Polypropylene alloy resin composite material and application thereof

Abstract

The invention relates to the field of medical materials, and discloses a polypropylene alloy resin composite material and application thereof. The composite material comprises irregular co-polypropylene resin, polybutylene-1 resin and an auxiliary agent, on the basis of the total weight of the irregular co-polypropylene resin and the polybutylene-1 resin, the content of the irregular co-polypropylene resin is 75-90 wt%, and the content of the polybutylene-1 resin is 10-25 wt%; the polybutylene-1 resin comprises a butylene-1 structural unit and an ethylene structural unit; on the basis of the total weight of the polybutylene-1 resin, the content of the ethylene structural unit is 5-10 wt%; the melt index of the polybutylene-1 resin is 10 to 18 g / 10 min; the auxiliaries comprise antioxidants, and the antioxidants are phosphite antioxidants and hindered amine antioxidants. The material has good impact resistance, transparency and irradiation resistance, meets the requirements of medical products, and has good application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of medical materials, and particularly relates to a polypropylene alloy resin composite material and its application. Background Art

[0002] Irradiation sterilization is an increasingly emerging method for sterilizing medical devices. Among them, radiation-resistant polypropylene-based resins can be used to prepare medical device products such as syringes and infusion bags. In these application fields, products have relatively high requirements for the impact resistance and transparency of the resin.

[0003] In the prior art, high-transparency and high-impact polypropylene mainly uses alloy technology and high-transparency agent addition schemes. The polypropylene alloy technology mainly includes in-kettle polymerization of ethylene-propylene rubber or external addition of vinyl elastomer / propylene elastomer to improve the high impact resistance of polypropylene. However, the addition of these rubbers or elastomers will cause a decrease in the transparency of the polypropylene matrix, and a large amount of transparency agent needs to be added to improve the transparency of the resin. However, in the medical field, a high addition of transparency agent often causes obvious precipitation and difficulties in medical certification. Summary of the Invention

[0004] The purpose of the present invention is to overcome the problems existing in the prior art that medical device products cannot simultaneously have high impact resistance, transparency, and a high addition amount of transparency agent. The present invention provides a polypropylene alloy resin composite material and its application. This composite material can simultaneously have good impact resistance, transparency, and radiation resistance, meet the requirements of medical device products, and has good application prospects.

[0005] To achieve the above purpose, the first aspect of the present invention provides a polypropylene alloy resin composite material, wherein the composite material includes random copolymerized polypropylene resin, polybutene-1 resin, and additives; based on the total weight of the random copolymerized polypropylene resin and polybutene-1 resin, the content of the random copolymerized polypropylene resin is 75-90% by weight, and the content of the polybutene-1 resin is 10-25% by weight;

[0006] Among them, the polybutene-1 resin includes butene-1 structural units and ethylene structural units;

[0007] Among them, based on the total weight of the polybutene-1 resin, the content of the ethylene structural unit is 5-10% by weight;

[0008] Among them, under the test conditions of 190°C and 2.16 kg, the melt index of the polybutene-1 resin is 10-18 g / 10 min;

[0009] Among them, the additives include antioxidants, and the antioxidants are phosphite antioxidants and hindered amine antioxidants.

[0010] In the second aspect of the present invention, there is provided an application of the composite material described in the first aspect in medical device products.

[0011] The inventors of the present invention found in their research that by selecting polybutene-1 resins, random copolymer polypropylene resin matrices and additives with specific molecular structures to prepare composite materials, with the specific ethylene structural monomer content, specific melt index and specific antioxidant type of the polybutene-1 resins, the three cooperate with each other and act synergistically, which can improve the impact resistance, transparency and radiation resistance of the composite materials, making the prepared composite materials have good impact resistance, transparency and radiation resistance at the same time, greatly reducing the addition amount of clarifying agents, improving impact resistance and high transparency and radiation resistance, and improving the adaptability of the composite materials for application in the medical field. Specific embodiments

[0012] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0013] In the present invention, the notched Izod impact strength of the polypropylene alloy resin composite material is tested according to the method of GB / T 1043.1-2008. The specific test conditions are as follows: at 200 °C and 5 MPa, injection molding for 45 s to prepare a rectangular sample bar of 4 mm × 10 mm × 80 mm, and machining the rectangular sample bar to prepare a Type A notch. After storing in a constant temperature and humidity chamber for 48 h, the notched Izod impact strength at 25 °C (room temperature) is measured. Among them, for the impact strength at 0 °C, the test sample bar needs to be kept at a constant temperature in a 0 °C refrigerator for 2 h.

[0014] In the present invention, the flexural modulus of the polypropylene alloy resin composite material is tested according to the method of GB / T 9341-2008. The specific test conditions are as follows: at 200 °C and 5 MPa, injection molding for 45 s to prepare a rectangular sample bar of 4 mm × 10 mm × 80 mm. After storing in a constant temperature and humidity chamber for 48 h, the flexural modulus is measured.

[0015] In the present invention, the light transmittance and haze of the polypropylene alloy resin composite material are tested according to the method of GB / T 2410-2008. The specific test conditions are as follows: at 200 °C, 5 MPa and injection molding for 45 s, a 1 mm thin plate sample bar is prepared. After storing in a constant temperature and humidity chamber for 48 h, the light transmittance and haze are tested.

