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is preferably 1 to 10wt%, more preferably 5 to 7wt%, specifically 1wt%, 2wt %, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%; the melt flow rate of the ethylene-propylene random copolymer is preferably 5 to 30g/10min, more preferably It is 20~25g/10min, specifically it can be 5g/10min, 6g/10min, 7g/10min, 8g/10min, 9g/10min, 10g/10min, 11g/10min, 12g/10min, 13g/10min, 14g/10min, 15g/10min, 16g/10min, 17g/10min, 18g/10min, 19g/10min, 20g/10min, 21g/10min, 22g/10min, 23g/10min, 24g/10min, 25g/10min, 26g/10min, 27g/ 10min, 28g/10min, 29g/10min or 30g/10min; the mass ratio of the homopolymer polypropylene and the ethylene-propylene random copolymer is preferably 1: (0.1~1), more preferably 1: (0.7~0.85 ), specifically 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, 1 :0.65, 1:0.7, 1:0.75, 1:0.8, 1:0.85, 1:0.9, 1:0.95 or 1:1; the propylene polymer is preferably propylene polymer powder, and the propylene polymer powder is The average particle size is preferably 10 to 100 μm, specifically 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm or 100 μm.

In the composition provided by the present invention, the reactive hindered phenol-grafted propylene polymer is made by mixing and reacting a propylene polymer with a reactive hindered phenol after plasma treatment. Among them, the propylene polymer is preferably the propylene polymer introduced above, which will not be described in detail here; the reactive hindered phenol is 2,6-bis-tert-butyl-4-[2-(2-epoxyethyl Alkyl)ethyl]phenol and/or 2,6-bis-tert-butyl-4-[(2-oxiranyl)methyl]phenol; plasma-treated propylene polymer and reactive hindered phenol The mass ratio of 0.35, 1:0.4, 1:0.45 or 1:0.5, most preferably 1:0.1.

In the composition provided by the present invention, the reactive hindered phenol grafted propylene polymer is preferably prepared according to the following steps:

A) Plasma treatment is performed on the propylene polymer under an oxygen atmosphere to obtain a pretreated propylene polymer; under acidic conditions, the pretreated propylene polymer and the reactive hindered phenol are mixed and reacted in a solvent to obtain a reactive hindered phenol polymer. propylene polymer;

or,

A') Plasma treatment of the propylene polymer in an ammonia atmosphere to obtain a pretreated propylene polymer; mix and react the pretreated propylene polymer with a reactive hindered phenol in a solvent to obtain a reactive hindered phenol grafted propylene polymer things.

In the above preparation steps provided by the present invention, in step A), the specific operation process of the plasma treatment includes: placing the propylene polymer in a plasma reactor with a vibrator, vacuuming, and flowing in oxygen; After the oxygen is finished, the radio frequency power source is started for plasma treatment. Wherein, the vacuum degree of the vacuum is preferably 10 to 30 Pa, specifically 10 Pa, 12 Pa, 15 Pa, 17 Pa, 20 Pa, 23 Pa, 25 Pa, 27 Pa or 30 Pa; the air flow of oxygen is preferably 10 to 15 cm ³ / min, specifically it can be 10cm ³ /min, 11cm ³ /min, 12cm ³ /min, 13cm ³ /min, 14cm ³ /min or 15cm ³ /min; the oxygen ventilation time is preferably 10 to 15min, specifically it can be 10min, 11min, 12min, 13min, 14min or 15min; the discharge power of the radio frequency power source is preferably 100-500W, specifically 100W, 150W, 200W, 250W, 300W, 350W, 400W, 450W or 500W; the plasma The time for body treatment is preferably 30s to 5min, specifically 30s, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5min.

In the above preparation steps provided by the present invention, in step A), the acidic condition is preferably provided by an acidic reagent; the acidic reagent preferably includes one of sulfuric acid, aluminum trichloride, ferric chloride and zinc chloride or Various; the pH value of the acidic condition is preferably 1 to 6, specifically 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5 or 6; the solvent preferably includes cyclohexane, One or more of ethyl acetate, methyl acetate, butyl acetate, acetone, butanone and chloroform; the mass ratio of the solvent to the pretreated propylene polymer is preferably (20-100): 1, Specifically, it can be 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100:1; the temperature of the mixed reaction is preferably 50 to 70 ℃, specifically it can be 50℃, 51℃, 52℃, 53℃, 54℃, 55℃, 56℃, 57℃, 58℃, 59℃, 60℃, 61℃, 62℃, 63℃, 64℃, 65°C, 66°C, 67°C, 68°C, 69°C or 70°C; the mixing reaction time is preferably 1 to 3h, specifically 1h, 1.2h, 1.5h, 1.7h, 2h, 2.3h, 2.5 h, 2.7h or 3h.

In the above preparation steps provided by the present invention, in step A'), the specific operation process of the plasma treatment includes: placing the propylene polymer in a plasma reactor with a vibrator, vacuuming, and flowing in ammonia gas ; After the ammonia flow is completed, start the radio frequency power source for plasma treatment. Among them, the vacuum degree of the vacuum is preferably 10 to 30 Pa, specifically 10 Pa, 12 Pa, 15 Pa, 17 Pa, 20 Pa, 23 Pa, 25 Pa, 27 Pa or 30 Pa; the air flow of the ammonia gas is preferably 10 to 15 cm ³ /min, specifically it can be 10cm ³ /min, 11cm ³ /min, 12cm ³ /min, 13cm ³ /min, 14cm ³ /min or 15cm ³ /min; the ammonia ventilation time is preferably 10 to 15min, specifically It can be 10min, 11min, 12min, 13min, 14min or 15min; the discharge power of the radio frequency power source is preferably 100~500W, specifically it can be 100W, 150W, 200W, 250W, 300W, 350W, 400W, 450W or 500W; so The plasma treatment time is preferably 30s to 5min, specifically 30s, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5min.

