Polyphenylene sulfide composite material and preparation method and application thereof

Abstract

The application discloses a kind of polyphenylene sulfide composite material and its preparation method and application, belong to high polymer material field.The polyphenylene sulfide composite material of the application comprises the following components by weight: PPS resin 49~91 parts, PC resin 2~15 parts, glass fiber 10~50 parts, epoxy resin 0.1~3 parts;Wherein the viscosity ratio of PC resin and PPS resin is (2~11):1.The application adds PC resin and epoxy resin in glass fiber reinforced polyphenylene sulfide composite material, and controls the viscosity ratio of PPS resin and PC resin in suitable range and the dosage of above-mentioned components in specific range, so that the material is short after injection molding flash length, not easy to float fiber, appearance is good, suitable for being used in automobile, electronic appliances, mechanical parts and the like product.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high polymer materials, in particular to a kind of polyphenylene sulfide composite material and its preparation method and application. BACKGROUND

[0002] Polyphenylene sulfide (PPS) is a kind of semi-crystalline polymer with symmetry and regularity, in which benzene ring and sulfur atom are alternately connected in the main chain. Due to the presence of benzene ring in the chain segment, the material is not sensitive to shear, and has low viscosity and high shear flow. At the same time, the chain segment is slow, and the crystallization is slow during injection molding, which leads to large flash during injection molding. The existence of flash affects the appearance and assembly of the product, so it is necessary to clean the flash, which increases the cost of manpower and material resources. At present, the flash problem of PPS is mainly improved by adding silane coupling agent, polyphenyl ether resin, etc. However, these methods are not suitable for glass fiber reinforced system, and the obtained material is prone to floating fiber appearance problem.

[0003] Therefore, it is urgent to develop a kind of flash problem suitable for glass fiber reinforced PPS composite material. SUMMARY

[0004] Based on the defects existing in the prior art, the purpose of the present application is to provide a kind of polyphenylene sulfide composite material and its preparation method and application. The obtained polyphenylene sulfide composite material has less flash after injection molding, is not easy to float fiber, has good appearance and high toughness.

[0005] In order to achieve the above purpose, in the first aspect, the present application provides a kind of polyphenylene sulfide composite material, which comprises the following components by weight:

[0006]

[0007] The viscosity ratio of the PC resin to the PPS resin is (2-11): 1.

[0008] The addition of PC resin and epoxy resin in glass fiber reinforced polyphenylene sulfide composite material can improve its processing performance and reduce the length of flash. In the processing process, PC resin can promote the crystallization of PPS resin and improve the flash problem. Epoxy resin can react with PPS resin and PC resin, which can connect PPS molecules and PC molecules as a bridge, increase the shear strain of PPS resin and improve the flash problem. In addition, the inventors found that too large or too small viscosity ratio of PC resin and PPS resin will lead to the deterioration of flash problem, so it is necessary to control the viscosity ratio of PPS resin and PC resin in the above suitable range, so as to effectively improve the flash problem.

[0009] The application adds PC resin and epoxy resin in the glass fiber reinforced polyphenylene sulfide composite material, controls the viscosity ratio of PPS resin and PC resin in a suitable range, and controls the use amount of each component in a specific range, so that the material has short flash length after injection molding, is not easy to float fiber, has good appearance, and high toughness.

[0010] The polyphenylene sulfide resin is 49-91 parts by weight, such as 49 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 91 parts by weight, or an interval range formed by any two of the above values. Preferably, the weight percentage content of the polyphenylene sulfide resin in the polyphenylene sulfide composite material is 35% or more, such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88.3% or an interval range formed by any two of the above values.

[0011] The PC resin is 2-15 parts by weight, such as 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, or an interval range formed by any two of the above values.

[0012] The glass fiber is 10-50 parts by weight, such as 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, or an interval range formed by any two of the above values.

[0013] The epoxy resin is 0.1-3 parts by weight, such as 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, or an interval range formed by any two of the above values.

[0014] The viscosity ratio of the PC resin to the PPS resin is (2-11):1, such as 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, or an interval range formed by any two of the above values.