[0016] In the present invention, the yellowness index of the polypropylene alloy resin composite material is measured in accordance with GB / T 39822-2021. The specific test conditions are as follows: irradiate the polypropylene alloy resin composite material with cobalt-60, the irradiation intensity is 25 kGy, and the sample with a yellowness index less than 1 is a qualified sample resistant to irradiation.

[0017] In the present invention, the melt index of the polybutene-1 resin is measured in accordance with GB / T 37199.2-2018. The specific test conditions are as follows: the temperature is 190 °C and the load is 2.16 kg.

[0018] In the present invention, the melt index of the polypropylene alloy resin composite material is measured in accordance with GB / T 3682.2-2018. The specific test conditions are as follows: the temperature is 230 °C and the load is 2.16 kg.

[0019] In the present invention, the melt index of the random copolymer polypropylene resin is measured in accordance with GB / T 3682.2-2018. The specific test conditions are as follows: the temperature is 230 °C and the load is 2.16 kg.

[0020] In the present invention, the content of each structural unit in the polybutene-1 resin and the random copolymer polypropylene resin is measured by infrared spectroscopy analysis.

[0021] In the first aspect of the present invention, a polypropylene alloy resin composite material is provided. Among them, the composite material includes a random copolymer polypropylene resin, a polybutene-1 resin and an additive; based on the total weight of the random copolymer polypropylene resin and the polybutene-1 resin, the content of the random copolymer polypropylene resin is 75-90% by weight, and the content of the polybutene-1 resin is 10-25% by weight;

[0022] Among them, the polybutene-1 resin includes a butene-1 structural unit and an ethylene structural unit;

[0023] Among them, based on the total weight of the polybutene-1 resin, the content of the ethylene structural unit is 5-10% by weight;

[0024] Among them, under the test conditions of 190 °C and 2.16 kg, the melt index of the polybutene-1 resin is 10-18 g / 10 min;

[0025] Among them, the additive includes an antioxidant, and the antioxidant is a phosphite antioxidant and a hindered amine antioxidant.

[0026] In the research, the inventors of the present invention found that by using polybutene-1 resins with a specific molecular structure in combination with a random copolymerized polypropylene resin matrix and additives, and by virtue of the appropriate ethylene structural monomer content, specific melt index and specific antioxidant type of the polybutene-1 resins, the three cooperate with each other and act synergistically to improve the impact resistance and transparency of the composite material, enabling the prepared composite material to have good impact resistance, transparency and radiation resistance at the same time, greatly reducing the addition amount of the clarifying agent, improving the impact resistance and high transparency and radiation resistance, and improving the adaptability of the composite material for medical applications.

[0027] In the present invention, the composite material has good impact resistance (including room temperature impact resistance and low temperature impact resistance), transparency and radiation resistance, enabling it to be better applied to medical device products and meeting the use requirements of radiation sterilization. Preferably, the 25°C impact strength of the composite material is above 8 kJ / m 2 ², the 0°C impact strength is above 3.5 kJ / m 2 ², the haze is below 15, and the light transmittance is above 90%; more preferably, the 25°C impact strength of the composite material is 8-12 kJ / m 2 ², the 0°C impact strength is 4-5.5 kJ / m 2 ², the haze is 8-15, and the light transmittance is 90-93%.

[0028] In the present invention, preferably, under the test conditions of 230°C and 2.16 kg, the melt index of the composite material is 20-35 g / 10 min, and more preferably 23-32 g / 10 min. The advantage of adopting this preferred embodiment is that an appropriate melt index can balance the processing performance and mechanical performance of the polypropylene alloy resin.

[0029] In the present invention, the composite material has good radiation resistance, is particularly suitable for medical device products, and improves the application prospect of the composite material. Preferably, the yellow index of the composite material is below 1, and more preferably (-2)-1. The advantage of adopting this preferred embodiment is to ensure that the product has good appearance and optical properties after radiation sterilization.

[0030] In the present invention, by controlling the contents of the random copolymerized polypropylene resin and the polybutene-1 resin, the synergistic effect is exerted to improve the impact resistance, transparency and radiation resistance of the composite material. Preferably, based on the total weight of the random copolymerized polypropylene resin and the polybutene-1 resin, the content of the random copolymerized polypropylene resin is 80-85% by weight, and the content of the polybutene-1 resin is 15-20% by weight.

[0031] In the present invention, random copolymer polypropylene with a specific melt index is selected as the matrix resin and cooperates with polybutene-1 resin to improve the impact resistance, transparency and radiation resistance of the composite material. Under the test conditions of 230 °C and 2.16 kg, the melt index of the random copolymer polypropylene resin is 21-35 g / 10 min, preferably 23-32 g / 10 min.

[0032] In the present invention, preferably, the random copolymer polypropylene resin exists in the form of powder. The advantage of adopting this preferred embodiment is that it will not introduce additive components that are harmful to the radiation resistance of the resin.

[0033] In the present invention, preferably, the random copolymer polypropylene resin comprises propylene structural units and ethylene structural units.

[0034] In the present invention, random copolymer polypropylene with a specific molecular structure is selected as the matrix resin and cooperates with polybutene-1 resin to improve the impact resistance, transparency and radiation resistance of the composite material. Preferably, based on the total weight of the random copolymer polypropylene, the content of the ethylene structural units is 3-5 wt%.

