Anti-warping reinforced PBT (polybutylene terephthalate) resin composite material as well as preparation method and application thereof

Abstract

The invention provides an anti-warping reinforced PBT (polybutylene terephthalate) resin composite material as well as a preparation method and application thereof. The anti-warping reinforced PBT resin composite material comprises the following components in parts by weight: 60-90 parts of PBT, 10-40 parts of glass beads, 0.1-5 parts of a compatilizer, 1-5 parts of a first toughening agent and 1-5 parts of a second toughening agent. Through cooperation of the glass beads, the compatilizer, the first flexibilizer and the second flexibilizer, the toughness of the PBT material can be enhanced, and the problems of poor appearance, serious ore floating and the like caused by non-uniform mineral distribution are solved.

Description

Technical Field

[0001] The invention belongs to the field of composite resin materials and relates to an anti-warping reinforced PBT resin composite material and a preparation method and application thereof. Background Art

[0002] PBT stands for polybutylene terephthalate, which is a thermoplastic epoxy resin. It has excellent physical and chemical properties and is widely used in electronics, automobiles, home appliances and other fields. PBT material has high strength and rigidity, as well as good heat resistance, chemical resistance and electrical properties. It is an engineering plastic with excellent performance. Excellent mechanical properties, including high strength, high stiffness and good wear resistance; excellent insulation properties, suitable for the fields of electronics and electrical appliances; good heat resistance, can be used for a long time at higher temperatures; excellent chemical resistance, good tolerance to oil, grease, solvents, etc.; excellent processing performance, easy to shape and process; excellent stability, not easy to absorb moisture, etc.

[0003] PBT is a semi-crystalline plastic. The benzene ring and ester group in its structure form a large conjugated system, which reduces the flexibility of the molecular chain and increases the molecular rigidity, resulting in poor toughness. When PBT is compounded with glass fiber (GF), the orientation of the glass fiber in the flow direction limits the shrinkage of the resin, resulting in the shrinkage rate of the product in the flow direction (longitudinal direction) being less than the shrinkage rate in the perpendicular flow direction (transverse direction). This uneven shrinkage leads to warping.

[0004] Glass beads (GB) are a material with a wide range of uses and special properties. The product is made from borosilicate raw materials through high-tech processing, with a particle size of 10-250 microns. The product has the advantages of light weight, low thermal conductivity, high strength, good chemical stability, and isotropy, making it very suitable for reinforcing semi-crystalline materials, but its addition will greatly reduce the toughness of the material. Summary of the invention

[0005] In view of the deficiencies in the prior art, the object of the present invention is to provide an anti-warping reinforced PBT resin composite material and a preparation method and application thereof.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In one aspect, the present invention provides a warpage-resistant reinforced PBT resin composite material, wherein the warpage-resistant reinforced PBT resin composite material comprises the following components in parts by weight:

[0008]

[0009] The compatibilizer is an aminosilane coupling agent.

[0010] In the present invention, the glass microspheres are modified by an aminosilane coupling agent, and then combined with a first toughening agent and a second toughening agent, so that the toughness of the PBT material can be enhanced, and the problems of poor appearance and serious floating ore caused by uneven mineral distribution can be solved. The present invention aims to improve the material performance by surface treating the glass microspheres and synergistically increasing the volume and toughness through toughening agents.

[0011] In the anti-warping reinforced PBT resin composite material of the present invention, the content of PBT is 60 parts by weight, 63 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 75 parts by weight, 78 parts by weight, 80 parts by weight, 85 parts by weight, 88 parts by weight or 90 parts by weight.

[0012] In the anti-warpage reinforced PBT resin composite material of the present invention, the amount of the aminosilane coupling agent modified glass microspheres can be 10 parts by weight, 15 parts by weight, 18 parts by weight, 20 parts by weight, 25 parts by weight, 28 parts by weight, 30 parts by weight, 35 parts by weight, 38 parts by weight or 40 parts by weight.

