Polypropylene composition as well as preparation method and application thereof

Abstract

The invention provides a polypropylene composition as well as a preparation method and application thereof, and belongs to the technical field of high polymer materials. The polypropylene composition disclosed by the invention is prepared from the following components in parts by weight: 40 to 95 parts of polypropylene resin, 5 to 40 parts of a styrene toughening agent, 1 to 20 parts of an isobutylene toughening agent, 4 to 35 parts of aluminosilicate, 0.05 to 1 part of a nucleating agent and 0.1 to 1 part of an anti-aging agent, wherein the isobutylene toughening agent is at least one of butyl rubber, halogenated butyl rubber and brominated isobutylene-p-methylstyrene copolymer. The styrene flexibilizer, the isobutylene flexibilizer and the nucleating agent are added into the polypropylene composition, so that the polypropylene composition has good light transmittance, toughness and solvent resistance at the same time.

Description

Technical Field

[0001] The present disclosure relates to the technical field of polymer materials, and in particular to a polypropylene composition and a preparation method and application thereof. Background Art

[0002] As an important member of the polyolefin field, polypropylene has been widely used in many fields such as the automotive industry, home appliances, food packaging, and building decoration due to its excellent comprehensive properties such as abundant raw material sources, light weight, and easy processing. It is an important component of general plastic products.

[0003] With the development of Internet technology and electronic technology, interior and exterior surfaces have become decorative surfaces with a sense of design, integrating decoration and functionality, which has put forward new requirements for light transmittance and solvent resistance for automotive materials. Traditional automotive polypropylene interior and exterior materials are usually made by blending raw materials such as polypropylene, elastomers, and talcum powder through processing equipment such as twin-screw extruders. However, on the one hand, this solution will cause greater light reflection, light absorption and light scattering problems, which will reduce the light transmittance of polypropylene materials. On the other hand, elastomers will absorb alkanes, which will cause the solvent resistance of polypropylene materials to decrease.

[0004] Therefore, how to achieve good transparency and solvent resistance of polypropylene materials while maintaining good processing performance and physical and mechanical properties is an important issue that needs to be solved in this direction. Summary of the invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a polypropylene composition and a preparation method and application thereof.

[0006] To achieve the above-mentioned purpose, the technical solution adopted by the present disclosure is as follows: In the first aspect, a polypropylene composition is provided, comprising the following components in parts by weight: 40-95 parts of polypropylene resin, 5-40 parts of styrene toughening agent, 1-20 parts of isobutylene toughening agent, 4-35 parts of aluminosilicate, and 0.05-1 part of nucleating agent;

[0007] The isobutylene toughening agent is at least one of butyl rubber, halogenated butyl rubber and brominated isobutylene-p-methylstyrene copolymer.

[0008] In some embodiments, the isobutylene toughening agent is brominated isobutylene-p-methylstyrene copolymer.

[0009] In some embodiments, the styrene-based toughening agent is at least one of styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer, styrene-isoprene-styrene block copolymer, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, and acrylonitrile-styrene-acrylate copolymer.

[0010] In some embodiments, the aluminosilicate is glass fiber powder and / or mica.

[0011] In some embodiments, the nucleating agent is at least one of a sorbitol nucleating agent and an aromatic carboxylate.

[0012] In some embodiments, the anti-aging agent is at least one of an antioxidant and a light stabilizer.

[0013] In some embodiments, the antioxidant is at least one of a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant.

[0014] In some embodiments, the light stabilizer is a hindered amine light stabilizer.

[0015] On the other hand, a method for preparing the polypropylene composition is provided, comprising the following steps: mixing the components uniformly according to a certain proportion, and then performing melt extrusion granulation to obtain the polypropylene composition.

[0016] In another aspect, provided is a use of the polypropylene composition in preparing automotive interior trims and / or automotive exterior trims.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention adds styrene toughening agents, isobutylene toughening agents and nucleating agents to polypropylene resin, thereby improving toughness, light transmittance and solvent resistance. DETAILED DESCRIPTION

[0018] In order to facilitate understanding of the present disclosure, the present disclosure will be described more fully below. However, the present disclosure can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present disclosure more thorough and comprehensive.