In the above preparation steps provided by the present invention, in step A'), the solvent preferably includes one of cyclohexane, ethyl acetate, methyl acetate, butyl acetate, acetone, butanone and chloroform or Various; the mass ratio of the solvent to the pretreated propylene polymer is preferably (20-100): 1, specifically 20:1, 30:1, 40:1, 50:1, 60:1, 70: 1. 80:1, 90:1 or 100:1; the temperature of the mixed reaction is preferably 30-50°C, specifically 30°C, 32°C, 35°C, 37°C, 40°C, 42°C, 45°C , 47°C or 50°C; the mixing reaction time is preferably 1 to 3h, specifically 1h, 1.2h, 1.5h, 1.7h, 2h, 2.3h, 2.5h, 2.7h or 3h.

In the above preparation steps provided by the present invention, in steps A) and A'), after the mixing reaction is completed, the reaction product is preferably post-processed. The specific process of the post-processing preferably includes: cooling the reaction product, The precipitate is then filtered, washed and dried. Wherein, the washing method is preferably alcohol washing and water washing in sequence; the drying method is preferably vacuum drying; and the drying time is preferably 3 to 5 hours.

In the composition provided by the invention, based on the content of propylene polymer in the raw material components being 100 parts by weight, the content of the reactive hindered phenol grafted propylene polymer in the raw material components is 0.1 to 1 part by weight. , specifically it can be 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight or 1 part by weight.

In the composition provided by the present invention, the reactive hindered amine-grafted propylene polymer is made by mixing and reacting a propylene polymer with a reactive hindered amine after plasma treatment. Among them, the propylene polymer is preferably the propylene polymer introduced above, which will not be described in detail here; the reactive hindered amine is 1-acetyl-2,2,6,6-tetramethyl-4-[ (2-oxiranyl)methoxy]piperidine and/or 1,2,2,6,6-pentamethyl-4-[(2-oxiranyl)methoxy]piperidine ; The mass ratio of propylene polymer and reactive hindered amine after plasma treatment is preferably 1: (0.05~0.5), specifically 1:0.05, 1:0.07, 1:0.1, 1:0.12, 1:0.15 , 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45 or 1:0.5, the most preferred is 1:0.1.

In the composition provided by the present invention, the reactive hindered amine grafted propylene polymer is preferably prepared according to the following steps:

B) Plasma treatment of the propylene polymer under an oxygen atmosphere to obtain a pretreated propylene polymer; under alkaline conditions, the pretreated propylene polymer and the reactive hindered amine are mixed and reacted in a solvent to obtain the reactive hindered amine. Grafted propylene polymer;

or,

B') Plasma treatment of the propylene polymer in an ammonia atmosphere to obtain a pre-treated propylene polymer; mix and react the pre-treated propylene polymer with a reactive hindered amine in a solvent to obtain a reactive hindered amine grafted propylene polymer things.

In the above preparation steps provided by the present invention, in step B), the specific operation process of the plasma treatment includes: placing the propylene polymer in a plasma reactor with a vibrator, evacuating, and flowing in oxygen; After the oxygen is finished, the radio frequency power source is started for plasma treatment. Wherein, the vacuum degree of the vacuum is preferably 10 to 30 Pa, specifically 10 Pa, 12 Pa, 15 Pa, 17 Pa, 20 Pa, 23 Pa, 25 Pa, 27 Pa or 30 Pa; the air flow of oxygen is preferably 10 to 15 cm ³ / min, specifically it can be 10cm ³ /min, 11cm ³ /min, 12cm ³ /min, 13cm ³ /min, 14cm ³ /min or 15cm ³ /min; the oxygen ventilation time is preferably 10 to 15min, specifically it can be 10min, 11min, 12min, 13min, 14min or 15min; the discharge power of the radio frequency power source is preferably 100-500W, specifically 100W, 150W, 200W, 250W, 300W, 350W, 400W, 450W or 500W; the plasma The time for body treatment is preferably 30s to 5min, specifically 30s, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5min.

In the above preparation steps provided by the present invention, in step B), the alkaline condition is preferably provided by an alkaline reagent; the alkaline reagent preferably includes sodium hydroxide and/or potassium hydroxide; the alkaline condition is The pH value is preferably 8 to 11, specifically 8, 8.5, 9, 9.5, 10, 10.5 or 11; the solvent preferably includes one or more of cyclohexane, acetone, methyl ethyl ketone and chloroform; The mass ratio of the solvent to the pretreated propylene polymer is preferably (20-100):1, specifically 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80 :1, 90:1 or 100:1; the temperature of the mixed reaction is preferably 50-70°C, specifically 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C , 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C or 70°C; the mixing reaction time is preferably 1 to 3h, specifically it can be 1h, 1.2h, 1.5h, 1.7h, 2h, 2.3h, 2.5h, 2.7h or 3h.

In the above preparation steps provided by the present invention, in step B'), the specific operation process of the plasma treatment includes: placing the propylene polymer in a plasma reactor with a vibrator, vacuuming, and flowing in ammonia gas ; After the ammonia flow is completed, start the radio frequency power source for plasma treatment. Among them, the vacuum degree of the vacuum is preferably 10 to 30 Pa, specifically 10 Pa, 12 Pa, 15 Pa, 17 Pa, 20 Pa, 23 Pa, 25 Pa, 27 Pa or 30 Pa; the air flow of the ammonia gas is preferably 10 to 15 cm ³ /min, specifically it can be 10cm ³ /min, 11cm ³ /min, 12cm ³ /min, 13cm ³ /min, 14cm ³ /min or 15cm ³ /min; the ammonia ventilation time is preferably 10 to 15min, specifically It can be 10min, 11min, 12min, 13min, 14min or 15min; the discharge power of the radio frequency power source is preferably 100~500W, specifically it can be 100W, 150W, 200W, 250W, 300W, 350W, 400W, 450W or 500W; so The plasma treatment time is preferably 30s to 5min, specifically 30s, 1min, 1.5min, 2min, 2.5min, 3min, 3.5min, 4min, 4.5min or 5min.

In the above preparation steps provided by the present invention, in step B'), the solvent preferably includes one or more of cyclohexane, acetone, methyl ethyl ketone and chloroform; the solvent and the pretreated propylene polymer The mass ratio is preferably (20-100): 1, specifically 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100: 1; The temperature of the mixed reaction is preferably 30 to 50°C, specifically 30°C, 32°C, 35°C, 37°C, 40°C, 42°C, 45°C, 47°C or 50°C; the temperature of the mixed reaction The time is preferably 1 to 3h, specifically 1h, 1.2h, 1.5h, 1.7h, 2h, 2.3h, 2.5h, 2.7h or 3h.