[0035] In the present invention, there is no particular limitation on the source of the random copolymer polypropylene, and it can be obtained by commercial purchase, for example.

[0036] In the present invention, preferably, the polybutene-1 resin further comprises a main catalyst, a cocatalyst, and an electron donor.

[0037] In the present invention, the selection range of the type of the main catalyst is relatively wide, and it can be various main catalysts conventionally defined in the art and applicable to the preparation of polyolefin-1 resin. Preferably, the main catalyst is a Ziegler-Natta catalyst.

[0038] In the present invention, the selection range of the type of the cocatalyst is relatively wide, and it can be various existing cocatalysts applicable to the preparation of polyolefin-1 resin. Preferably, the cocatalyst is an alkyl aluminum, preferably selected from at least one of trimethyl aluminum, triethyl aluminum, triisobutyl aluminum and tri-n-butyl aluminum, and more preferably triisobutyl aluminum.

[0039] In the present invention, the selection range of the type of the electron donor is relatively wide, and a conventional electron donor in the art can be adopted. Preferably, the electron donor is a siloxane external electron donor, preferably selected from at least one of trimethylmethoxysilane, trimethylethoxysilane, methyl tert-butyl dimethoxysilane and cyclohexylmethyl dimethoxysilane, and more preferably cyclohexylmethyl dimethoxysilane.

[0040] In the present invention, preferably, based on the total weight of the polybutene-1 resin, the total content of the main catalyst, the cocatalyst and the electron donor is 0.015 - 0.2% by weight.

[0041] In the present invention, the total content of the main catalyst, the cocatalyst and the electron donor is controlled by feeding.

[0042] In the present invention, preferably, the mass ratio of the main catalyst, the cocatalyst and the electron donor is 0.01 - 0.02:0.08 - 0.75:0.1 - 0.8.

[0043] In the present invention, preferably, based on the total weight of the polybutene-1 resin, the content of the butene-1 structural unit is 89.8 - 94.9% by weight.

[0044] In the present invention, preferably, the polybutene-1 resin is prepared by the following method, which includes the following steps: adding butene-1, the main catalyst, the cocatalyst and the electron donor into a polymerization kettle, carrying out a polymerization reaction with ethylene and hydrogen under different pressures, and then drying to obtain the polybutene-1 resin.

[0045] In the present invention, preferably, the main catalyst is provided by a suspension containing the main catalyst, and preferably the content of the main catalyst in the suspension containing the main catalyst is 0.5 - 5 mg / mL.

[0046] In the present invention, preferably, the cocatalyst is provided by a solution containing the cocatalyst, and preferably the content of the cocatalyst in the cocatalyst solution is 0.1 - 0.5 mol / L.

[0047] In the present invention, preferably, the electron donor is provided by a solution containing the electron donor, and preferably the content of the electron donor in the electron donor solution is 0.5 - 1.5 mol / L.

[0048] In the present invention, the types of the main catalyst, the cocatalyst and the electron donor have been described above and will not be elaborated here.

[0049] In the present invention, there is no particular limitation on the sources of the main catalyst, the cocatalyst, the electron donor and the auxiliary agent. They can be obtained through commercial purchase or prepared by existing methods, and preferably obtained through commercial purchase.

[0050] In the present invention, the suspension of the main catalyst, the cocatalyst solution and the electron donor solution can be prepared by dilution with a solvent. There is no particular limitation on the type of the solvent in the present invention. For example, it can be an inert organic solvent. Preferably, the inert organic solvent is selected from at least one of white oil, n-hexane, n-octane, isohexane and heptane, and more preferably n-hexane.

[0051] In the present invention, there is no particular limitation on the mixing order of the suspension of the main catalyst, the cocatalyst solution and the electron donor solution with 1-butene. For example, it can be carried out by any one of Method 1 and / or Method 2. Method 1 is to sequentially add the suspension of the main catalyst, the cocatalyst solution and the electron donor solution to 1-butene. Method 2 is to first mix the suspension of the main catalyst, the cocatalyst solution and the electron donor solution for pre-complexation reaction, and then mix it with 1-butene. Preferably, it is carried out by Method 2. In the present invention, before the main catalyst, the cocatalyst and the electron donor enter the autoclave, pre-complexation treatment is carried out, and after the pre-complexation treatment, it is used for the polymerization reaction. The pre-complexation treatment is beneficial to improving the polymerization activity of the catalyst system. The conditions of the pre-complexation treatment are not particularly limited, and conventional methods in the art can be used. Preferably, the temperature of the pre-complexation treatment is 5-20 °C and the time is 5-15 min.

[0052] In the present invention, preferably, the amounts of 1-butene, the main catalyst, the cocatalyst, the electron donor and the solvent are such that in the prepared polybutene-1 resin, the total content of the main catalyst, the cocatalyst and the electron donor is 0.015-0.2% by weight.

[0053] In the present invention, preferably, the amounts of the main catalyst, the cocatalyst, the electron donor and the solvent are such that in the prepared polybutene-1 resin, the mass ratio of the main catalyst, the cocatalyst and the electron donor is 0.01-0.02:0.08-0.75:0.1-0.8.

