Polybutylene terephthalate composite material as well as preparation method and application thereof

Abstract

The invention discloses a PBT composite material and a preparation method thereof, and relates to the technical field of modified PBT composite materials. The invention provides a polybutylene terephthalate composite material. The polybutylene terephthalate composite material is prepared from the following components in parts by weight: 50-85 parts of polybutylene terephthalate, 1-10 parts of a titanium dioxide coloring agent, 1-10 parts of an acrylic acid toughening agent, 6-20 parts of ionic liquid and 0.1-1.5 parts of an antioxidant, the ionic liquid is composed of positive ions and negative ions, the positive ions comprise at least one of 1-methylpyridinium ions, 1-butylpyridinium ions, 1-butyl-4-methylpyridinium ions, 1-allyl-1-methylpyrrolidinium ions and 1-butyl-1-methylpyrrolidinium ions, and the negative ions comprise at least one of 1-methylpyridinium ions, 1-butylpyridinium ions, 1-butyl-4-methylpyridinium ions, 1-allyl-1-methylpyrrolidinium ions and 1-butyl-1-methylpyrrolidinium ions. The anions comprise at least one of chloride ions, bromide ions, iodide ions and bis (trifluoromethylsulfonyl) imine ions. Through the special compounding effect of all the components, the polybutylene terephthalate composite material with good fluidity and excellent hydrolysis resistance is prepared.

Description

Technical Field

[0001] The present invention relates to the technical field of modified polybutylene terephthalate composites, and in particular to a polybutylene terephthalate composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Polybutylene terephthalate (PBT) is a semi-crystalline engineering plastic with good mechanical properties, electrical properties, heat resistance, chemical resistance, etc., and is widely used in industries such as automobiles, electronics, and electrical appliances. At present, under the use environment, especially under the dual action of humidity and heat, the modified PBT material is still prone to yellowing and embrittlement. Not only the appearance of the final product is affected, but also the service life of the material is greatly reduced. With the continuous expansion of the application fields of PBT, many industries, especially in the fields of construction, automobiles, lighting fixtures, etc., not only have thin walls but also have high color requirements, which put forward higher requirements for the hydrolysis resistance of PBT materials. Therefore, the materials suitable for the above-mentioned parts not only need to have good fluidity and high strength, but also hydrolysis resistance is very crucial.

[0003] CN101490172A discloses a polybutylene terephthalate with excellent mechanical properties and hydrolysis resistance, which mainly adds a thermoplastic elastomer and a small amount of acrylic oligomers. The process of this method is relatively simple, but the ability to improve fluidity is limited, and it has some negative effects on the hydrolysis resistance of the material. CN104379670A discloses a polybutylene terephthalate composition and a preparation method of a hydrolysis resistance improver: adding (B) a carbodiimide compound and (C) a polyhydroxy compound-containing compound to (A) a polybutylene terephthalate resin with a terminal carboxyl group content of 30 meq / kg or less. As the (C) polyhydroxy compound-containing compound, a substance with a hydroxyl value of 200 or more is used. The preparation process of this method is simple and has a certain hydrolysis resistance effect, but the preparation cost is expensive.

[0004] Therefore, developing a PBT composite material with good fluidity and hydrolysis resistance has broad market application prospects. Summary of the Invention

[0005] Based on this, the purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a PBT composite material with good fluidity and hydrolysis resistance.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows: A polybutylene terephthalate composite material, comprising the following components in parts by weight: 50-85 parts of polybutylene terephthalate, 1-10 parts of titanium dioxide colorant, 1-10 parts of acrylic toughening agent, 6-20 parts of ionic liquid, 0.1-1.5 parts of antioxidant; The ionic liquid is composed of a cation and an anion, and the cation includes at least one of 1-methylpyridinium ion, 1-butylpyridinium ion, 1-butyl-4-methylpyridinium ion, 1-allyl-1-methylpyrrolidinium ion, 1-butyl-1-methylpyrrolidinium ion, and the anion includes at least one of chloride ion, bromide ion, iodide ion, bis(trifluoromethylsulfonyl)imide ion.