[0013] In the anti-warpage reinforced PBT resin composite material of the present invention, the amount of the compatibilizer is 0.1 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight or 5 parts by weight.

[0014] In the anti-warpage reinforced PBT resin composite material of the present invention, the amount of the first toughening agent can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight or 5 parts by weight.

[0015] In the anti-warpage reinforced PBT resin composite material of the present invention, the amount of the second toughening agent can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight or 5 parts by weight.

[0016] In the present invention, the glass microspheres are surface-modified with a compatibilizer to obtain compatibilizer-modified glass microspheres.

[0017] In the present invention, the preparation method of the compatibilizer-modified glass microspheres is: baking the glass microspheres, and then blending with the compatibilizer to obtain the compatibilizer-modified glass microspheres.

[0018] Preferably, the baking temperature is 100-130° C., for example, 100° C., 110° C., 120° C. or 130° C., and the baking time is 4-6 h, for example, 4 h, 4.5 h, 5 h, 5.5 h or 6 h.

[0019] Preferably, the blending is carried out in a high-speed mixer.

[0020] In the present invention, the aminosilane coupling agent is selected from any one of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane or N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane or a combination of at least two thereof.

[0021] Preferably, the first toughening agent is selected from ethylene-octene copolymer grafted with maleic anhydride (POE-g-MAH).

[0022] Preferably, the second toughening agent is selected from styrene-ethylene-butylene-styrene block copolymer (SEBS).

[0023] Preferably, the anti-warpage reinforced PBT resin composite material also includes a lubricant.

[0024] Preferably, the content of the lubricant in the anti-warpage reinforced PBT resin composite material is 0.1-0.5 parts by weight, for example, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight or 0.5 parts by weight.

[0025] Preferably, the lubricant is selected from any one or a combination of at least two of pentaerythritol stearate (PETS), PTFE lubricant, silicone powder, PE wax, ethylene bis stearamide, butyl stearate or oleamide.

[0026] Preferably, the anti-warpage reinforced PBT resin composite material also includes an antioxidant.

[0027] Preferably, the antioxidant is selected from any one or a combination of at least two of 1098 (N, N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine), tris(2,4-di-tert-butylphenyl)phosphite, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(2,4-di-tert-butyl)phosphite or hindered phenol (octadecyl 3,5-dibutyl-4-hydroxy-phenylpropionate).

[0028] Preferably, the content of the antioxidant in the anti-warpage reinforced PBT resin composite material is 0.5-1.5 parts by weight, for example, 0.5 parts by weight, 0.7 parts by weight, 1.0 parts by weight, 1.2 parts by weight, 1.4 parts by weight or 1.5 parts by weight.

[0029] On the other hand, the present invention provides a method for preparing the anti-warpage reinforced PBT resin composite material as described above, the preparation method comprising the following steps:

[0030] PBT, compatibilizer-modified glass microbeads, a first toughening agent, a second toughening agent, an optional lubricant, and an optional antioxidant are mixed, melt-extruded and granulated to obtain the anti-warpage reinforced PBT resin composite material.

[0031] Preferably, the mixing speed is 300-1200rpm / min, for example 300rpm / min, 500rpm / min, 800rpm / min, 1000rpm / min or 1200rpm / min, and the mixing time is 5-10min, for example 5min, 6min, 7min, 8min, 9min or 10min.

[0032] In the present invention, the mixing is carried out in a high-speed mixer.

[0033] Preferably, the extrusion is carried out in a twin-screw extruder.

[0034] Preferably, the rotation speed of the twin-screw extruder is 400-700r / min (for example, 400r / min, 450r / min, 480r / min, 500r / min, 550r / min, 600r / min, 650r / min or 700r / min), the feeding speed of the main feeding port is 15-25kg / h (for example, 15kg / h, 18kg / h, 20kg / h, 22kg / h or 25kg / h), and the vacuum degree is -0.09 to -0.099Mpa (for example, -0.09Mpa, -0.093Mpa, -0.095Mpa or -0.099Mpa).