[0015] Preferably, the viscosity of the PPS resin is 50-110 Pa·s, such as 50 Pa·s, 55 Pa·s, 60 Pa·s, 65 Pa·s, 70 Pa·s, 75 Pa·s, 80 Pa·s, 85 Pa·s, 90 Pa·s, 95 Pa·s, 100 Pa·s, 110 Pa·s, or an interval range formed by any two of the above values. When the viscosity of the PPS resin is in the above range, it is more conducive to processing.

[0016] The viscosity of the PPS resin is measured by using a capillary rheometer at 300°C and a shear rate of 1000 s -1 The viscosity is tested as follows.

[0017] Preferably, the viscosity of the PC resin is 100-1000 Pa-s, such as 100 Pa-s, 150 Pa-s, 200 Pa-s, 250 Pa-s, 300 Pa-s, 350 Pa-s, 400 Pa-s, 450 Pa-s, 500 Pa-s, 550 Pa-s, 600 Pa-s, 650 Pa-s, 700 Pa-s, 750 Pa-s, 800 Pa-s, 850 Pa-s, 900 Pa-s, 950 Pa-s, 1000 Pa-s, or a range formed by any two of the above values. When the viscosity of the PC resin is within the above range, it is more advantageous for processing.

[0018] The viscosity of the PC resin is measured by using a capillary rheometer at 300°C and a shear rate of 1000 s -1 The viscosity is tested as follows.

[0019] The content of carboxyl groups in the PPS resin is ≥0 mmol / kg, such as 0 mmol / kg, 10 mmol / kg, 20 mmol / kg, 40 mmol / kg, 60 mmol / kg, 80 mmol / kg, 100 mmol / kg, 120 mmol / kg, 140 mmol / kg, 160 mmol / kg, 180 mmol / kg, 200 mmol / kg, 220 mmol / kg, 240 mmol / kg, 260 mmol / kg, or a range formed by any two of the above values.

[0020] The content of carboxyl groups in the PPS resin is measured by hot-pressing PPS resin particles into an amorphous film at 315°C using a hot press, and then testing the infrared spectrum of the amorphous film by transmission using a Thermo Scientific Nicolet iN10 micro-infrared spectrometer, measuring the peak height of the 1704 cm -1 and 3065 cm -1 absorption peaks, and correcting to H 1704 and H 3065 , and calculating the carboxyl content C of the PPS resin according to the following formula: C = (H 1704 / H 3065 × 4) / 40 / 108.161 × 1000000.

[0021] Preferably, the content of carboxyl groups in the PPS resin is ≥ 40 mmol / kg. When the content of carboxyl groups in the PPS resin is within this specific range, the degree of connection between PPS molecules and PC molecules is higher, the shear strain of the PPS resin is better, and the length of the flash after injection molding of the polyphenylene sulfide composite material is shorter.

[0022] More preferably, the content of carboxyl groups in the PPS resin is 45-260 mmol / kg, so that the length of the flash after injection molding of the polyphenylene sulfide composite material is shorter.

[0023] Preferably, the PC resin comprises bisphenol A type aromatic polycarbonate.

[0024] Preferably, the glass fibers comprise at least one of round glass fibers or flat glass fibers.

[0025] Preferably, the average diameter of the round glass fibers is 9-15 μm, and the average length is 2-4 mm. For example, the average diameter of the round glass fibers is 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, or any interval range formed by any two of the above values; and the average length is 2.2 mm, 2.4 mm, 2.6 mm, 2.8 mm, 3 mm, 3.2 mm, 3.4 mm, 3.6 mm, 3.8 mm, 4 mm, or any interval range formed by any two of the above values.

[0026] The average diameter and the average length of the round glass fibers are tested by using a scanning electron microscope to observe the glass fiber sample, measuring the size of 300 glass fibers, and taking the average value.

[0027] Preferably, the average flat ratio of the flat glass fibers is 3-4, the average long side length of the cross section is 15-25 μm, the average short side length of the cross section is 4-8 μm, and the average length is 2-4 mm. The flat ratio refers to the ratio of the long side length to the short side length of the cross section of the flat glass fiber.

[0028] For example, the average flat ratio of the flat glass fibers is 3, 3.2, 3.4, 3.6, 4, or any interval range formed by any two of the above values; the average long side length of the cross section is 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, or any interval range formed by any two of the above values; the average short side length of the cross section is 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, or any interval range formed by any two of the above values; and the average length is 2 mm, 2.2 mm, 2.4 mm, 2.6 mm, 2.8 mm, 3 mm, 3.2 mm, 3.4 mm, 3.6 mm, 3.8 mm, 4 mm, or any interval range formed by any two of the above values.