[0007] Preferably, the weight percentage content of the polybutylene terephthalate in the polybutylene terephthalate composite material is not less than 60%.

[0008] Optionally, the weight parts of the PBT are one or any range value between any two of 50 parts, 51 parts, 53 parts, 55 parts, 58 parts, 60 parts, 61 parts, 63 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 80 parts, 82 parts, 85 parts; the titanium dioxide colorant is one or any range value between any two of 1 part, 2 parts, 3 parts, 5 parts, 8 parts, 10 parts; the acrylic toughening agent is one or any range value between any two of 1 part, 2 parts, 3 parts, 5 parts, 8 parts, 10 parts; the ionic liquid is one or any range value between any two of 6 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts; the antioxidant is one or any range value between any two of 0.1 part, 0.2 part, 0.5 part, 0.8 part, 1 part, 1.1 part, 1.3 part, 1.5 part.

[0009] Through the special compounding effect of the titanium dioxide colorant, acrylic toughening agent, and ionic liquid, the present invention improves the dispersion of the titanium dioxide and acrylic toughening agent in the material, thereby preparing a white polybutylene terephthalate composite material with good fluidity and good hydrolysis resistance. The present invention selects pyridine or pyrrole-based ionic liquids, and the cation is a cyclic N-alkyl-containing ion. The selected anion further increases the asymmetry of the ionic liquid molecular structure, preventing the cations and anions from regularly stacking into crystals, thereby weakening the force between the cations and anions and making it easier to melt; at the same time, it also further increases the dissolution ability of the ionic liquid to substances, and can better cooperate with the titanium dioxide colorant and acrylic toughening agent, thereby preparing a white polybutylene terephthalate composite material with good fluidity and good hydrolysis resistance.

[0010] Preferably, the weight ratio of the titanium dioxide colorant, acrylic toughening agent, and ionic liquid is titanium dioxide colorant: acrylic toughening agent: ionic liquid = (1-2):(1-2):2.

[0011] During the actual experiment, the inventors found that when the weight ratio of titanium dioxide colorant, acrylic toughening agent, and ionic liquid is within the above specific range, the prepared polybutylene terephthalate composite material has better hydrolysis resistance and better fluidity.

[0012] Preferably, the ionic liquid includes at least one of 1-butylpyridinium chloride and 1-butyl-4-methylpyridinium bromide.

[0013] Preferably, the acrylic toughening agent is at least one of ethylene-acrylate-glycidyl methacrylate terpolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and glycidyl methacrylate grafted ethylene-octene copolymer.

[0014] Preferably, the melt mass flow rate of the acrylic toughening agent is 0.5-15 g / 10 min at a test temperature of 190 °C and a load of 2.16 kg according to ISO 1133-2022.

[0015] Preferably, the mass percentage content of TiO2 in the titanium dioxide colorant is ≥92%. The test method for the mass percentage content of TiO2 in the titanium dioxide is the XFR method.

[0016] Optionally, the mass percentage content of TiO2 in the titanium dioxide colorant is one of 92%, 93%, 95%, 96%, 97% or the range value of any two of them.

[0017] Preferably, the melt mass flow rate of the PBT is 1-50 g / 10 min at a test temperature of 250 °C and a load of 2.16 kg according to ISO 1133-2022, and the intrinsic viscosity of the PBT is 0.5-1.5 dL / g; the intrinsic viscosity of the PBT resin is measured with reference to the standard GB / T 1632.5-08-2008. Accurately weigh 0.25 g of PBT and dissolve it in a mixed solution of 50 mL of phenol and 1,2-dichlorobenzene (concentration about 0.5 g / dL) at a temperature of 130 °C, cool it, and measure the time for the solution to flow through the Ubbelohde viscometer at 25 °C, and calculate the intrinsic viscosity of the sample.

[0018] The antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.

[0019] Preferably, the PBT has a melt mass flow rate of 1 g / 10 min, 3 g / 10 min, 5 g / 10 min, 10 g / 10 min, 15 g / 10 min, 18 g / 10 min, 25 g / 10 min, 30 g / 10 min, 35 g / 10 min, 40 g / 10 min, 43 g / 10 min, 45 g / 10 min, or 50 g / 10 min under the conditions of a test temperature of 250 °C and a load of 2.16 kg according to ISO 1133-2022. The intrinsic viscosity of the PBT is in the range of one or any two of 0.5 dL / g, 0.8 dL / g, 1.0 dL / g, 1.3 dL / g, and 1.5 dL / g.