[0054] In the present invention, preferably, the amount of 1-butene is such that in the prepared polybutene-1 resin based on the total weight of the polybutene-1 resin, the content of the 1-butene structural unit is 89.8-94.9% by weight.

[0055] In the present invention, preferably, the polymerization reaction includes a first-stage polymerization reaction and a second-stage polymerization reaction.

[0056] In the present invention, by controlling the conditions of the first-stage polymerization reaction, the content of the ethylene structural unit and the melt index of the resin in the polybutene-1 resin are controlled to obtain a polybutene-1 resin with a specific molecular structure. Preferably, the conditions of the first-stage polymerization reaction include: the ethylene partial pressure is 0.2-3.2 bar, preferably 0.8-2 bar, the hydrogen partial pressure is 0.5-2.5 bar, preferably 1-1.5 bar, and the time is 0.5-2.5 h.

[0057] In the present invention, the content of ethylene structural units and the melt index of the polybutene-1 resin are controlled by coordinating the conditions of the second-stage polymerization reaction with those of the first-stage polymerization reaction, thereby obtaining a polybutene-1 resin with a specific molecular structure. Preferably, the conditions of the second-stage polymerization reaction include: ethylene partial pressure of 0.2-3.2 bar, preferably 0.8-2 bar, hydrogen partial pressure of 0.5-2.5 bar, preferably 1-2.5 bar, and time of 0.5-2.5 h.

[0058] In the present invention, preferably, the temperatures of the first-stage polymerization reaction and the second-stage polymerization reaction are independently 70-80 °C.

[0059] In the present invention, controlling the conditions of the first-stage polymerization reaction and the second-stage polymerization reaction within the above ranges is beneficial for the melt index of the prepared polybutene-1 resin to be 10-18 g / 10 min and the content of ethylene structural units to be 5-10 wt% under the test conditions of 230 °C and 2.16 kg, which is beneficial for improving the impact resistance, transparency, and radiation resistance of the polypropylene alloy resin composite material.

[0060] In the present invention, the polymerization reaction can be carried out in a continuous or batch form. The batch polymerization can be carried out in an autoclave equipped with a stirring and temperature device. The content of ethylene structural units is controlled by controlling the partial pressure of ethylene, the melt index of the resin is controlled by controlling the partial pressure of hydrogen, and the molecular weight distribution is controlled by changing the reaction conditions of the two stages.

[0061] In the present invention, hydrogen is used as the melt index regulator in the polymerization process, that is, according to the requirements of the polybutene-1 resin, the addition amount of hydrogen in the polymerization autoclave is controlled to adjust the melt index of the polybutene-1 resin. In the present invention, there is no particular limitation on the source of hydrogen, and those skilled in the art can select according to actual needs.

[0062] In the present invention, preferably, the method for preparing the polybutene-1 resin further includes adding a deactivator to terminate the reaction after the second-stage polymerization reaction. In the present invention, there is no particular limitation on the type of the water reducing agent, and the deactivators defined in the art are applicable to the present invention. For example, it can be at least one of water, oxygen, carbon dioxide, and carbon monoxide, preferably water, and more preferably deionized water. Preferably, the mass ratio of the deactivator to the cocatalyst is 1-50:1.

[0063] According to a specific embodiment of the present invention, the preparation method of the polybutene-1 resin comprises the following steps: first, dilute the Ziegler-Natta catalyst, the alkylaluminum cocatalyst and the siloxane external donor with n-hexane solution respectively for use, mix the above three and carry out a pre-complexation reaction; then add butene-1 and the complexation reaction product into a reaction kettle, at the polymerization reaction temperature, introduce ethylene and hydrogen to carry out the first-stage polymerization reaction, continue to introduce ethylene and hydrogen to carry out the second-stage polymerization reaction, after the second-stage polymerization reaction is completed, obtain a polymer solution, mix the obtained polymer solution with a deactivator to deactivate the active centers, and after washing, filtering and drying, obtain the polybutene-1 resin. In the present invention, the washing conditions are not particularly limited, and preferably, washing is carried out with ethanol. In the present invention, the drying conditions are not specifically limited. Preferably, the drying conditions include: the temperature is 50-60 °C and the time is 8-12 h.

[0064] In the present invention, there is no particular limitation on the specific type of the antioxidant, and those skilled in the art can select according to actual needs. Preferably, the antioxidant is selected from phosphite antioxidant 705T and / or phosphite antioxidant 168, and hindered amine antioxidant 770 and / or hindered amine antioxidant HS-944. Using the antioxidant within the above preferred range has the advantage of resistance to radiation yellowing.

[0065] In the present invention, there is no particular limitation on the dosage of the antioxidant. Preferably, relative to 1 kg of the random copolymerized polypropylene resin and the polybutene-1 resin, the content of the antioxidant is 1.5-3 g.

[0066] In the present invention, preferably, the weight ratio of the phosphite antioxidant to the hindered amine antioxidant is 2:1-1:1.

[0067] In the present invention, preferably, the additive also includes a clarifying agent and / or an acid scavenger.

[0068] In the present invention, there is no particular limitation on the specific type of the clarifying agent, and the clarifying agents defined in the art are all applicable to the present invention. Preferably, the clarifying agent is a sorbitol clarifying agent and / or a phosphate clarifying agent. The present invention has no particular limitation on the specific types of the sorbitol clarifying agent and the phosphate clarifying agent, and those skilled in the art can select according to actual needs, for example, it can be clarifying agent NX 8000, clarifying agent NA-21.