[0019] As used herein:

[0020] "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0021] The conjunction "consisting of excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed-ended so that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0022] When amount, concentration or other value or parameter is represented by range, preferred range or a series of upper preferred value and lower preferred value, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value and any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when disclosing range "1-5", described range should be interpreted as including range "1-4", "1-3", "1-2", "1-2 and 4-5", "1-3 and 5" etc. When numerical range is described in this article, unless otherwise stated, the range is intended to include its end value and all integers and fractions within the range.

[0023] In these examples, parts and percentages are by mass unless otherwise indicated.

[0024] "Parts by mass" refers to the basic unit of measurement for expressing the mass ratio of multiple components. 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass of component A is a parts and the mass of component B is b parts, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that, unlike the mass parts, the sum of the mass of all components is not limited to 100 parts.

[0025] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0026] In a first aspect, a polypropylene composition is provided, comprising the following components in parts by weight: 40-95 parts of a polypropylene resin, 5-40 parts of a styrene toughening agent, 1-20 parts of an isobutylene toughening agent, 4-35 parts of an aluminosilicate, and 0.05-1 parts of a nucleating agent;

[0027] The isobutylene toughening agent is at least one of butyl rubber, halogenated butyl rubber and brominated isobutylene-p-methylstyrene copolymer.

[0028] In the present disclosure, a styrene toughening agent, an isobutylene toughening agent and a nucleating agent are added to a polypropylene resin to improve toughness, light transmittance and solvent resistance; wherein the styrene toughening agent can provide rigidity, toughness and light transmittance of the polypropylene composition; the styrene toughening agent and the isobutylene toughening agent work together to improve the solvent resistance, rigidity and toughness of the polypropylene composition; the nucleating agent can not only improve the light transmittance of the polypropylene composition, but also work together with the isobutylene toughening agent to reduce the influence of surface energy and improve the solvent resistance of the polypropylene composition.

[0029] Specifically, the weight parts of the polypropylene resin can be, but are not limited to, 40 parts, 42 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 93 parts, and 95 parts;

[0030] Specifically, the weight parts of the styrene-based toughening agent can be, but are not limited to, 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 32 parts, 35 parts, 37 parts, and 40 parts;

[0031] Specifically, the weight parts of the isobutylene toughening agent can be 1 part, 3 parts, 5 parts, 7 parts, 10 parts, 12 parts, 15 parts, 17 parts, 20 parts;

[0032] Specifically, the weight parts of the aluminosilicate can be, but are not limited to, 4 parts, 8 parts, 10 parts, 12 parts, 15 parts, 17 parts, 20 parts, 23 parts, 25 parts, 28 parts, 30 parts, 33 parts, 35 parts;

[0033] Specifically, the nucleating agent can be, but is not limited to, 0.05 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.7 parts, 1 part;

[0034] Specifically, the amount of the anti-aging agent may be, but is not limited to, 0.1 part, 0.3 part, 0.5 part, 0.7 part, or 1 part.

[0035] Specifically, based on 100% by weight of the polypropylene composition, the content of the polypropylene resin is not less than 30%.

[0036] Specifically, according to ISO 1133-1-2022 standard test, the melt flow rate of the polypropylene resin at 230°C and 2.16kg is 1-100g / 10min, for example, it can be but not limited to 1g / 10min, 5g / 10min, 10g / 10min, 20g / 10min, 30g / 10min, 40g / 10min, 50g / 10min, 60g / 10min, 70g / 10min, 80g / 10min, 90g / 10min, and 100g / 10min.

[0037] In some embodiments, the halogenated butyl rubber is brominated butyl rubber and / or chlorinated butyl rubber.

[0038] In some embodiments, the isobutylene toughening agent is brominated isobutylene-p-methylstyrene copolymer.

[0039] The applicant has found that when the isobutylene toughening agent is a brominated isobutylene-p-methylstyrene copolymer, the solvent resistance of the obtained polypropylene composition is higher.

[0040] Specifically, according to the ASTM D1646-2017 standard test, the Mooney viscosity (ML1+8, 125° C.) of the isobutylene toughening agent is 30-55, for example, it can be but not limited to 30, 32, 35, 37, 40, 43, 45, 48, 50, 52, 55.

[0041] In some embodiments, the styrene-based toughening agent is at least one of styrene-butadiene rubber (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-isoprene copolymer (SIS), acrylonitrile-butadiene-styrene copolymer (ABS), methyl methacrylate-butadiene-styrene copolymer (MBS), and acrylonitrile-styrene-acrylate copolymer (ASA).