[0020] More preferably, the hindered phenol antioxidant includes at least one of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, and bis[β-(3,5-di-tert-butyl-4-hydroxybenzoyl)] hydrazine; the phosphite antioxidant includes at least one of bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite and tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyldiphosphite.

[0021] In addition, the present invention provides a method for preparing the PBT composite material, comprising the following steps: mixing the components evenly, followed by melt extrusion and pelletization to obtain the PBT composite material.

[0022] Preferably, the conditions for melt extrusion are: 180 ± 10 °C, 240 ± 10 °C, 250 ± 10 °C, 250 ± 10 °C, 250 ± 10 °C, 240 ± 10 °C, and the rotation speed is 250 - 300 rpm.

[0023] Furthermore, the present invention provides the application of the PBT composite material in the preparation of mobile phones, tablet computers, and automotive interior housing parts.

[0024] Compared with the prior art, the beneficial effects of the present invention are as follows: Through the special compounding effect of titanium dioxide colorant, toughening agent, and ionic liquid, the present invention prepares a white PBT composite material with good fluidity and good hydrolysis resistance. Detailed Embodiments

[0025] To better illustrate the objectives, technical solutions, and advantages of the present invention, the following will further explain the present invention in conjunction with specific embodiments. The purpose is to understand the content of the present invention in detail, rather than to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention. The experimental reagents and instruments involved in the implementation of the present invention are all common ordinary reagents and instruments unless otherwise specified.

[0026] The raw materials used in the examples and comparative examples are described as follows, but are not limited to these materials:

[0027] PBT Resin - 1: Intrinsic viscosity 1.3 dL / g, melt index 12 g / 10 min (250 °C, 2.16 kg), purchased from Yizheng Chemical, grade PBT GL236.

[0028] PBT Resin - 2: Intrinsic viscosity 1.0 dL / g, melt index 30 g / 10 min (250 °C, 2.16 kg), purchased from Yizheng Chemical, grade PBT GX121.

[0029] PBT Resin - 3: Intrinsic viscosity 0.8 dL / g, melt index 50 g / 10 min (250 °C, 2.16 kg), purchased from Yizheng Chemical, grade PBT GX112.

[0030] Toughening Agent 1: Ethylene - acrylate - glycidyl methacrylate terpolymer, grade PTW, DuPont;

[0031] Toughening Agent 2: Ethylene - ethyl acrylate copolymer, grade AC 2615, DuPont

[0032] Toughening Agent 3: Ethylene - methyl acrylate copolymer, grade AC 1125, DuPont;

[0033] Toughening Agent 4: Maleic anhydride grafted POE, grade FUSABOND N493, DuPont;

[0034] Titanium Dioxide Colorant - 1: TiO2 content 95%, grade KRONOS2225, KRONOS;

[0035] Titanium Dioxide Colorant - 2: TiO2 content 92%, grade PC - 3, ISK Japan;

[0036] Titanium Dioxide Colorant - 3: TiO2 content 97%, grade R - 103, Chemours;

[0037] Ionic liquid - 1: Purity 97%, 1 - butylpyridinium chloride (CAS: 1124 - 64 - 7), purchased from TCI (Tokyo Chemical Industry) Chemical Company; Anion: chloride ion, Cation: 1 - butylpyridinium ion;

[0038] Ionic liquid - 2: Purity 96%, 1 - butyl - 4 - methylpyridinium bromide (CAS: 65350 - 59 - 6), purchased from TCI Chemical Company; Anion: bromide ion, Cation: 1 - butyl - 4 - methylpyridinium ion;

[0039] Ionic liquid - 3: Purity 97%, 1 - methylpyridinium bis(trifluoromethanesulfonyl)imide (CAS: 742086 - 10 - 8), purchased from TCI Chemical Company; Anion: bis(trifluoromethanesulfonyl)imide ion, Cation: 1 - methylpyridinium ion;