In the above preparation steps provided by the present invention, in steps B) and B'), after the mixing reaction is completed, the reaction product is preferably post-processed. The specific process of the post-processing preferably includes: cooling the reaction product, The precipitate is then filtered, washed and dried. Wherein, the washing method is preferably alcohol washing and water washing in sequence; the drying method is preferably vacuum drying; and the drying time is preferably 3 to 5 hours.

In the composition provided by the present invention, based on the content of propylene polymer in the raw material components being 100 parts by weight, the content of the reactive hindered amine grafted propylene polymer in the raw material components is 0.1 to 1 part by weight. , specifically it can be 0.1 part by weight, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, 0.9 part by weight or 1 part by weight.

In the composition provided by the present invention, the raw material components preferably further include a toughening agent; the toughening agent is preferably a star structure SEBS, more preferably a three-arm star structure SEBS and/or a four-arm star structure. SEBS, most preferably four-arm star structure SEBS; the melt flow rate (200°C, 5kg) of the star structure SEBS is preferably 0.1 to 5g/10min, more preferably 1 to 2g/10min, specifically 0.1 or 5g/10min; the styrene content of the star structure SEBS is preferably 5 to 30wt%, more preferably 10 to 15wt%, specifically 5wt%, 7wt%, 10wt%, 12wt%, 15wt%, 17wt%, 20wt%, 23wt%, 25wt%, 27wt% or 30wt%.

In the composition provided by the present invention, based on the content of propylene polymer in the raw material components being 100 parts by weight, the content of the toughening agent in the raw material components is preferably 5 to 15 parts by weight, specifically 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight or 15 parts by weight.

In the composition provided by the present invention, the raw material components preferably further include a nucleating agent; the nucleating agent is preferably an organic phosphate nucleating agent, and more preferably is an organic phosphate metal salt or an organic phosphate metal salt. The compound, alkali metal organophosphate salt or a compound of alkali metal organophosphate salt is most preferably one of nucleating agent NA-21, nucleating agent NA-11 and nucleating agent TMP-6 or There are many, the most preferred are nucleating agent NA-21 or nucleating agent TMP-6.

In the composition provided by the present invention, based on 100 parts by weight of the propylene polymer in the raw material components, the content of the nucleating agent in the raw material components is preferably 0.01 to 0.5 parts by weight, specifically 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.15 parts by weight, 0.2 parts by weight, 0.25 parts by weight, 0.3 parts by weight, 0.35 parts by weight, 0.4 parts by weight, 0.45 parts by weight or 0.5 parts by weight.

In the composition provided by the present invention, the raw material components preferably further include a halogen absorber; the halogen absorber preferably includes one or more of calcium stearate, zinc stearate and hydrotalcite, more preferably It is calcium stearate.

In the composition provided by the present invention, based on 100 parts by weight of the propylene polymer in the raw material components, the content of the halogen absorber in the raw material components is preferably 0.01 to 0.2 parts by weight, specifically 0.01 parts by weight, 0.02 parts by weight, 0.05 parts by weight, 0.07 parts by weight, 0.1 parts by weight, 0.12 parts by weight, 0.15 parts by weight, 0.17 parts by weight or 0.2 parts by weight.

In the composition provided by the present invention, the raw material component preferably further includes a lubricant; the lubricant preferably includes one or more of Montan wax E wax, oleic acid amide and erucic acid amide, and more preferably Montan wax E wax.

In the composition provided by the present invention, based on the content of the propylene polymer in the raw material components being 100 parts by weight, the content of the lubricant in the raw material components is preferably 0.05 to 0.15 parts by weight, specifically 0.05 parts by weight. part, 0.06 part by weight, 0.07 part by weight, 0.08 part by weight, 0.09 part by weight, 0.1 part by weight, 0.11 part by weight, 0.12 part by weight, 0.13 part by weight, 0.14 part by weight or 0.15 part by weight.

The present invention also provides a method for preparing the propylene polymer composition described in the above technical solution, which includes the following steps:

The raw materials used to prepare the propylene polymer composition are melt-blended and extruded to obtain the propylene polymer composition.

In the preparation method provided by the present invention, the raw materials are preferably premixed before being melt-blended; the premixing is preferably performed in a high-speed mixer.

In the preparation method provided by the present invention, the melt blending extrusion is preferably performed in a twin-screw extruder; the temperature from the feeding section to the die when the twin-screw extruder is running is preferably 125 to 210°C; The temperature of the machine head and die when the twin-screw extruder is running is preferably 200-210°C; the screw speed of the main engine when the twin-screw extruder is running is 100-150 r/min.

The technical solution provided by the present invention is to graft a hindered amine and a hindered phenol respectively after plasma treatment on the propylene polymer, and then add the graft modification to the propylene polymer base material, and finally obtain a polymer with excellent electron beam resistance. The propylene polymer composition with irradiation properties solves the problems of easy degradation by irradiation and obvious "post-irradiation effect" existing in existing polypropylene resin materials. More specifically, the technical solution provided by the present invention uses plasma to treat propylene polymer and graft hindered amines and hindered phenols onto the main chain of the propylene polymer, so that the hindered amines and hindered phenols can enter the crystalline region of the propylene polymer. , effectively eliminate free radicals trapped in the crystal area of propylene polymer, reduce the "post-irradiation effect", improve radiation resistance, reduce migration, and maintain color. In addition, in the preferred technical solution provided by the present invention, star structure SEBS is added as a toughening agent in the composition. Compared with linear structure SEBS, star structure SEBS has more physical cross-linking points and the star arms are easier to It is in an anchored state, so the amount of addition can be reduced with the same toughening effect. Therefore, using star-shaped structure SEBS as a toughening agent can greatly improve the toughness of the material while better maintaining the rigidity, heat resistance and welding performance of the material. , thereby further broadening the applicable fields of the material.

For greater clarity, detailed description is provided below through the following examples and comparative examples. Among them, Comparative Examples 1 to 6 correspond to Examples 1 to 6 respectively. The difference is that in Comparative Examples 1 to 6, non-reactive hindered phenols and hindered amines are added to the system in the form of blends; Examples 7 to 8 The purpose is to compare with Example 6. The difference is that Examples 7 to 8 use linear structure SEBS for toughening. The SEBS addition amount of Example 7 and Example 6 is the same. The impact strength of Example 8 and Example 6 is the same. Under basically the same circumstances, the amount of SEBS added is much higher than that in Example 6.