[0069] In the present invention, there is no particular limitation on the specific type of the acid scavenger, and the acid scavengers defined in the art are all applicable to the present invention. Preferably, the acid scavenger is selected from at least one of hydrotalcite, calcium stearate and zinc stearate.

[0070] In the present invention, there is no particular limitation on the sources of the antioxidant, clarifying agent and acid scavenger in the additives, and they can be obtained by commercial purchase.

[0071] In the present invention, there is no particular limitation on the total content of the additives. Preferably, relative to 1 kg of the random copolymerized polypropylene resin and polybutene-1 resin, the content of the additives is 2 - 6 g, and more preferably 2.5 - 5 g.

[0072] In the present invention, by selecting polybutene-1 resin and random copolymerized polypropylene to cooperate with each other, the transparency of the composite material can be improved while enhancing the impact resistance, thereby reducing the amount of the clarifying agent and avoiding the precipitation of the clarifying agent, which may cause the product to be unqualified. As a result, the composite material can be better applied to the field of medical device products, improving the application prospects of the composite material. Preferably, relative to 1 kg of the random copolymerized polypropylene resin and polybutene-1 resin, the content of the clarifying agent is 0.5 - 1 g, and more preferably 0.5 - 0.8 g.

[0073] In the present invention, there is no particular limitation on the amount of the acid scavenger, as long as it can remove the residual acidic substances in the composite material. Preferably, relative to 1 kg of the random copolymerized polypropylene resin and polybutene-1 resin, the content of the acid scavenger is 0.2 - 1 g.

[0074] In the present invention, preferably, the polypropylene alloy resin composite material is prepared by the following method, which includes the following steps: mixing the polybutene-1 resin, random copolymerized polypropylene resin, antioxidant, clarifying agent and acid scavenger, and performing melt blending and pelletizing to obtain the polypropylene alloy resin composite material.

[0075] According to a specific embodiment of the present invention, the polypropylene alloy resin composite material is prepared by the following method, which includes the following steps: pre-mix polybutene-1 resin, random copolymerized polypropylene resin, antioxidant, clarifying agent and acid scavenger to obtain a pre-mixture; the pre-mixture is subjected to blending and pelletizing to obtain the polypropylene alloy resin composite material. In the present invention, there is no particular limitation on the conditions of pre-mixing. Preferably, the time of pre-mixing is 1-5 min. In the present invention, there is no particular limitation on the operation mode and equipment used for pre-mixing. For example, it can be carried out in a high-speed mixer defined in the art, and those skilled in the art can select the specific operation conditions according to actual needs. In the present invention, there is no particular limitation on the operation mode of blending and pelletizing. Preferably, the blending and pelletizing includes melting, extrusion, pelletizing and homogenization. In the present invention, there is no particular limitation on the conditions of blending and pelletizing. Preferably, the blending time is 1-20 min, the conveying temperature is 150-200 °C, the homogenization temperature is 210-240 °C, the extrusion temperature is 180-250 °C, and the die temperature is 200-240 °C. In the present invention, the equipment used for blending and pelletizing can be carried out, for example, in a twin-screw extruder defined in the art.

[0076] In the second aspect of the present invention, there is provided an application of the composite material described in the first aspect in medical device products.

[0077] In the present invention, preferably, the composite material is particularly suitable for the preparation of syringes and infusion bags.

[0078] The present invention will be described in detail below through examples.

[0079] In the present invention, the notched Izod impact strength of the polypropylene alloy resin composite material is tested according to the method of GB / T 1043.1-2008. The specific test conditions are as follows: at 200 °C and 5 MPa, injection mold for 45 s to prepare a rectangular sample bar of 4 mm × 10 mm × 80 mm, and machine-process the rectangular sample bar to prepare a Type A notch. After storing in a constant temperature and humidity chamber for 48 h, measure the notched Izod impact strength at 25 °C. Among them, for the impact strength at 0 °C, the test sample bar needs to be kept at a constant temperature in a 0 °C refrigerator for 2 h.

[0080] In the present invention, the flexural modulus of the polypropylene alloy resin composite material is tested according to the method of GB / T 9341-2008. The specific test conditions are as follows: at 200 °C and 5 MPa, injection mold for 45 s to prepare a rectangular sample bar of 4 mm × 10 mm × 80 mm. After storing in a constant temperature and humidity chamber for 48 h, measure the flexural modulus.

[0081] In the present invention, the light transmittance and haze of the polypropylene alloy resin composite material are tested according to the method of GB / T 2410-2008. The specific test conditions are as follows: under the conditions of 200 °C, 5 MPa and injection molding for 45 s, a 1-mm thin plate spline is prepared. After being stored in a constant temperature and humidity box for 48 h, the light transmittance and haze are tested.

[0082] In the present invention, the yellowness index of the polypropylene alloy resin composite material is determined according to GB / T 39822-2021. The specific test conditions are as follows: the polypropylene alloy resin composite material is irradiated with cobalt-60, the irradiation intensity is 25 kGy, and the sample with a yellowness index less than 1 is a qualified sample resistant to irradiation.