[0042] Specifically, the styrene content in the styrene toughening agent is 15-35%, for example, it can be but not limited to 15%, 17%, 19%, 21%, 23%, 25%, 27%, 29%, 31%, 33%, 35%; the test standard is GOST R54551-2011.

[0043] Specifically, the melt index of the styrene-based toughening agent at 230°C and 2.16kg is 1-40g / 10min, for example, it can be but not limited to 1g / 10min, 5g / 10min, 10g / 10min, 15g / 10min, 20g / 10min, 25g / 10min, 30g / 10min, 35g / 10min, 40g / 10min, and the test standard is ISO1133-1-2022.

[0044] In some embodiments, the aluminosilicate is glass fiber powder and / or mica.

[0045] The present invention uses aluminosilicate as filler. Aluminosilicate has high whiteness and transparency, and can obtain a polypropylene composition with higher light transmittance, rigidity, toughness and solvent resistance at a high content.

[0046] Specifically, the whiteness of the aluminosilicate is greater than 94; the testing standard is GB T 17749-2008.

[0047] Specifically, the average particle size of the aluminosilicate is 50-100 μm, and the testing method is GB / T19077-2016.

[0048] In some embodiments, the nucleating agent is at least one of a sorbitol nucleating agent and an aromatic carboxylate.

[0049] The nucleating agent can further improve the light transmittance and solvent resistance of the polypropylene composition.

[0050] In some embodiments, the polypropylene composition further comprises 0.1-1 parts by weight of an anti-aging agent, wherein the anti-aging agent is at least one of an antioxidant and a light stabilizer.

[0051] In some embodiments, the antioxidant is at least one of a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant.

[0052] Specific examples of the antioxidant include antioxidant 1010, antioxidant 1076, antioxidant 3114, antioxidant 168, antioxidant PEP-36, and antioxidant 412S.

[0053] In some embodiments, the light stabilizer is a hindered amine light stabilizer.

[0054] Specific examples of the light stabilizer include UV-3808, LA-402XP, and LA-402AF.

[0055] In some embodiments, the polypropylene composition further includes a processing aid; the processing aid includes at least one of an antistatic agent, a foaming agent, a lubricant, a plasticizer, a release agent, and a pigment; the amount of the processing aid, while ensuring the rigidity, toughness, light transmittance and solvent resistance of the polypropylene composition, the technicians in this field can choose to add a suitable and appropriate amount of processing aid according to actual needs.

[0056] The production method of the polypropylene composite of the present invention is not particularly strictly limited, and is carried out using a blending device such as a banbury mixer, a single screw or a twin screw extruder. The order of addition between the components is not particularly strictly limited, and can be added simultaneously or in a certain order, and two or more components can be selected from all components for pre-mixing or banburying. For example, fillers can be pre-formed into master batches, and then added to the melt of other components in the form of master batches according to a set ratio, and extruded. Under the condition that the mixing capacity of the equipment allows, the particles formed by the master batch and other components can also be mixed and melt-processed in a set ratio when molding or producing parts. The resin used in the master batch can be the polypropylene resin described in the present invention.

[0057] Specifically, the preparation method of the polypropylene composition comprises the following steps: after uniformly mixing the components in proportion, adding the components into a screw extruder for melt extrusion granulation to obtain the polypropylene composition.

[0058] In some embodiments, the temperature of the melt extrusion granulation is 200-220°C; for example, it can be but not limited to 200°C, 205°C, 210°C, 215°C, 220°C.

[0059] In some embodiments, the mixing speed is 300-500 rpm.

[0060] In some embodiments, the mixing speed is 350-450 rpm.

[0061] On the other hand, provided is the use of the polypropylene composition in the preparation of automotive interior and / or automotive exterior parts; for example, an integrated luminous front face, a luminous tailgate back panel, a luminous door panel, a luminous fender, a luminous trim, and an intelligent control panel.

