CN116970243A

CN116970243A - Oil-seepage-free modified polypropylene weather-resistant material and preparation method thereof

Info

Publication number: CN116970243A
Application number: CN202310771946.7A
Authority: CN
Inventors: 岑建达; 岑光; 岑昶
Original assignee: Cixi Shanjin Polymer Plastic Co ltd
Current assignee: Cixi Shanjin Polymer Plastic Co ltd
Priority date: 2023-06-28
Filing date: 2023-06-28
Publication date: 2023-10-31

Abstract

The invention relates to the technical field of C08L29/04, in particular to an oil-impermeable modified polypropylene weather-resistant material and a preparation method thereof, wherein the weather-resistant material at least comprises the following raw materials in parts by weight: 30-80 parts of polypropylene, 40-60 parts of thermoplastic elastomer and 0.2-0.5 part of anti-aging agent, and the provided material has excellent toughness and rigidity at the same time by optimizing the formula design, thereby meeting the use requirement of the suspension floor, effectively prolonging the service life of the suspension floor and having high popularization and application values.

Description

Oil-seepage-free modified polypropylene weather-resistant material and preparation method thereof

Technical Field

The invention relates to the technical field of C08L29/04, in particular to an oil-impermeable modified polypropylene weather-resistant material and a preparation method thereof.

Background

Polypropylene (PP) is one of five general-purpose resins, which is nontoxic, odorless, light, but has limited application in many fields due to insufficient toughness, especially when applied to outdoor fields as a suspension floor, the suspension floor has a short life due to the influence of external sunlight, temperature change, impact force, etc., and because the suspension floor is used for outdoor sports fields, the short-term replacement of the suspension floor causes an increase in time cost and energy cost.

The toughness of polypropylene is improved by introducing a toughening agent into a polypropylene system in the prior art, for example, china patent application (issued to No. CN 105985582B) discloses a toughened polypropylene blend and application thereof, and the impact toughness of polypropylene is mainly improved by introducing a polymer obtained by copolymerizing ethylene and alpha-olefin into the polypropylene system. The Chinese patent application (issued publication No. CN 1063199C) discloses a high-toughness polypropylene composition, wherein POE is adopted to toughen polypropylene, and 10-25% of POE is specifically introduced to improve toughness, and the introduction of a toughener can improve the toughness of the polypropylene to a certain extent, but the toughness of a product and the addition amount of the toughener are directly influenced, so that the addition amount is lower, the toughness of the product cannot be effectively improved, the rigidity of the product is inevitably reduced due to the excessively high addition amount, and the use requirement of a suspended floor cannot be met. Therefore, how to improve the toughness of polypropylene and reduce the influence of introduction of a toughening agent on the rigidity of a product as much as possible is a technical problem which needs to be solved at present.

Disclosure of Invention

In order to solve the problems, the invention provides the oil-impermeable modified polypropylene weather-resistant material, and the provided material has excellent toughness and rigidity through optimizing the formula design, so that the use requirement of the suspended floor is met, the service life of the suspended floor is effectively prolonged, and the oil-impermeable modified polypropylene weather-resistant material has high popularization and application values.

The invention provides an oil-impermeable modified polypropylene weather-resistant material, which at least comprises the following raw materials in parts by weight: 30-80 parts of polypropylene, 40-60 parts of thermoplastic elastomer and 0.2-0.5 part of anti-aging agent.