[0040] Ionic liquid - 4: Purity 97%, 1 - butyl - 1 - methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (CAS: 223437 - 11 - 4), purchased from TCI Chemical Company; Anion: bis(trifluoromethanesulfonyl)imide ion, Cation: 1 - butyl - 1 - methylpyrrolidinium ion;

[0041] Ionic liquid - 5: Purity 96%, tetrabutylphosphonium tetrafluoroborate (CAS: 1813 - 60 - 1), purchased from TCI Chemical Company; Anion: tetrafluoroborate ion, Cation: tetrabutylphosphonium ion;

[0042] Ionic liquid - 6: Purity 97%, trihexyl(tetradecyl)phosphonium dicyanamide (CAS: 701921 - 71 - 3), purchased from TCI Chemical Company; Anion: dicyanamide ion, Cation: trihexyl(tetradecyl)phosphonium ion;

[0043] Ionic liquid - 7: Purity 96%, triethylsulfonium bis(trifluoromethanesulfonyl) - imide salt (CAS: 321746 - 49 - 0), purchased from TCI Chemical Company; Anion: bis(trifluoromethanesulfonyl) - imide ion, Cation: triethylsulfonium ion;

[0044] The antioxidant is a composite of commercially available hindered phenol antioxidant 1010 and commercially available phosphite antioxidant PEP - 36 in a mass ratio of 1:5.

[0045] Examples 1 - 14 and Comparative Examples 1 - 6

[0046] Examples of the polybutylene terephthalate composite material described in the present invention. The composition components of the PBT composite material are shown in Table 1 and Table 2. The preparation method of the PBT composite material includes the following steps:

[0047] Mix all components evenly, followed by melt extrusion and pelletization to obtain the PBT composite material. The conditions for the melt extrusion are: 180°C, 240°C, 250°C, 250°C, 250°C, 240°C, and the rotation speed is 250 rpm.

[0048] The difference between each comparative example and the example lies only in the types and ratios of the components, as shown in Table 3.

[0049] Table 1

[0050]

[0051]

[0052] Table 2

[0053]

[0054]

[0055] Table 3

[0056]

[0057]

[0058] Performance testing

[0059] To verify the performance of the PBT composite material of the present invention, the products prepared in each example and comparative example were subjected to the following performance tests. The specific steps are as follows:

[0060] Respectively dry the PBT materials provided in the above examples and comparative examples in an oven at 120°C for 3 - 4 hours and then perform injection molding. The injection molding temperature is 250°C; Izod notched impact strength test: According to the ISO 179 / 1eA - 2010 standard method, inject each product into an impact specimen with dimensions of 80×10×4 mm, and the pendulum energy is 1 J. Place the injection - molded standard specimens at 25°C and 50% relative humidity for 24 hours and then test the performance.

[0061] (1) The helix length measures the injection molding fluidity: Mould the dried particles above into a spiral product with a thickness of 2.0 mm and a width of 5 mm, and judge the fluidity based on its flow length. Among them, the injection molding temperature is 250°C, the mold temperature is 65°C, the injection molding speed is 70 mm / s, and the pressure holding is 50 Mpa for 10 seconds for comparative evaluation.

[0062] (2) Hydrolysis resistance: Inject the notched impact specimens of each product well, and immerse them in hot water at 80 ± 2 °C for 500 h, and then adjust for 24 h at room temperature and environment, and then test the notched impact strength of the simply supported beam. The test of the notched impact strength of the simply supported beam is measured in the same way as in (1). The retention rate of the notched impact strength of the simply supported beam after hydrolysis % = the notched impact strength of the simply supported beam after hydrolysis ÷ the notched impact strength of the simply supported beam before hydrolysis × 100%. The higher the retention rate of the notched impact strength of the simply supported beam after hydrolysis, the stronger the hydrolysis resistance performance.

[0063] The test results are shown in Table 4.