[0062] The raw materials used in the embodiments and comparative examples are described below, but this scheme is not limited to these materials:

[0063] Polypropylene resin: PP H9018, melt flow rate 60 g / 10 min at 230 °C and 2.16 kg, Lanzhou Petrochemical;

[0064] Styrene toughening agent:

[0065] Styrene-ethylene / butylene-styrene block copolymer (SEBS): SEBS1643, Kraton;

[0066] Styrene-butadiene-styrene block copolymer (SBS): H3591, Zhongli Technology;

[0067] Styrene-isoprene copolymer (SIS): I4045, Zhongli Technology;

[0068] Isobutylene toughening agent:

[0069] Bromobutyl rubber-1 (IIR-1): Exxon 2222, Mooney viscosity (ML1+8, 125°C) is 32, Exxon;

[0070] Bromobutyl rubber-2 (IIR-2): Exxon 2255, Mooney viscosity (ML1+8, 125°C) is 46, Exxon;

[0071] Brominated isobutylene-p-methylstyrene copolymer-1 (BIMSM-1): Exxpro 3035, Mooney viscosity (ML1+8, 125°C) is 45, Exxon;

[0072] Brominated isobutylene-p-methylstyrene copolymer-2 (BIMSM-2): Exxpro 3433, Mooney viscosity (ML1+8, 125°C) is 35, Exxon;

[0073] Aluminosilicates:

[0074] Glass fiber powder: EMG-70, Taian Zhongshuo;

[0075] Mica: 60-D, Huajing Mica;

[0076] Calcium carbonate: commercially available;

[0077] Nucleating agent 1: 1,2,3-trideoxy-4,6:5,7-bis-O-[(4-propylphenyl)methylene]-nonanol, MILLADNX8000K, Milliken;

[0078] Nucleating agent 2: monohydroxybis(p-tert-butyl)aluminum benzoate, A1-PTBBA, DIC Japan;

[0079] Nucleating agent 3: 2,2'-methylene-bis(4,6-di-tert-butylphenyl phosphate) basic aluminum, NA-21, Japan Aidico;

[0080] Antioxidant 1010: commercially available;

[0081] Antioxidant 168: Commercially available;

[0082] Light stabilizer: UV-3808, commercially available.

[0083] Examples and Comparative Examples

[0084] The components and weight proportions of the polypropylene compositions of the embodiments and comparative examples are shown in Table 1 and Table 2, wherein the preparation method of the polypropylene compositions of the embodiments and comparative examples comprises the following steps:

[0085] After the components are uniformly mixed according to Table 1 and Table 2, the resulting mixture is added to a twin-screw extruder for melt extrusion granulation to obtain a polypropylene composition; wherein the twin-screw extruder has an aspect ratio of 40:1, a screw speed of 400 rpm, and an extrusion temperature of 200-220°C.

[0086] The polypropylene compositions obtained in the examples and comparative examples were subjected to performance tests, and the test methods were as follows:

[0087] (1) Light transmittance: The polypropylene composition was injection molded into a 100 mm*100 mm*3 mm sample, and the light transmittance of the sample was measured according to the test method of GB 2410-2008;

[0088] (1) Solvent resistance: The polypropylene composition was injection molded into a 100 mm*100 mm*3 mm sample, and an equal amount of 70# white oil was titrated on the surface of the sample. After being stored at 23°C and 50% humidity for 24 hours, the surface was wiped with alcohol until there was no obvious oil stain. Oil absorption rate = (weight of sample after test - weight of sample before test) / weight of sample before test * 100%;

[0089] (3) Flexural modulus: The polypropylene composition was injection molded into a 80 mm*10 mm*4 mm sample and tested according to standard ISO 178-2010. The test conditions were: 23°C, bending speed 2 mm / min;

[0090] (4) Izod notched impact strength: The polypropylene composition was injection molded into a 80 mm*10 mm*4 mm specimen and tested according to standard ISO180-2019. The test conditions were: A-notch, 23°C, and pendulum energy 4 J.

[0091] The test results are shown in Table 1 and Table 2.

[0092] Table 1

[0093]

[0094]

[0095] Table 2

[0096]

[0097] From the experimental data in Table 1, it can be seen that the light transmittance of the polypropylene composition disclosed in the present invention can reach more than 57%, the flexural modulus can reach more than 1510 MPa, and the cantilever beam notched impact strength can reach 40 kJ / m 2 As shown above, the oil absorption rate is 0.19-0.31%, which indicates that the polypropylene composition disclosed in the present invention has high rigidity, toughness, light transmittance and solvent resistance.

[0098] Comparative Examples 3-5 show that when the styrene toughening agent is SEBS, the light transmittance of the obtained polypropylene composition is 65%, the flexural modulus is 2050 MPa, and the Izod notched impact strength is 48 kJ / m 2 The oil absorption rate is 0.24%, which indicates that when the styrene toughening agent is SEBS, the obtained polypropylene composition has higher rigidity, toughness, light transmittance and solvent resistance.