As a preferable technical scheme, the thermoplastic elastomer is at least one selected from styrene-butadiene rubber, ethylene-propylene-diene rubber, polyisobutylene rubber and EVA, SEBS, POE. Preferably, the Shore hardness (Shore A) of the POE is 54-73, and the melt mass flow rate (190 ℃ C., 2.16 kg) is 0.5-13g/10min. Preferably, the POE is a combination of POE1 and POE2, and the Shore hardness (Shore A) of the POE1 and the POE2 is 54-66; preferably, the Shore hardness (Shore A) of the POE1 is 54-60, and the melt mass flow rate (190 ℃ C., 2.16 kg) is 0.5-3.6g/10min. The Shore hardness (Shore A) of the POE2 is 60-66, and the mass flow rate (190 ℃ C., 2.16 kg) of the melt is 9.1-13g/10min. Preferably, the mass ratio of the POE1 to the POE2 is (0.5-2): 1.

the Shore hardness (Shore A) of POE1 is 58, the melt mass flow rate (190 ℃ C., 2.16 kg) is 0.5g/10min, and the model is Japanese three-well DF605; the Shore hardness (Shore A) of POE2 is 63, the melt mass flow rate (190 ℃ C., 2.16 kg) is 13g/10min, and the model is the ceramic 8130.

According to the invention, toughness of polypropylene is improved by introducing POE, adverse effects of POE introduction on hardness of a product are considered, so that a POE product with higher hardness is preferably selected from theory, but in the actual research and development process, the fact that introduction of POE with too high hardness cannot effectively balance toughness and strength of the product, but can lead to strength reduction of the product is found, in the research process, the inventor surprisingly found that the reduction trend of POE introduction on the product strength can be reduced to a certain extent by controlling the Shore hardness (Shore A) of POE introduced into a system to be 54-73, especially POE1 with Shore hardness of 54-60 and POE2 with Shore hardness of 60-66 are simultaneously introduced, and the mass ratio of POE1 to POE2 is controlled to be (0.5-2): 1, effectively toughening the product and ensuring that the tensile strength of the product is more than 90% of the original tensile strength. The inventors analyzed the cause may be: in the melt flow process, POE2 with the melt mass flow rate of 9.1-13g/10min is introduced, so that the regularity of a polypropylene molecular chain is reduced to a certain extent, the difficulty of entering a crystal lattice by the polypropylene molecular chain and a chain segment thereof is reduced, the strength reduction trend of a product is reduced, meanwhile, dispersed phases POE1 and POE2 are partially compatible with a dispersion medium polypropylene, and when the product is impacted by external force, the dispersed phases induce silver lines and shearing bands, and the toughness of the product is improved; when POE with higher hardness is introduced into the system, the interface between POE and the polypropylene molecular chain has stronger action and larger entanglement degree, so that the strength of the product is reduced.

As a preferable technical scheme, the mass ratio of the polypropylene to the POE is 1: (0.8-1.2). As a preferred technical scheme, the polypropylene is isotactic polypropylene, and the melt mass flow rate (GB/T3682) of the isotactic polypropylene is 20-33g/10min, preferably 28-33g/10min. Preferably, the isotactic polypropylene is of the type Z30S medium petrochemical.

Based on the system of the invention, the mass ratio of polypropylene to POE is controlled to be 1: (0.8-1.2), in particular to isotactic polypropylene with a melt mass flow rate of 28-33g/10min, so as to further reduce the adverse effect of POE introduction on the strength of the product, and ensure that the provided product has excellent toughness and toughness retention rate. The inventors analyzed the cause may be: under the mass ratio, because POE1 and POE2 molecular chains introduced into the system are saturated, the whole product has relatively pure polypropylene material with improved ageing resistance and ultraviolet resistance, but isotactic polypropylene with the melt mass flow rate of 28-33g/10min is required to be matched, so that adverse effects on the strength of the product caused by the introduction of POE are further reduced, the degree of mutual entanglement between the POE molecular chains and the polypropylene molecular chains is probably increased under the condition of high addition of POE, the dispersibility of POE1 and POE2 in the isotactic polypropylene is influenced in the melt flow process, and if the melt mass flow rate of the isotactic polypropylene is lower, the locally concentrated high entanglement disturbs the regularity of the isotactic polypropylene molecular chains, so that the strength of the product is reduced, and the toughness and the strength of the product are effectively balanced under the addition of 28-33g/10min by adopting the isotactic polypropylene, so that the use requirement of a suspension floor is met.