[0035] Preferably, the temperature of the melt extrusion is 240-270°C, such as 240°C, 250°C, 260°C or 270°C.

[0036] Preferably, the rotation speed during granulation is 700-900 rpm, for example, 700 rpm, 750 rpm, 800 rpm, 850 rpm or 900 rpm.

[0037] In another aspect, the present invention provides an application of the anti-warpage reinforced PBT resin composite material as described above in automotive interior and exterior decoration materials.

[0038] The anti-warping reinforced PBT resin composite material of the present invention can be used in automobile interior and exterior decoration frames such as interior rearview mirror brackets and air outlet brackets.

[0039] Compared with the prior art, the present invention has the following beneficial effects:

[0040] The PBT resin composite material of the present invention can enhance the toughness of the PBT material by combining the glass microspheres modified by the aminosilane coupling agent with the compatibilizer and the first toughening agent and the second toughening agent, and solve the problems of poor appearance and serious floating ore caused by uneven mineral distribution, and has good application prospects. DETAILED DESCRIPTION

[0041] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0042] The materials used in the following examples are as follows:

[0043] PBT: DuPont, LW9030FR;

[0044] Compatibilizer: aminosilane coupling agent, γ-aminopropyltriethoxysilane, Union Carbide, USA, KH-550;

[0045] First toughening agent: POE-g-MAH: Dow, 8402;

[0046] Second toughening agent: SEBS: Kraton G 1652;

[0047] Lubricant: Pentaerythritol stearate, Italian hair base PETS-T0104;

[0048] Antioxidant: BASF, 1098.

[0049] Example

[0050] The compositions and amounts (parts by weight) of the PBT resin composite materials provided in the examples and comparative examples are shown in Table 1.

[0051] The preparation method comprises the following steps:

[0052] Preparation of high performance anti-warpage reinforced PBT resin:

[0053] After glass microspheres (Wensheng New Materials) were baked at 120°C for 5 hours, they were added to a high-speed mixer with an aminosilane coupling agent γ-aminopropyltriethoxysilane and blended for 6 minutes to perform surface treatment on the glass microspheres;

[0054] The PBT resin was dried in a blast dryer at 80°C for 5 hours; PBT, surface treated glass beads, a first toughening agent, a second toughening agent, an antioxidant, and a lubricant were added to a high-speed mixer, respectively, and mixed at 500rpm / min for 10 minutes to be fully mixed and discharged; the mixture was added to a twin-screw extruder (ZSK-26Mc twin-screw extruder produced by Coperion, Germany), the screw speed of the twin-screw extruder was 600r / min, the main feed was 20kg / h, the vacuum degree was -0.09Mpa, and the mixture was melt-mixed and extruded at 250°C, cooled and granulated, and the speed of the pelletizer was 800rpm to obtain the finished product.

[0055] Comparative Example

[0056] The preparation method of the composite material in the comparative example is the same as that in the embodiment, and the composite material formula is shown in Table 2.

[0057] The prepared composite material was subjected to performance testing, and the testing method was as follows:

[0058] Impact strength is tested according to ISO 179-1 / eU, and the sample size is 80mm*10mm*4mmm;

[0059] The tensile modulus is tested according to ISO 527, and the specimen specification is 1A tensile.

[0060] Table 1

[0061]

[0062] Table 2

[0063]

[0064]

[0065] From the results of the comparative examples and embodiments, it can be seen that the glass microspheres treated with aminosilane coupling agent improve the interface adsorption between glass microspheres and PBT, improve the tensile modulus of the material, and greatly increase the toughness after toughening with maleic anhydride toughening agent. SEBS has limited toughening effect on glass microspheres to strengthen PBT, but SEBS can play a synergistic toughening role with POE-g-MAH, which can greatly improve the toughness of enhanced PBT resin. Aminosilane coupling agent is used as a compatibilizer, and glass microspheres carry active amino groups after surface treatment. Maleic anhydride in the toughening agent reacts with amino molecules, and maleic anhydride groups react with PBT terminal hydroxyl groups. Therefore, maleic anhydride toughening agent further improves the compatibility of PBT and glass microspheres while improving the toughness of PBT materials.