[0083] In the present invention, the melt index of the polybutene-1 resin is determined according to GB / T 37199.2-2018. The specific test conditions are as follows: the temperature is 190 °C and the load is 2.16 kg.

[0084] In the present invention, the melt index of the polypropylene alloy resin composite material is determined according to GB / T 3682.2-2018. The specific test conditions are as follows: the temperature is 230 °C and the load is 2.16 kg.

[0085] In the present invention, the melt index of the random copolymer polypropylene resin is determined according to GB / T 3682.2-2018. The specific test conditions are as follows: the temperature is 230 °C and the load is 2.16 kg.

[0086] In the present invention, the content of each structural unit in the polybutene-1 resin and the random copolymer polypropylene resin is measured by infrared spectroscopy analysis.

[0087] In the following preparation examples and examples, unless otherwise specified, the raw materials used are commercially available products. The raw materials used in the following preparation examples are shown in Table 1, and the raw materials used in the examples are shown in Table 2.

[0088] Table 1

[0089]

[0090] Table 2

[0091]

[0092]

[0093] Preparation Examples 1-2 and Comparative Preparation Examples 1-4 are used to illustrate the preparation of the polybutene-1 resin

[0094] Preparation Example 1

[0095] (1) A pre-complexation reaction was carried out on 3 mL of a hexane suspension of Ziegler-Natta catalyst (5 mg / mL), 7 mL of a hexane solution of triisobutylaluminum (0.1 mol / L), and 3.5 mL of a hexane solution of cyclohexylmethyldimethoxysilane (0.5 mol / L) at 10 °C for 5 min to obtain a pre-complexation reaction product;

[0096] (2) Under the conditions of a temperature of 140 °C and high vacuum, a 3 L autoclave (Buchiglas, Switzerland) was activated for 2 h. After the temperature of the autoclave dropped to room temperature, 1200 g of 1-butene was added into the autoclave. Then the temperature of the autoclave was raised to 75 °C. Finally, the complexation reaction product obtained in step (1) was injected into the reaction kettle to carry out the first-stage polymerization reaction and the second-stage polymerization reaction. The conditions of the first-stage polymerization reaction were: hydrogen was introduced into the autoclave at a pressure of 1.5 bar, and then ethylene was introduced at a pressure of 0.8 bar, and the reaction was carried out for 1 h; the conditions of the second-stage polymerization reaction were: hydrogen was introduced at a pressure of 1.5 bar, and then ethylene was introduced at a pressure of 0.8 bar, and the reaction was carried out for 1 h; after the second-stage polymerization was completed, the obtained polymer solution was mixed with 5 mL of deionized water in a mixer to terminate the reaction. After washing, filtering, and drying (the drying temperature was 60 °C and the time was 8 h), 300 g of polybutene-1 resin was obtained.

[0097] Preparation Example 2

[0098] According to the method of Preparation Example 1, the difference is that the conditions of the first-stage polymerization reaction are: hydrogen is introduced into the autoclave at a pressure of 1.5 bar, and then ethylene is introduced at a pressure of 2 bar, and the reaction is carried out for 1 h; the conditions of the second-stage polymerization reaction are: hydrogen is introduced at a pressure of 2.5 bar, and then ethylene is introduced at a pressure of 2 bar, and the reaction is carried out for 1 h, and 295 g of polybutene-1 resin is obtained.

[0099] Comparative Preparation Example 1

[0100] According to the method of Preparation Example 1, the difference is that the conditions of the first-stage polymerization reaction are: hydrogen is introduced into the autoclave at a pressure of 0.8 bar, and then ethylene is introduced at a pressure of 0.9 bar, and the reaction is carried out for 1 h; the conditions of the second-stage polymerization reaction are: hydrogen is introduced at a pressure of 1 bar, and then ethylene is introduced at a pressure of 0.9 bar, and the reaction is carried out for 1 h, and 305 g of polybutene-1 resin is obtained.

[0101] Comparative Preparation Example 2

[0102] According to the method of Preparation Example 1, except that the polymerization reaction conditions in the first stage were as follows: hydrogen was introduced into the autoclave at a pressure of 2.5 bar, and then ethylene was introduced at a pressure of 1.5 bar, and the reaction was carried out for 1 h; the polymerization reaction conditions in the second stage were as follows: hydrogen was introduced at a pressure of 2.5 bar, and then ethylene was introduced at a pressure of 1.5 bar, and the reaction was carried out for 1 h, to obtain 320 g of polybutene-1 resin.

[0103] Comparative Preparation Example 3

[0104] According to the method of Preparation Example 1, except that the polymerization reaction conditions in the first stage were as follows: hydrogen was introduced into the autoclave at a pressure of 1.5 bar, and then ethylene was introduced at a pressure of 0.2 bar, and the reaction was carried out for 1 h; the polymerization reaction conditions in the second stage were as follows: hydrogen was introduced at a pressure of 1.8 bar, and then ethylene was introduced at a pressure of 0.2 bar, and the reaction was carried out for 1 h, to obtain 295 g of polybutene-1 resin.