As a preferable technical scheme, the antioxidant is selected from one or a combination of more of antioxidant 1010, antioxidant 168, UV-531, UV-9, UV-944, UV-326, UV-327 and UV-770; preferably, the antioxidant is a combination of antioxidant 1010, antioxidant 168, UV-944 and UV-531; the mass ratio of the antioxidant 1010 to the antioxidant 168 to the UV-944 to the UV-531 is 1: (1-2): 1:1.

based on the system of the invention, the mass ratio is 1: (1-2): 1: the antioxidant 1010, the antioxidant 168, the UV-944 and the UV-531 are led into a polymer system, so that the suspension floor prepared from the provided material keeps good appearance and mechanical properties when used outdoors for a long time, and the service life of the suspension floor is prolonged. The inventor analyzes that the reason is probably that under the combined action of the anti-aging agent, the oxidative decomposition of the polymer in the system is effectively inhibited, the degree of polymer molecular chain breakage of the product under the action of temperature change or illumination is reduced, and meanwhile, the phenomenon of oil seepage caused by the fact that small molecular substances in the polymer system are excited by illumination to migrate to the surface layer of the material is avoided.

The invention further provides a preparation method of the oil-impermeable modified polypropylene weather-resistant material, which comprises the steps of mixing polypropylene, thermoplastic elastomer and anti-aging agent according to parts by weight, adding the mixture into a screw extruder, and granulating. The heating temperature of the melting section of the screw extruder is 220-240 ℃.

Advantageous effects

1. The invention provides an oil-seepage-free modified polypropylene weather-resistant material, which has excellent toughness and rigidity through optimizing the formula design, meets the use requirement of a suspension floor, effectively prolongs the service life of the suspension floor, and has high popularization and application values.

2. According to the invention, the Shore hardness (Shore A) of POE introduced into the system is controlled to be 54-73, so that the reduction trend of POE introduction on the product strength can be reduced to a certain extent.

3. Based on the system of the invention, POE1 with the Shore hardness of 54-60 and POE2 with the Shore hardness of 60-66 are simultaneously introduced, and the mass ratio of the POE1 to the POE2 is controlled to be (0.5-2): 1, effectively toughening the product and ensuring that the tensile strength of the product is more than 90% of the original tensile strength.

4. Based on the system of the invention, the mass ratio of polypropylene to POE is controlled to be 1: (0.8-1.2), in particular to isotactic polypropylene with a melt mass flow rate of 28-33g/10min, so as to further reduce the adverse effect of POE introduction on the strength of the product, and ensure that the provided product has excellent toughness and toughness retention rate.

5. Based on the system of the invention, the mass ratio is 1: (1-2): 1: the antioxidant 1010, the antioxidant 168, the UV-944 and the UV-531 are led into a polymer system, so that the suspension floor prepared from the provided material keeps good appearance and mechanical properties when used outdoors for a long time, and the service life of the suspension floor is prolonged.

Drawings

FIG. 1 is a diagram of a suspension flooring product prepared by using the oil-impermeable modified polypropylene weather-resistant material provided in example 1 of the present invention.

Detailed Description

Example 1

In one aspect, the embodiment 1 of the invention provides an oil-impermeable modified polypropylene weather-resistant material, which is prepared from the following raw materials in parts by weight: 50 parts of polypropylene, 50 parts of thermoplastic elastomer and 0.4 part of anti-aging agent.

The POE is a combination of POE1 and POE2, and the mass ratio of the POE1 to the POE2 is 1:1.

The polypropylene is isotactic polypropylene, and the melt mass flow rate (GB/T3682) of the isotactic polypropylene is 28g/10min, and the model is medium petrochemical Z30S.