Example 1

Place 100g of homopolypropylene (melt flow rate 18g/10min, isotacticity 98%, average particle size 10μm) in a plasma reactor equipped with a vibrator, evacuate it to 10Pa, and introduce oxygen for 10min. The oxygen flow rate is 10cm ³ /min; start the radio frequency power source, adjust the discharge power to 100W and process for 5 minutes to obtain plasma pretreated polypropylene.

Mix 10g of plasma pretreated polypropylene, 200g of butanone, and 1g of 2,6-bis-tert-butyl-4-[2-(2-oxiranyl)ethyl]phenol, and add chlorine to the mixed system Adjust the pH value to 6 with zinc, react for 1 hour at 50°C, then cool to room temperature, filter the precipitate, wash the precipitate 3 times with ethanol, rinse 3 times with deionized water, and dry under vacuum for 3 hours to obtain the interface. Branch-reactive hindered phenol polypropylene.

Mix 10g of plasma pretreated polypropylene, 200g of acetone, and 1g of 1-acetyl-2,2,6,6-tetramethyl-4-[(2-oxiranyl)methoxy]piperidine , add sodium hydroxide to the mixed system to adjust the pH value to 8, react at 50°C for 3 hours, then cool to room temperature, filter the precipitate, wash the precipitate 3 times with ethanol, and then rinse 3 times with deionized water. Dry under vacuum for 3 hours to obtain graft-reactive hindered amine polypropylene.

10kg (melt flow rate 18g/10min, isotacticity 98%, average particle size 10μm), 10g graft-reactive hindered phenol polypropylene, 10g graft-reactive hindered amine polypropylene, 1g NA-21 nucleating agent, 1g calcium stearate, 5g Mondan wax E wax, 1.5kg four-arm star structure SEBS (melt flow rate 1g/10min, styrene content 10%) were added to the high-speed mixer to premix, and then the premixed resin was added Melt and blend extrusion in a twin-screw to obtain a propylene polymer composition. The temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, and the temperature of the machine head and die is 210°C. The main screw speed is 100r/min.

Example 2

Put 1000g of ethylene-propylene random copolymer (melt flow rate 20g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 5wt%, the average particle size is 100μm), as for the vibrator In the plasma reactor, after vacuuming to 30Pa, oxygen was introduced for 15 minutes, and the oxygen flow rate was 15cm ³ /min; the radio frequency power source was started, and the discharge power was adjusted to 500W for 30 seconds to obtain plasma pretreated polypropylene.

Mix 200g of plasma pretreated polypropylene, 20000g of cyclohexane, and 20g of 2,6-bis-tert-butyl-4-[(2-oxiranyl)methyl]phenol, and add chlorine to the mixed system. Adjust the pH value of zinc to 1, react at 70°C for 1 hour, then cool to room temperature, filter the precipitate, wash the precipitate 3 times with ethanol, rinse 3 times with deionized water, and dry under vacuum for 3 hours to obtain grafting Reactive hindered phenol polypropylene.

Mix 200g of plasma pretreated polypropylene, 20000g of cyclohexane, and 20g of 1,2,2,6,6-pentamethyl-4-[(2-oxiranyl)methoxy]piperidine, Add sodium hydroxide to the mixed system to adjust the pH value to 11, react at 70°C for 1 hour, then cool to room temperature, filter the precipitate, wash the precipitate 3 times with ethanol, and then rinse 3 times with deionized water, and place in a vacuum Dry for 3 hours to obtain graft-reactive hindered amine polypropylene.

10kg ethylene-propylene random copolymer (melt flow rate 20g/10min, content of structural units corresponding to ethylene monomer in the ethylene-propylene random copolymer is 5wt%, average particle size 100μm), 100g graft reaction type Hindered phenol polypropylene, 100g graft-reactive hindered amine polypropylene, 50g TMP-6 nucleating agent, 20g calcium stearate, 15g Mondan wax E wax, 500g four-arm star structure SEBS (melt flow rate 2g/10min , styrene content 15%) is added to the high-speed mixer for premixing, and then the premixed resin is added to the twin-screw for melt blending and extrusion to obtain a propylene polymer composition. The temperature of each zone of the extruder is set to: the temperature of the feeding section The temperature of other sections is 210°C, the temperature of the machine head and die is 210°C, and the main screw speed is 100r/min.

Example 3

70g of ethylene-propylene random copolymer (melt flow rate 25g/10min, content of structural units corresponding to ethylene monomer in the ethylene-propylene random copolymer is 7wt%, average particle size 50μm), 100g homopolymerized polypropylene (Melt flow rate 12g/10min, isotacticity 97%, average particle size 50μm) After mixing evenly, place it in a plasma reactor with a vibrator. After vacuuming to 20Pa, oxygen is introduced for 12min, and the oxygen flow rate is 12cm ³ /min; start the radio frequency power source, adjust the discharge power to 200W and process for 2 minutes to obtain plasma pretreated polypropylene.

Combine 100g plasma pretreated polypropylene, 5000g cyclohexane, 5g 2,6-bis-tert-butyl-4-[2-(2-oxiranyl)ethyl]phenol, 5g 2,6-bis-tert-butyl 4-[(2-oxiranyl)methyl]phenol was mixed, zinc chloride was added to the mixed system to adjust the pH value to 3, react at 60°C for 2 hours, and then cooled to room temperature to filter the precipitate. , wash the precipitate 3 times with ethanol, rinse 3 times with deionized water, and dry under vacuum for 3 hours to obtain graft-reactive hindered phenol polypropylene.

100g plasma pre-treated polypropylene, 5000g cyclohexane, 5g 1-acetyl-2,2,6,6-tetramethyl-4-[(2-oxiranyl)methoxy]piperidine , 5g of 1,2,2,6,6-pentamethyl-4-[(2-oxiranyl)methoxy]piperidine were mixed, and potassium hydroxide was added to the mixed system to adjust the pH value to 10 , react at 60°C for 2 hours, then cool to room temperature, filter the precipitate, wash the precipitate 3 times with ethanol, rinse 3 times with deionized water, and dry under vacuum for 3 hours to obtain graft-reactive hindered amine polypropylene. .