[0064] Table 4

[0065]

[0066]

[0067] As can be seen from the above table, for the PBT composite material prepared in the embodiment of the present invention, through the compounding of specific components and parts by weight of titanium dioxide colorant, acrylic toughening agent, and ionic liquid, the retention rate of the notched impact strength is above 60%, and the injection molding spiral length before hydrolysis is 20 - 40 mm, and injection molding can be well completed.

[0068] It can be seen from the comparison of Example 1, Examples 6 - 8, and Comparative Example 6 that the type of toughening agent will affect the hydrolysis resistance and fluidity of the prepared PBT composite material. When the toughening agent is an acrylic toughening agent, the prepared PBT composite material has better hydrolysis resistance and better fluidity.

[0069] It can be seen from the comparison of Example 1, Examples 9 - 10, and Comparative Examples 1 - 3 that the selection of ionic liquid has a great influence on the retention rate of the notched impact strength and fluidity of the PBT composite material after hydrolysis. When the ionic liquid includes at least one of 1 - butylpyridinium chloride and 1 - butyl - 4 - methylpyridinium bromide, the retention rate of the notched impact strength of the PBT composite material after hydrolysis is better, and the fluidity can better meet the actual use requirements.

[0070] It can be seen from the comparison of Example 1, Examples 11 - 14, and Comparative Example 4 that through the special compounding effect of titanium dioxide colorant, acrylic toughening agent, and ionic liquid of the present invention, a white PBT composite material with good fluidity and good hydrolysis resistance is prepared. When the ratio of the titanium dioxide colorant: acrylic toughening agent: ionic liquid = (1 - 2):(1 - 2):2, the prepared PBT composite material has better hydrolysis resistance and better fluidity to meet the injection molding requirements.

[0071] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polybutylene terephthalate composite material, characterized in that, It comprises the following components in parts by weight: 50 - 85 parts of polybutylene terephthalate, 1 - 10 parts of titanium dioxide colorant, 1 - 10 parts of acrylic toughening agent, 6 - 20 parts of ionic liquid, and 0.1 - 1.5 parts of antioxidant; the ionic liquid is composed of a cation and an anion, the cation includes at least one of 1 - methylpyridinium ion, 1 - butylpyridinium ion, 1 - butyl - 4 - methylpyridinium ion, 1 - allyl - 1 - methylpyrrolidinium ion, 1 - butyl - 1 - methylpyrrolidinium ion, and the anion includes at least one of chloride ion, bromide ion, iodide ion, bis(trifluoromethylsulfonyl)imide ion.

2. The polybutylene terephthalate composite material according to claim 1, characterized in that, The weight ratio of the titanium dioxide colorant, acrylic toughening agent, and ionic liquid is titanium dioxide colorant:acrylic toughening agent:ionic liquid = (1 - 2):(1 - 2):

2.

3. The polybutylene terephthalate composite material according to claim 1, characterized in that The ionic liquid includes at least one of 1 - butylpyridinium chloride salt and 1 - butyl - 4 - methylpyridinium bromide salt.

4. The polybutylene terephthalate composite material according to claim 1, wherein, The toughening agent is at least one of ethylene - acrylate - glycidyl methacrylate terpolymer, ethylene - methyl acrylate copolymer, ethylene - ethyl acrylate copolymer, glycidyl methacrylate grafted ethylene - octene copolymer.

5. The polybutylene terephthalate composite material according to claim 1, wherein The mass percentage content of TiO₂ in the titanium dioxide colorant is ≥92%.

6. The polybutylene terephthalate composite material according to claim 1, wherein The polybutylene terephthalate has a melt mass flow rate of 1 - 50 g / 10 min at a test temperature of 250 °C and a load of 2.16 kg according to ISO 1133 - 2022, and the intrinsic viscosity of the polybutylene terephthalate is 0.5 - 1.5 dL / g; the antioxidant is at least one of hindered phenol antioxidants and phosphite antioxidants.

7. A method for preparing the polybutylene terephthalate composite material according to any one of claims 1-6, characterized in that, It includes the following steps: mixing the components evenly, followed by melt extrusion and granulation to obtain the polybutylene terephthalate composite material.

8. The application of the polybutylene terephthalate composite material according to any one of claims 1 - 6 in the preparation of mobile phones, tablet computers, and automotive interior housing parts.

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