The antioxidant is a combination of antioxidant 1010, antioxidant 168, UV-944 and UV-531; the mass ratio of the antioxidant 1010 to the antioxidant 168 to the UV-944 to the UV-531 is 1:1:1:1.

the embodiment 1 of the invention provides a preparation method of an oil-impermeable modified polypropylene weather-resistant material, which comprises the steps of mixing polypropylene, a thermoplastic elastomer and an anti-aging agent according to parts by weight, adding the mixture into a screw extruder, and granulating. The melting section heating temperature of the screw extruder is 230 ℃.

Example 2

In one aspect, the embodiment 2 of the invention provides an oil-impermeable modified polypropylene weather-resistant material, which is prepared from the following raw materials in parts by weight: 40 parts of polypropylene, 60 parts of thermoplastic elastomer and 0.4 part of anti-aging agent.

the Shore hardness (Shore A) of POE1 is 57, the melt mass flow rate (190 ℃ C., 2.16 kg) is 1.2g/10min, and the model is Japanese three-well DF610; or the Shore hardness (Shore A) of the POE1 is 57, the melt mass flow rate (190 ℃ C., 2.16 kg) is 1.2g/10min, and the model is Japanese three well DF610. The Shore hardness (Shore A) of POE2 is 63, the melt mass flow rate (190 ℃ C., 2.16 kg) is 13g/10min, and the model is the ceramic 8130.

The antioxidant is a combination of antioxidant 1010, antioxidant 168, UV-944 and UV-9; the mass ratio of the antioxidant 1010 to the antioxidant 168 to the UV-944 to the UV-531 is 1:1:1:1.

the embodiment 2 of the invention provides a preparation method of an oil-impermeable modified polypropylene weather-resistant material, which comprises the steps of mixing polypropylene, a thermoplastic elastomer and an anti-aging agent according to parts by weight, adding the mixture into a screw extruder, and granulating. The melting section heating temperature of the screw extruder is 230 ℃.

Example 3

In one aspect, embodiment 3 of the invention provides an oil-impermeable modified polypropylene weather-resistant material, which is prepared from the following raw materials in parts by weight: 60 parts of polypropylene, 40 parts of thermoplastic elastomer and 0.4 part of anti-aging agent.

The POE is a combination of POE1 and POE2, and the mass ratio of the POE1 to the POE2 is 1.2:1.

the embodiment 3 of the invention provides a preparation method of an oil-impermeable modified polypropylene weather-resistant material, which comprises the steps of mixing polypropylene, a thermoplastic elastomer and an anti-aging agent according to parts by weight, adding the mixture into a screw extruder, and granulating. The melting section heating temperature of the screw extruder is 230 ℃.

Comparative example 1

Comparative example 1 of the present invention provides an oil-impermeable modified polypropylene weather-resistant material and a preparation method thereof, and the specific mode is the same as example 1, except that the POE is replaced with 87 shore hardness (shore a), the melt mass flow rate (190 ℃,2.16 kg) is 0.5g/10min, and the model is japanese three well DF805POE.

Comparative example 2

The invention provides an oil-impermeable modified polypropylene weather-resistant material and a preparation method thereof, which are similar to the embodiment 1 in specific mode, and are characterized in that the mass ratio of POE1 to POE2 is 1:4.

comparative example 3

The comparative example 3 of the present invention provides an oil-impermeable modified polypropylene weather-resistant material and a preparation method thereof, and a specific embodiment thereof is the same as example 1, wherein the mass ratio of POE1 to POE2 is 4:1.

comparative example 4

Comparative example 4 of the present invention provides an oil-impermeable modified polypropylene weather-resistant material and a preparation method thereof, and a specific embodiment thereof is the same as example 1, except that the melt mass flow rate (GB/T3682) of the isotactic polypropylene is 6g/10min, and the model is medium petrochemical Y600.