7kg ethylene-propylene random copolymer (melt flow rate 25g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 7wt%), 10kg homopolymer polypropylene (melt flow rate 12g/10min, isotacticity 97%), 85g graft-reactive hindered phenol polypropylene, 85g graft-reactive hindered amine polypropylene, 17g TMP-6 nucleating agent, 5g calcium stearate, 20g Mondan wax E wax , 1.7kg four-arm star structure SEBS (melt flow rate 1.5g/10min, styrene content 13%) is added to the high-speed mixer for premixing, and then the premixed resin is added to the twin-screw for melting, blending and extrusion to obtain propylene For the polymer composition, the temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, the temperature of the machine head and die is 210°C, and the main screw speed is 100r/min.

Example 4

280g ethylene-propylene random copolymer (melt flow rate 23g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 6wt%, the average particle size is 50μm), 400g homopolymerized polypropylene (Melt flow rate 15g/10min, isotacticity 97%, average particle size 50μm) After mixing evenly, place it in a plasma reactor with a vibrator. After vacuuming to 20Pa, ammonia gas is introduced for 12min. The ammonia gas flow rate is 12cm ³ /min; start the radio frequency power source, adjust the discharge power to 200W and process for 2 minutes to obtain plasma pretreated polypropylene.

Combine 200g plasma pretreated polypropylene, 4000g cyclohexane, 10g 2,6-bis-tert-butyl-4-[2-(2-oxiranyl)ethyl]phenol, 10g 2,6-bis-tert-butyl Butyl-4-[(2-oxiranyl)methyl]phenol was mixed, reacted at 30°C for 3 hours, then cooled to room temperature, filtered the precipitate, washed the precipitate 3 times with ethanol, and then used it Rinse with ionized water three times and dry under vacuum for 3 hours to obtain graft-reactive hindered phenol polypropylene.

200g plasma pre-treated polypropylene, 4000g cyclohexane, 10g 1-acetyl-2,2,6,6-tetramethyl-4-[(2-oxiranyl)methoxy]piperidine , 10g of 1,2,2,6,6-pentamethyl-4-[(2-oxiranyl)methoxy]piperidine were mixed, reacted at 30°C for 3 hours, then cooled to room temperature and filtered The precipitate was washed three times with ethanol, rinsed three times with deionized water, and dried under vacuum for 3 hours to obtain graft-reactive hindered amine polypropylene.

7kg ethylene-propylene random copolymer (melt flow rate 23g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 6wt%), 10kg homopolymer polypropylene (melt flow rate 15g/10min, isotacticity 97%), 170g graft-reactive hindered phenol polypropylene, 170g graft-reactive hindered amine polypropylene, 17g TMP-6 nucleating agent, 5g calcium stearate, 20g Montan wax E Wax and 1.7kg four-arm star structure SEBS (melt flow rate 1.5g/10min, styrene content 13%) were added to a high-speed mixer for premixing, and then the premixed resin was added to the twin-screw for melting, blending and extrusion to obtain For propylene polymer composition, the temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, the temperature of the machine head and die is 210°C, and the main screw speed is 100r/min.

Example 5

340g of ethylene-propylene random copolymer (melt flow rate 23g/10min, content of structural units corresponding to ethylene monomer in the ethylene-propylene random copolymer is 6wt%, average particle size 50μm), 400g homopolymerized polypropylene (Melt flow rate 15g/10min, isotacticity 97%, average particle size 50μm) After mixing evenly, place it in a plasma reactor with a vibrator. After vacuuming to 20Pa, ammonia gas is introduced for 12min. The ammonia gas flow rate is 12cm ³ /min; start the radio frequency power source, adjust the discharge power to 200W and process for 2 minutes to obtain plasma pretreated polypropylene.

Combine 200g plasma pretreated polypropylene, 4000g cyclohexane, 10g 2,6-bis-tert-butyl-4-[2-(2-oxiranyl)ethyl]phenol, 10g 2,6-bis-tert-butyl 4-[(2-oxiranyl)methyl]phenol was mixed, reacted at 50°C for 1 hour, then cooled to room temperature, filtered the precipitate, washed the precipitate 3 times with ethanol, and then used deionization Rinse with water three times and dry under vacuum for 3 hours to obtain graft-reactive hindered phenol polypropylene.

200g plasma pre-treated polypropylene, 4000g cyclohexane, 10g 1-acetyl-2,2,6,6-tetramethyl-4-[(2-oxiranyl)methoxy]piperidine, 10g of 1,2,2,6,6-pentamethyl-4-[(2-oxiranyl)methoxy]piperidine were mixed, reacted at 50°C for 1 hour, and then cooled to room temperature to filter the precipitate. , wash the precipitate 3 times with ethanol, rinse 3 times with deionized water, and dry under vacuum for 3 hours to obtain graft-reactive hindered amine polypropylene.

8.5kg of ethylene-propylene random copolymer (melt flow rate 23g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 6wt%), 10kg homopolypropylene (melt flow Rate 15g/10min, isotacticity 97%), 185g graft-reactive hindered phenol polypropylene, 185g graft-reactive hindered amine polypropylene, 18.5g TMP-6 nucleating agent, 5.5g calcium stearate, 22g mondan Wax E wax and 1.85kg four-arm star structure SEBS (melt flow rate 1.5g/10min, styrene content 13%) are added to the high-speed mixer for premixing, and then the premixed resin is added to the twin-screw for melt blending and extrusion , to obtain the propylene polymer composition, the temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, the temperature of the die and die is 210°C, and the main screw speed is 100r/min.

Example 6

320g of ethylene-propylene random copolymer (melt flow rate 23g/10min, content of structural units corresponding to ethylene monomer in the ethylene-propylene random copolymer is 6wt%, average particle size 50μm), 400g homopolymerized polypropylene (Melt flow rate 15g/10min, isotacticity 97%, average particle size 50μm) After mixing evenly, place it in a plasma reactor with a vibrator. After vacuuming to 20Pa, ammonia gas is introduced for 12min. The ammonia gas flow rate is 12cm ³ /min; start the radio frequency power source, adjust the discharge power to 200W and process for 2 minutes to obtain plasma pretreated polypropylene.