[0066] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the anti-warpage reinforced PBT resin composite material and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A warpage-resistant reinforced PBT resin composite material, characterized in that: The anti-warpage enhanced PBT resin composite material comprises the following components in parts by weight: The compatibilizer is an aminosilane coupling agent.

2. The anti-warpage reinforced PBT resin composite material according to claim 1, characterized in that: Using a compatibilizer to modify the surface of glass microspheres to obtain compatibilizer-modified glass microspheres; Preferably, the compatibilizer-modified glass microspheres are prepared by baking the glass microspheres and then blending them with an aminosilane coupling agent to obtain the compatibilizer-modified glass microspheres; Preferably, the baking temperature is 100-130° C., and the baking time is 4-6 hours.

3. The anti-warpage reinforced PBT resin composite material according to claim 1 or 2, characterized in that: The compatibilizer is an aminosilane coupling agent; Preferably, the aminosilane coupling agent is selected from any one of γ-aminopropyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane or N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, or a combination of at least two thereof.

4. The anti-warpage reinforced PBT resin composite material according to any one of claims 1 to 3, characterized in that: The first toughening agent is selected from ethylene-octene copolymer grafted with maleic anhydride; Preferably, the second toughening agent is selected from styrene-ethylene-butylene-styrene block copolymers.

5. The anti-warpage reinforced PBT resin composite material according to any one of claims 1 to 4, characterized in that: The anti-warpage enhanced PBT resin composite material also includes a lubricant; Preferably, the content of lubricant in the anti-warpage reinforced PBT resin composite material is 0.1-0.5 parts by weight; Preferably, the lubricant is selected from any one or a combination of at least two of pentaerythritol stearate, PTFE lubricant, silicone powder, PE wax, ethylene bisstearamide, butyl stearate or oleamide.

6. The anti-warpage reinforced PBT resin composite material according to any one of claims 1 to 5, characterized in that: The anti-warpage enhanced PBT resin composite material also includes an antioxidant; Preferably, the antioxidant is selected from any one or a combination of at least two of N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine), tris(2,4-di-tert-butylphenyl)phosphite, tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(2,4-di-tert-butyl)phosphite or hindered phenol (octadecyl 3,5-dibutyl-4-hydroxy-phenylpropionate); Preferably, the content of the antioxidant in the anti-warpage reinforced PBT resin composite material is 0.5-1.5 parts by weight.

7. The method for preparing the anti-warpage reinforced PBT resin composite material according to any one of claims 1 to 6, characterized in that: The preparation method comprises the following steps: PBT, compatibilizer-modified glass microbeads, a first toughening agent, a second toughening agent, an optional lubricant, and an optional antioxidant are mixed, melt-extruded and granulated to obtain the anti-warpage reinforced PBT resin composite material.

8. The preparation method according to claim 7, characterized in that: The mixing speed is 300-1200 rpm / min, and the mixing time is 5-10 min; In the present invention, the mixing is carried out in a high-speed mixer; Preferably, the extrusion is carried out in a twin-screw extruder; Preferably, the rotation speed of the twin-screw extruder is 400-700 r / min, the feeding speed of the main feeding port is 15-25 kg / h, and the vacuum degree is -0.09 to -0.099 Mpa.

9. The preparation method according to claim 7, characterized in that: The temperature of the melt extrusion is 240-270°C; Preferably, the rotation speed during granulation is 700-900 rpm.

10. Use of the anti-warpage reinforced PBT resin composite material according to any one of claims 1 to 6 in automobile interior and exterior decoration materials.

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