Comparative example 5

The invention provides an oil-impermeable modified polypropylene weather-resistant material and a preparation method thereof in comparative example 5, and the specific implementation mode is the same as example 1, except that the antioxidant is a combination of antioxidant 1010 and UV-9; the mass ratio of the antioxidant 1010 to the UV-9 is 1:1.

performance test method

1. Oil bleeding performance: reference is made to GB/T16422.3/ISO 4892-3-2006 section 3 of Plastic laboratory light Source Exposure test method: the method A (artificial climate aging) in the fluorescent ultraviolet lamp takes the cycle number 1 as an exposure condition, the ultraviolet rapid aging test is carried out on the materials provided by the embodiment and the comparative example, the exposed surface of the suspended floor is observed, and if the surface of the suspended floor has no oil seepage and warping and has no obvious change in color, the oil seepage performance of the product is marked as 'qualified'; if oil bleeding, warping and a significant change in color occurred on the surface of the suspended floor, the oil bleeding performance of the product was recorded as "off-specification" results in Table 1.

2. Weather resistance: after the materials provided in examples and comparative examples of the present invention were subjected to a high and low temperature aging test (retention at 80℃for 8 hours and a low temperature of-40℃for 8 hours, and high and low temperature cycles) for 500 hours, the appearance of the materials was observed, and the toughness retention (notched impact strength after the high and low temperature aging test/notched impact strength before the high and low temperature aging test) of the materials was measured, and the results were recorded in Table 1.

3. With reference to GB/T1043, the materials provided in examples and comparative examples were prepared into bars of 80mm by 10mm by 4mm, and the materials were tested for notched Izod impact strength (-40 ℃ C.) at a maximum impact energy of 5J using a Izod impact tester, the results of which are shown in Table 1.

4. With reference to GB/T1040, the materials provided in examples and comparative examples were made into bars to be tested having a size of 80mm by 10mm by 4mm, and the tensile strength of the materials was measured at a tensile rate of 50mm/min using a universal tensile machine, and the results are shown in Table 1.

TABLE 1,

Claims

1. The oil-impermeable modified polypropylene weather-resistant material is characterized by at least comprising the following raw materials in parts by weight: 30-80 parts of polypropylene, 40-60 parts of thermoplastic elastomer and 0.2-0.5 part of anti-aging agent.

2. The oil-impermeable modified polypropylene weather-resistant material according to claim 1, wherein the thermoplastic elastomer is at least one selected from styrene-butadiene rubber, ethylene-propylene-diene monomer rubber, polyisobutylene rubber and EVA, SEBS, POE.

3. The oil-impermeable modified polypropylene weather-resistant material according to claim 2, wherein the shore hardness of the POE is 54-87, and the melt mass flow rate is 0.5-13g/10min.

4. The oil-impermeable modified polypropylene weather-resistant material according to claim 3, wherein the POE is a combination of POE1 and POE2, and the Shore hardness of the POE1 and the POE2 is 54-66.

5. The oil-impermeable modified polypropylene weather-resistant material according to claim 4, wherein the shore hardness of POE1 is 54-60, and the melt mass flow rate is 0.5-3.6g/10min.

6. The oil-impermeable modified polypropylene weather-resistant material according to claim 4, wherein the shore hardness of POE2 is 60-66, and the melt mass flow rate is 9.1-13g/10min.

7. The oil-impermeable modified polypropylene weather-resistant material according to claim 4, wherein the mass ratio of the polypropylene to the POE is 1: (0.8-1.2).

8. The oil-impermeable modified polypropylene weather-resistant material according to claim 7, wherein the polypropylene is isotactic polypropylene, and the isotactic polypropylene has a melt mass flow rate of 20-33g/10min.

9. The oil-impermeable modified polypropylene weather-resistant material according to claim 1, wherein the anti-aging agent is selected from one or a combination of several of antioxidant 1010, antioxidant 168, UV-531, UV-9, UV-944, UV-326, UV-327 and UV-770.

10. A method for preparing the oil-impermeable modified polypropylene weather-resistant material according to any one of claims 1 to 9, which is characterized in that polypropylene, a thermoplastic elastomer and an anti-aging agent are mixed according to parts by weight and added into a screw extruder for granulation.