Combine 200g plasma pretreated polypropylene, 4000g cyclohexane, 10g 2,6-bis-tert-butyl-4-[2-(2-oxiranyl)ethyl]phenol, 10g 2,6-bis-tert-butyl 4-[(2-oxiranyl)methyl]phenol was mixed, reacted at 50°C for 1 hour, then cooled to room temperature, filtered the precipitate, washed the precipitate 3 times with ethanol, and then used deionization Rinse with water three times and dry under vacuum for 3 hours to obtain graft-reactive hindered phenol polypropylene.

200g plasma pre-treated polypropylene, 4000g cyclohexane, 10g 1-acetyl-2,2,6,6-tetramethyl-4-[(2-oxiranyl)methoxy]piperidine , 10g of 1,2,2,6,6-pentamethyl-4-[(2-oxiranyl)methoxy]piperidine were mixed, reacted at 50°C for 1 hour, and then cooled to room temperature and filtered to precipitate. The precipitate was washed three times with ethanol, rinsed three times with deionized water, and dried under vacuum for 3 hours to obtain graft-reactive hindered amine polypropylene.

8kg ethylene-propylene random copolymer (melt flow rate 23g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 6wt%), 10kg homopolymer polypropylene (melt flow rate 15g/10min, isotacticity 97%), 180g graft-reactive hindered phenol polypropylene, 180g graft-reactive hindered amine polypropylene, 18g TMP-6 nucleating agent, 5.3g calcium stearate, 21g Montan wax E Wax and 1.8kg four-arm star structure SEBS (melt flow rate 1.5g/10min, styrene content 13%) were added to a high-speed mixer for premixing, and then the premixed resin was added to the twin-screw for melting, blending and extrusion to obtain For propylene polymer composition, the temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, the temperature of the machine head and die is 210°C, and the main screw speed is 100r/min.

Example 7

320g of ethylene-propylene random copolymer (melt flow rate 23g/10min, content of structural units corresponding to ethylene monomer in the ethylene-propylene random copolymer is 6wt%, average particle size 50μm), 400g homopolymerized polypropylene (Melt flow rate 15g/10min, isotacticity 97%, average particle size 50μm) After mixing evenly, place it in a plasma reactor with a vibrator. After vacuuming to 20Pa, ammonia gas is introduced for 12min. The ammonia gas flow rate is 12cm ³ /min; start the radio frequency power source, adjust the discharge power to 200W and process for 2 minutes to obtain plasma pretreated polypropylene.

Combine 200g plasma pretreated polypropylene, 4000g cyclohexane, 10g 2,6-bis-tert-butyl-4-[2-(2-oxiranyl)ethyl]phenol, 10g 2,6-bis-tert-butyl 4-[(2-oxiranyl)methyl]phenol was mixed, reacted at 50°C for 1 hour, then cooled to room temperature, filtered the precipitate, washed the precipitate 3 times with ethanol, and then used deionization Rinse with water three times and dry under vacuum for 3 hours to obtain graft-reactive hindered phenol polypropylene.

200g plasma pre-treated polypropylene, 4000g cyclohexane, 10g 1-acetyl-2,2,6,6-tetramethyl-4-[(2-oxiranyl)methoxy]piperidine , 10g of 1,2,2,6,6-pentamethyl-4-[(2-oxiranyl)methoxy]piperidine were mixed, reacted at 50°C for 1 hour, and then cooled to room temperature and filtered to precipitate. The precipitate was washed three times with ethanol, rinsed three times with deionized water, and dried under vacuum for 3 hours to obtain graft-reactive hindered amine polypropylene.

8kg ethylene-propylene random copolymer (melt flow rate 23g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 6wt%), 10kg homopolymer polypropylene (melt flow rate 15g/10min, isotacticity 97%), 180g graft-reactive hindered phenol polypropylene, 180g graft-reactive hindered amine polypropylene, 18g TMP-6 nucleating agent, 5.3g calcium stearate, 21g Montan wax E Wax and 1.8kg linear structure SEBS (melt flow rate 1.5g/10min, styrene content 13%) are added to the high-speed mixer for premixing, and then the premixed resin is added to the twin-screw for melting, blending and extrusion to obtain propylene polymerization The temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, the temperature of the machine head and die is 210°C, and the main screw speed is 100r/min.

Example 8

320g of ethylene-propylene random copolymer (melt flow rate 23g/10min, content of structural units corresponding to ethylene monomer in the ethylene-propylene random copolymer is 6wt%, average particle size 50μm), 400g homopolymerized polypropylene (Melt flow rate 15g/10min, isotacticity 97%, average particle size 50μm) After mixing evenly, place it in a plasma reactor with a vibrator. After vacuuming to 20Pa, ammonia gas is introduced for 12min. The ammonia gas flow rate is 12cm ³ /min; start the radio frequency power source, adjust the discharge power to 200W and process for 2 minutes to obtain plasma pretreated polypropylene.

Combine 200g plasma pretreated polypropylene, 4000g cyclohexane, 10g 2,6-bis-tert-butyl-4-[2-(2-oxiranyl)ethyl]phenol, 10g 2,6-bis-tert-butyl 4-[(2-oxiranyl)methyl]phenol was mixed, reacted at 50°C for 1 hour, then cooled to room temperature, filtered the precipitate, washed the precipitate 3 times with ethanol, and then used deionization Rinse with water three times and dry under vacuum for 3 hours to obtain graft-reactive hindered phenol polypropylene.

200g plasma pre-treated polypropylene, 4000g cyclohexane, 10g 1-acetyl-2,2,6,6-tetramethyl-4-[(2-oxiranyl)methoxy]piperidine , 10g of 1,2,2,6,6-pentamethyl-4-[(2-oxiranyl)methoxy]piperidine were mixed, reacted at 50°C for 1 hour, and then cooled to room temperature and filtered to precipitate. The precipitate was washed three times with ethanol, rinsed three times with deionized water, and dried under vacuum for 3 hours to obtain graft-reactive hindered amine polypropylene.