[0105] Comparative Preparation Example 4

[0106] According to the method of Preparation Example 1, except that the polymerization reaction conditions in the first stage were as follows: hydrogen was introduced into the autoclave at a pressure of 1.5 bar, and then ethylene was introduced at a pressure of 3.2 bar, and the reaction was carried out for 1 h; the polymerization reaction conditions in the second stage were as follows: hydrogen was introduced at a pressure of 1.8 bar, and then ethylene was introduced at a pressure of 3.2 bar, and the reaction was carried out for 1 h, to obtain 310 g of polybutene-1 resin.

[0107] The contents of ethylene structural units and the melt indices of the polybutene-1 resins prepared in the above Preparation Examples 1-2 and Comparative Preparation Examples 1-4 are shown in Table 3.

[0108] Table 3

[0109] Melt Index (g / 10 min) (190 °C, 2.16 kg) Content of ethylene structural unit (wt.%) Preparation Example 1 10 5 Preparation Example 2 18 10 Comparative Preparation Example 1 4 5.3 Comparative Preparation Example 2 30 8.7 Comparative Preparation Example 3 15 1.2 Comparative Preparation Example 4 15 18.5

[0110] Examples 1-4 and Comparative Examples 1-8 are used to illustrate the preparation of polypropylene alloy resin composites.

[0111] Example 1

[0112] The polypropylene and polybutene-1 resin are in a mass ratio of 85:15. 4.25 kg of random copolymer polypropylene (M26ET) and 0.75 kg of the polybutene-1 resin in Preparation Example 1 are added to a high-speed mixer, and then 10 g of antioxidant 168, 5 g of hindered amine 770, 2.5 g of clarifying agent NX8000, and 2.5 g of zinc stearate are added and mixed for 5 min. Then, the obtained premix is fed into the main feed port of a twin-screw extruder and subjected to melting, extrusion, granulation, and homogenization. Among them, the blending time for melting, extrusion, and granulation is 2 min, the conveying temperature is 180 °C, the homogenization temperature is 220 °C, the extrusion temperature is 220 °C, and the die temperature is 200 °C to obtain a polypropylene alloy resin composite material.

[0113] Example 2

[0114] The polypropylene and polybutene-1 resin are in a mass ratio of 80:20. 4 kg of random copolymer polypropylene (M26ET) and 1 kg of the polybutene-1 resin in Preparation Example 2 are added to a high-speed mixer, and then 5 g of antioxidant 705T, 5 g of hindered amine HS-944, 4 g of clarifying agent NX8000, and 5 g of hydrotalcite are added and mixed for 5 min. Then, the obtained premix is fed into the main feed port of a twin-screw extruder and subjected to melting, extrusion, granulation, and homogenization. Among them, the blending time for melting, extrusion, and granulation is 2 min, the conveying temperature is 180 °C, the homogenization temperature is 220 °C, the extrusion temperature is 220 °C, and the die temperature is 200 °C to obtain a polypropylene alloy resin composite material.

[0115] Example 3

[0116] According to the method of Example 2, the difference is that random copolymer polypropylene M08ET is selected to replace the random copolymer polypropylene (M26ET) in Example 2, and the remaining operating conditions are the same as those in Example 2 to obtain a polypropylene alloy resin composite material.

[0117] Example 4

[0118] The polypropylene and polybutene-1 resin are in a mass ratio of 87:13. 4.35 kg of random copolymer polypropylene (M26ET) and 0.65 kg of that in Preparation Example 2 are added to a high-speed mixer, and then 5 g of antioxidant 705T, 5 g of hindered amine HS-944, 4 g of clarifying agent NA-21, and 1.5 g of hydrotalcite are added and mixed for 2 min. Then, the obtained premix is fed into the main feed port of a twin-screw extruder and subjected to melting, extrusion, granulation, and homogenization. Among them, the blending time for melting, extrusion, and granulation is 2 min, the conveying temperature is 180 °C, the homogenization temperature is 220 °C, the extrusion temperature is 240 °C, and the die temperature is 220 °C to obtain a polypropylene alloy resin composite material.

[0119] Comparative Example 1

[0120] According to the method of Example 2, except that the polybutene-1 resin in Comparative Preparation Example 1 was used to replace the polybutene-1 resin in Example 2, and the remaining operating conditions were the same as those in Example 2, a polypropylene alloy resin composite material was obtained.

[0121] Comparative Example 2

[0122] According to the method of Example 2, except that the polybutene-1 resin in Comparative Preparation Example 2 was used to replace the polybutene-1 resin in Example 2, and the remaining operating conditions were the same as those in Example 2, a polypropylene alloy resin composite material was obtained.

[0123] Comparative Example 3

[0124] According to the method of Example 2, except that the polybutene-1 resin in Comparative Preparation Example 3 was used to replace the polybutene-1 resin in Example 2, and the remaining operating conditions were the same as those in Example 2, a polypropylene alloy resin composite material was obtained.

[0125] Comparative Example 4

[0126] According to the method of Example 2, except that the polybutene-1 resin in Comparative Preparation Example 4 was used to replace the polybutene-1 resin in Example 2, and the remaining operating conditions were the same as those in Example 2, a polypropylene alloy resin composite material was obtained.

[0127] Comparative Example 5

[0128] According to the method of Example 2, except that vinyl elastomer 8137 was used to replace the polybutene-1 resin in Example 2, and the remaining operating conditions were the same as those in Example 2, a polypropylene alloy resin composite material was obtained.