[0099] By comparing Example 3 with Examples 6-8, it can be seen that when the isobutylene toughening agent is brominated isobutylene-p-methylstyrene copolymer, the oil absorption rate of the obtained polypropylene composition is 0.2-0.21%, indicating that when the isobutylene toughening agent is brominated isobutylene-p-methylstyrene copolymer, the solvent resistance of the obtained polypropylene composition is higher.

[0100] By comparing Example 3, Example 9 and Comparative Example 1, it can be seen that the type of filler affects the rigidity, toughness, light transmittance and solvent resistance of the polypropylene composition. The filler is aluminosilicate, and the light transmittance of the obtained polypropylene composition is 57-65%, the flexural modulus is 1930-2050MPa, and the cantilever beam notched impact strength is 43-48kJ / m 2 , the oil absorption rate is 0.24-0.28%, which indicates that the aluminosilicate is glass fiber powder and / or mica, and the obtained polypropylene composition has higher rigidity, toughness, light transmittance and solvent resistance.

[0101] By comparing Example 3, Example 10 and Comparative Example 5, it can be seen that when the nucleating agent is at least one of a sorbitol nucleating agent and an aromatic carboxylate, the light transmittance of the obtained polypropylene composition is 65-68%, the flexural modulus is 2050-2070 MPa, and the Izod notched impact strength is 43-48 kJ / m 2 , and the oil absorption rate is 0.24-0.25%, which indicates that the above nucleating agent can synergistically enhance the effect with the isobutylene toughening agent to improve the rigidity, toughness, light transmittance and solvent resistance of the polypropylene composition.

[0102] By comparing Example 3 with Comparative Examples 2-4, it can be seen that the light transmittance of the obtained polypropylene composition is lower than 50% and the notched Izod impact strength is lower than 32 kJ / m due to the lack of at least one of the nucleating agent or the isobutylene toughening agent. 2The oil absorption rate is higher than 0.38%, indicating that the lack of at least one of the nucleating agent or the isobutylene toughening agent cannot make the polypropylene composition have good light transmittance, toughness and solvent resistance at the same time.

[0103] Finally, it should be noted that the above embodiments are used to illustrate the technical solution of the present disclosure rather than to limit the protection scope of the present disclosure. Although the present disclosure has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present disclosure can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present disclosure.

Claims

1. A polypropylene composition, characterized in that The invention comprises the following components in parts by weight: 40-95 parts of polypropylene resin, 5-40 parts of styrene toughening agent, 1-20 parts of isobutylene toughening agent, 4-35 parts of aluminosilicate, and 0.05-1 parts of nucleating agent; The isobutylene toughening agent is at least one of butyl rubber, halogenated butyl rubber and brominated isobutylene-p-methylstyrene copolymer.

2. The polypropylene composition according to claim 1, characterized in that The isobutylene toughening agent is brominated isobutylene-p-methylstyrene copolymer.

3. The polypropylene composition according to claim 1, characterized in that The styrene-based toughening agent is at least one of styrene-butadiene rubber, styrene-butadiene-styrene block copolymer, styrene-ethylene / butylene-styrene block copolymer, styrene-isoprene-styrene block copolymer, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, and acrylonitrile-styrene-acrylate copolymer.

4. The polypropylene composition according to claim 1, characterized in that The aluminosilicate is glass fiber powder and / or mica.

5. The polypropylene composition according to claim 1, characterized in that The nucleating agent is at least one of a sorbitol nucleating agent and an aromatic carboxylate.

6. The polypropylene composition according to claim 1, characterized in that The polypropylene composition further comprises 0.1-1 parts by weight of an anti-aging agent, wherein the anti-aging agent is at least one of an antioxidant and a light stabilizer.

7. The polypropylene composition according to claim 6, characterized in that The antioxidant is at least one of a hindered phenol antioxidant, a phosphite antioxidant, and a thioester antioxidant.

8. The polypropylene composition according to claim 6, characterized in that The light stabilizer is a hindered amine light stabilizer.

9. The method for preparing the polypropylene composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: mixing the components uniformly according to a certain proportion, and then performing melt extrusion granulation to obtain a polypropylene composition.

10. Use of the polypropylene composition according to any one of claims 1 to 8 in the preparation of automotive interior trims and / or automotive exterior trims.

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