8kg ethylene-propylene random copolymer (melt flow rate 23g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 6wt%), 10kg homopolymer polypropylene (melt flow rate 15g/10min, isotacticity 97%), 180g graft-reactive hindered phenol polypropylene, 180g graft-reactive hindered amine polypropylene, 18g TMP-6 nucleating agent, 5.3g calcium stearate, 21g Montan wax E Wax and 3.9kg four-arm star structure SEBS (melt flow rate 1.5g/10min, styrene content 13%) were added to a high-speed mixer for premixing, and then the premixed resin was added to the twin-screw for melting, blending and extrusion to obtain For propylene polymer composition, the temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, the temperature of the machine head and die is 210°C, and the main screw speed is 100r/min.

Comparative example 1

Combine 10.02kg (melt flow rate 18g/10min, isotacticity 98%, average particle size 10μm), 1g hindered phenol antioxidant 1790, 1g hindered amine light stabilizer 944, 1g NA-21 nucleating agent, 1g stearin Calcium acid, 5g Montan wax E wax, 1.5kg four-arm star structure SEBS (melt flow rate 1g/10min, styrene content 10%) were added to the high-speed mixer to premix, and then the premixed resin was added to the twin-screw Melt blending and extrusion to obtain a propylene polymer composition. The temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, the temperature of the machine head and die is 210°C, and the main screw speed is is 100r/min.

Comparative example 2

10.2kg ethylene-propylene random copolymer (melt flow rate 20g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 5wt%, the average particle size is 100μm), 10g hindered phenol resistance Oxygen agent 1790, 10g hindered amine light stabilizer 944, 50g TMP-6 nucleating agent, 20g calcium stearate, 15g Mondan wax E wax, 500g four-arm star structure SEBS (melt flow rate 2g/10min, styrene Content 15%) is added to the high-speed mixer for premixing, and then the premixed resin is added to the twin-screw for melting, blending and extrusion to obtain a propylene polymer composition. The temperature of each zone of the extruder is set to: the temperature of the feeding section is 125°C. , the temperature of other sections is 210℃, the temperature of the machine head and die is 210℃, and the main screw speed is 100r/min.

Comparative example 3

7.07kg ethylene-propylene random copolymer (melt flow rate 25g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 7wt%), 10.1kg homopolypropylene (melt Flow rate 12g/10min, isotacticity 97%), 8.5g hindered phenol antioxidant 1790, 8.5g hindered amine light stabilizer 944, 17g TMP-6 nucleating agent, 5g calcium stearate, 20g Montan wax E wax , 1.7kg four-arm star structure SEBS (melt flow rate 1.5g/10min, styrene content 13%) is added to the high-speed mixer for premixing, and then the premixed resin is added to the twin-screw for melting, blending and extrusion to obtain propylene For the polymer composition, the temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, the temperature of the machine head and die is 210°C, and the main screw speed is 100r/min.

Comparative example 4

7.14kg ethylene-propylene random copolymer (melt flow rate 23g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 6wt%), 10.2kg homopolypropylene (melt Flow rate 15g/10min, isotacticity 97%), 17g hindered phenol antioxidant 1790, 17g hindered amine light stabilizer 944, 17g TMP-6 nucleating agent, 5g calcium stearate, 20g Mondan wax E wax, 1.7 kg four-arm star structure SEBS (melt flow rate 1.5g/10min, styrene content 13%) is added to the high-speed mixer for premixing, and then the premixed resin is added to the twin-screw for melting, blending and extrusion to obtain a propylene polymer For the composition, the temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, the temperature of the machine head and die is 210°C, and the host screw speed is 100r/min.

Comparative example 5

8.67kg ethylene-propylene random copolymer (melt flow rate 23g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 6wt%), 10.2kg homopolypropylene (melt Flow rate 15g/10min, isotacticity 97%), 18.5g hindered phenol antioxidant 1790, 18.5g hindered amine light stabilizer 944, 18.5g TMP-6 nucleating agent, 5.5g calcium stearate, 22g montan wax E wax and 1.85kg four-arm star structure SEBS (melt flow rate 1.5g/10min, styrene content 13%) are added to the high-speed mixer for premixing, and then the premixed resin is added to the twin-screw for melt blending and extrusion. The propylene polymer composition was obtained. The temperature of each zone of the extruder was set as follows: the temperature of the feeding section was 125°C, the temperature of other sections was 210°C, the temperature of the die and die was 210°C, and the main screw speed was 100r/min.

Comparative example 6

8.16kg ethylene-propylene random copolymer (melt flow rate 23g/10min, the content of the structural unit corresponding to the ethylene monomer in the ethylene-propylene random copolymer is 6wt%), 10.2kg homopolypropylene (melt Flow rate 15g/10min, isotacticity 97%), 18g hindered phenol antioxidant 1790, 18g hindered amine light stabilizer 944, 18g TMP-6 nucleating agent, 5.3g calcium stearate, 21g Montan wax E wax, 1.8kg four-arm star structure SEBS (melt flow rate 1.5g/10min, styrene content 13%) is added to the high-speed mixer for premixing, and then the premixed resin is added to the twin-screw for melting, blending and extrusion to obtain propylene polymerization The temperature of each zone of the extruder is set as follows: the temperature of the feeding section is 125°C, the temperature of other sections is 210°C, the temperature of the machine head and die is 210°C, and the main screw speed is 100r/min.

Performance Testing

(1) The test samples prepared from the propylene polymer compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were subjected to electron beam irradiation at a dose of 50 kGy, and the simple-supported beam notched impact strength and tensile strength were measured. , elongation at break and yellow index test. In order to compare and illustrate the advantages of the present invention in reducing post-irradiation effects, we stored the irradiated test samples under the same conditions for one year and tested them again. The results are as shown in the table Shown in 1～2:

Table 150kGy dose performance comparison test 2 days after electron beam irradiation

project Izod notched impact strength Tensile Strength Elongation at break yellow index unit kJ/m ² MPa / / Example 1 21.2 33.1 300% 2.1 Example 2 9.8 26.4 800% 2.1 Example 3 15.4 30.6 700% 2.0 Example 4 15.2 30.4 700% 2.1 Example 5 15.1 28.3 750% 2.0 Example 6 15.3 29.7 650% 2.0 Comparative example 1 18.9 32 260% 4.5 Comparative example 2 9.2 25 740% 4.4 Comparative example 3 13.3 29 640% 4.4 Comparative example 4 13.2 29 640% 4.6 Comparative example 5 13.2 27 710% 4.3 Comparative example 6 13.4 28 620% 4.2