[0129] Comparative Example 6

[0130] According to the method of Example 2, except that propylene-based elastomer 6202 was used to replace the polybutene-1 resin in Example 2, and the remaining operating conditions were the same as those in Example 2, a polypropylene alloy resin composite material was obtained.

[0131] Comparative Example 7

[0132] According to the method of Example 2, except that hindered phenol antioxidant 1010 was used to replace hindered amine HS-944 in Example 2, and the remaining operating conditions were the same as those in Example 2, a polypropylene alloy resin composite material was obtained.

[0133] Comparative Example 8

[0134] According to the method of Example 2, the difference is that polypropylene and polybutene-1 resin are in a mass ratio of 95:5. 4.75 kg of random copolymer polypropylene (M26ET) and 0.25 kg of the polybutene-1 resin in Preparation Example 2 are used, and the remaining operating conditions are the same as those in Example 2, obtaining a polypropylene alloy resin composite material.

[0135] The melt index, notched Izod impact strength at 25°C (room temperature) and 0°C, flexural modulus, light transmittance, haze, and yellowness index results of the polypropylene alloy resin composite materials in the above examples and comparative examples are shown in Table 4.

[0136] Table 4

[0137]

[0138]

[0139] It can be seen from the results in Table 4 that the composite materials of Examples 1-4 of the present invention can simultaneously have good transparency, good toughness, and radiation resistance. However, compared with Example 2 and Example 3, their processing performance is poor and cannot meet the processing requirements; compared with Examples 1-4, the composite materials in Comparative Examples 1-8 cannot simultaneously have good transparency, high impact toughness, and good radiation resistance, and cannot meet the performance requirements of medical device products.

[0140] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A polypropylene alloy resin composite material, characterized in that, the composite material comprises random copolymerized polypropylene resin, polybutene-1 resin and additives; based on the total weight of the random copolymerized polypropylene resin and polybutene-1 resin, the content of the random copolymerized polypropylene resin is 75-90% by weight, and the content of the polybutene-1 resin is 10-25% by weight; wherein, the polybutene-1 resin comprises butene-1 structural units and ethylene structural units; wherein, based on the total weight of the polybutene-1 resin, the content of the ethylene structural units is 5-10% by weight; wherein, under the test conditions of 190 °C and 2.16 kg, the melt index of the polybutene-1 resin is 10-18 g / 10 min; wherein, the additives include antioxidants, and the antioxidants are phosphite antioxidants and hindered amine antioxidants.

2. The composite material according to claim 1, wherein, The 25 °C impact strength of the composite material is above 8 kJ / m 2 or more, the 0 °C impact strength is above 3.5 kJ / m 2 or more, the haze is below 15, and the light transmittance is above 90%; Preferably, the composite material has an impact strength of 8 - 12 kJ / m at 25 °C 2 , an impact strength of 4 - 5.5 kJ / m at 0 °C 2 , a haze of 8 - 15, and a light transmittance of 90 - 93%.

3. The composite material according to claim 1 or 2, wherein, under the test conditions of 230 °C and 2.16 kg, the melt index of the composite material is 20-35 g / 10 min, preferably 23-32 g / 10 min.

4. The composite material according to claim 1 or 2, wherein, the yellow index of the composite material is below 1, and further preferably (-2)-1.

5. The composite material according to claim 1 or 2, wherein, based on the total weight of the random copolymerized polypropylene resin and polybutene-1 resin, the content of the random copolymerized polypropylene resin is 80-85% by weight, and the content of the polybutene-1 resin is 15-20% by weight.

6. The composite material according to claim 1 or 2, wherein, under the test conditions of 230 °C and 2.16 kg, the melt index of the random copolymerized polypropylene resin is 21-35 g / 10 min.

7. The composite material according to claim 1 or 2, wherein the random copolymerized polypropylene resin exists in the form of powder; preferably, the random copolymerized polypropylene resin comprises propylene structural units and ethylene structural units; preferably, based on the total weight of the random copolymerized polypropylene, the content of the ethylene structural units is 3-5% by weight.

8. The composite material according to claim 1 or 2, wherein, relative to 1 kg of the random copolymerized polypropylene resin and polybutene-1 resin, the content of the antioxidant is 1.5-3 g; preferably, the weight ratio of the phosphite antioxidant to the hindered amine antioxidant is 2:1-1:

1.

9. The composite material according to claim 1 or 2, wherein, the additives further comprise a clarifying agent and / or an acid scavenger; preferably, the clarifying agent is a sorbitol clarifying agent and / or a phosphate clarifying agent; preferably, the acid scavenger is selected from at least one of hydrotalcite, calcium stearate and zinc stearate.

10. The composite material according to claim 9, wherein, relative to 1 kg of the random copolymerized polypropylene resin and polybutene-1 resin, the content of the additives is 2-6 g, preferably 2.5-5 g; Preferably, relative to 1 kg of random copolymer polypropylene resin and polybutene-1 resin, the content of the clarifying agent is 0.5 - 1 g, more preferably 0.5 - 0.8 g; Preferably, relative to 1 kg of random copolymer polypropylene resin and polybutene-1 resin, the content of the acid scavenger is 0.2 - 1 g.

11. Use of the composite material according to any one of claims 1 - 10 in medical device products.

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