Table 2 1-year performance comparison test after electron beam irradiation at a dose of 250 kGy

project Izod notched impact strength Tensile Strength Elongation at break yellow index unit J/m ² MPa / / Example 1 19.8 32 290% 2.2 Example 2 9.5 25 780% 2.2 Example 3 14.9 29 680% 2.1 Example 4 14.8 29 680% 2.2 Example 5 14.8 27 730% 2.1 Example 6 15 28 630% 2.1 Comparative example 1 14.2 32 100% 7.7 Comparative example 2 5.1 25 300% 7.6 Comparative example 3 9.4 29 210% 7.6 Comparative example 4 9.3 29 210% 7.8 Comparative example 5 9.0 27 220% 7.5 Comparative example 6 9.2 28 200% 7.4

It can be seen from Table 1 and Table 2 that the propylene polymer composition of the comparative example has the properties of impact strength, tensile strength, elongation at break, and yellow index after 2 days and 1 year after being irradiated with a dose of 50 kGy electron beam. are worse than the corresponding examples, especially the corresponding performance indicators dropped significantly after one year of irradiation, while the performance indicators of the examples dropped very little, which shows that the method of the present invention can solve the problems existing in the existing polypropylene resin materials. It is easily degraded by irradiation and has very obvious advantages in terms of "post-irradiation effect".

(2) Test the simple beam notched impact strength, tensile strength, flexural modulus and load thermal deformation temperature on the test specimens prepared from the propylene polymer compositions prepared in Examples 6 to 8. The results are as shown in Table 3 Shown:

Table 3 Differences in physical properties between Example 6 and Examples 7 and 8 without electron beam irradiation

project Izod notched impact strength Tensile Strength Flexural modulus Load heat distortion temperature unit kJ/m ² MPa MPa ℃ Example 6 15.5 29.6 1250 98 Example 7 6.1 28 1200 95 Example 8 15.4 25.1 900 65

It can be seen from Table 3 that the method of using the star structure SEBS provided by the present invention as a toughening agent can greatly improve the toughness of the material while better maintaining the rigidity, heat resistance and welding performance of the material, thereby further broadening the scope of the material. applicable fields.

The above are only preferred embodiments of the present invention. It should be noted that those skilled in the art can make several improvements and modifications without departing from the principles of the present invention. These improvements and modifications can also be made. should be regarded as the protection scope of the present invention.

Claims (9)

1. The propylene polymer composition comprises the following raw materials in parts by weight:

100 parts of propylene polymer;

0.1 to 1 portion of reactive hindered phenol grafted propylene polymer;

0.1 to 1 portion of reactive hindered amine grafted propylene polymer;

5-15 parts of toughening agent;

the reactive hindered phenol grafted propylene polymer is prepared by mixing propylene polymer with reactive hindered phenol after plasma treatment; the reactive hindered phenol is 2, 6-di-tert-butyl-4- [2- (2-oxiranyl) ethyl ] phenol and/or 2, 6-di-tert-butyl-4- [ (2-oxiranyl) methyl ] phenol;

the reactive hindered amine grafted propylene polymer is prepared by mixing and reacting a propylene polymer with reactive hindered amine after plasma treatment; the reactive hindered amine is 1-acetyl-2, 6-tetramethyl-4- [ (2-oxiranyl) methoxy ] piperidine and/or 1,2, 6-pentamethyl-4- [ (2-oxiranyl) methoxy ] piperidine;

the toughening agent is a star-structured SEBS.

2. The propylene polymer composition of claim 1, wherein the mass ratio of propylene polymer to reactive hindered phenol used to prepare the reactive hindered phenol grafted propylene polymer is 1: (0.05-0.5).

3. The propylene polymer composition of claim 1, wherein the reactive hindered phenol grafted propylene polymer is prepared by:

A) Carrying out plasma treatment on the propylene polymer in an oxygen atmosphere to obtain a pretreated propylene polymer; under an acidic condition, mixing and reacting the pretreated propylene polymer with reactive hindered phenol in a solvent to obtain a reactive hindered phenol grafted propylene polymer;

or alternatively, the first and second heat exchangers may be,

carrying out plasma treatment on the propylene polymer in an ammonia atmosphere to obtain a pretreated propylene polymer; and mixing the pretreated propylene polymer and the reactive hindered phenol in a solvent for reaction to obtain the reactive hindered phenol grafted propylene polymer.

4. The propylene polymer composition of claim 1, wherein the mass ratio of propylene polymer to reactive hindered amine used to prepare the reactive hindered amine grafted propylene polymer is 1: (0.05-0.5).

5. The propylene polymer composition of claim 1, wherein the reactive hindered amine grafted propylene polymer is prepared by:

b) Carrying out plasma treatment on the propylene polymer in an oxygen atmosphere to obtain a pretreated propylene polymer; under alkaline condition, mixing and reacting the pretreated propylene polymer and the reactive hindered amine in a solvent to obtain a reactive hindered amine grafted propylene polymer;

Or alternatively, the first and second heat exchangers may be,

b') carrying out plasma treatment on the propylene polymer in an ammonia gas atmosphere to obtain a pretreated propylene polymer; and mixing the pretreated propylene polymer and the reactive hindered amine in a solvent for reaction to obtain the reactive hindered amine grafted propylene polymer.

6. Propylene polymer composition according to claim 1, characterized in that the propylene polymer comprises homo-polypropylene and/or ethylene-propylene random copolymer.

7. The propylene polymer composition of claim 1, wherein the feed component further comprises one or more of a nucleating agent, a halogen absorber and a lubricant.

8. The propylene polymer composition according to claim 7, wherein the nucleating agent is an organophosphate nucleating agent;

the halogen absorber comprises one or more of calcium stearate, zinc stearate and hydrotalcite;

the lubricant includes one or more of montan wax E wax, oleamide, and erucamide.

9. A process for the preparation of a propylene polymer composition as defined in any one of claims 1 to 8 comprising the steps of:

the raw materials for preparing the propylene polymer composition are melt blended and extruded to obtain the propylene polymer composition.