[0029] The average flat ratio, average long side length and average short side length of the cross section, and average length of the flat glass fiber are tested according to the following method: using a scanning electron microscope to observe the glass fiber sample, measuring the size of 300 glass fibers, and taking the average value.

[0030] Preferably, the epoxy resin comprises at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and epoxidized olefin compound.

[0031] Preferably, the epoxy equivalent weight of the epoxy resin is above 100 g / mol, such as 100 g / mol, 500 g / mol, 1000 g / mol, 1500 g / mol, 2000 g / mol, 2500 g / mol, 3000 g / mol, 3500 g / mol, 4000 g / mol, 4500 g / mol, 5000 g / mol, or any interval range formed by any two of the above values.

[0032] More preferably, the epoxy equivalent weight of the epoxy resin is 1700-5000 g / mol.

[0033] When the epoxy equivalent weight of the epoxy resin is above 100 g / mol, especially in the range of 1700-5000 g / mol, the degree of connection between PPS molecules and PC molecules is higher, and the shear strain property of the PPS resin is better, so that the flash length of the obtained polyphenylene sulfide composite material after injection molding is shorter.

[0034] The epoxy equivalent weight of the epoxy resin is measured according to the method of potentiometric titration in the standard GB / T 4612-2008, 1-2 g of sample is weighed and completely dissolved in 30 mL of chloroform, and is measured according to the method in the standard.

[0035] Preferably, the polyphenylene sulfide composite material further comprises at least one of a coupling agent, an antioxidant, a lubricant, etc.

[0036] In some embodiments, the content of the coupling agent in the polyphenylene sulfide composite material is 0-2 parts by weight, such as 0 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 1 parts by weight, 1.2 parts by weight, 1.5 parts by weight, 1.7 parts by weight, 2 parts by weight, or any interval range formed by any two of the above values. Exemplarily, the coupling agent comprises a silane coupling agent, which can be selected to comprise at least one of an amino silane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, etc.

[0037] In some embodiments, the content of the antioxidant in the polyphenylene sulfide composite material is 0-1 parts by weight, such as 0 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.7 parts by weight, 1 parts by weight, or any interval range formed by any two of the above values. Illustratively, the antioxidant includes at least one of hindered phenol antioxidant, phosphite antioxidant.

[0038] In some embodiments, the content of the lubricant in the polyphenylene sulfide composite material is 0-0.5 parts by weight, such as 0 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, or any interval range formed by any two of the above values. Illustratively, the lubricant includes at least one of silicone lubricant, amide lubricant, stearic acid lubricant, ester lubricant.

[0039] In a second aspect, the application provides a preparation method of the polyphenylene sulfide composite material, including the following steps:

[0040] Mixing and dispersing the raw materials except for the glass fiber to obtain a premix;

[0041] Feeding the premix from the main feeding port of the screw extruder, feeding the glass fiber from the side feeding port of the screw extruder, melting extruding, and granulating to obtain the polyphenylene sulfide composite material.

[0042] Preferably, the screw extruder is a twin-screw extruder, the length-diameter ratio is (40-48):1, the barrel temperature is 240-350℃, and the screw rotation speed is 200-550 rpm.

[0043] In a third aspect, the application also provides an application of the polyphenylene sulfide composite material in automobile, electronic appliance, or mechanical part. For example, the polyphenylene sulfide composite material is suitable for use as a shell material for mobile phones and watches.

[0044] Compared with the prior art, the application has the beneficial effects that: by adding PC resin and epoxy resin in the glass fiber reinforced polyphenylene sulfide composite material, and controlling the viscosity ratio of PPS resin and PC resin within a suitable range and the use amount of each component within a specific range, the material has a short flash length after injection molding, is not easy to float fiber, has a good appearance, high toughness, and is suitable for use in automobile, electronic appliance, mechanical part, and the like. DETAILED DESCRIPTION

[0045] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in conjunction with specific examples and comparative examples, which are intended to provide a detailed understanding of the content of the present application, rather than limiting the present application. All other examples obtained by those of ordinary skill in the art without making creative efforts fall within the protection scope of the present application. The experimental reagents and instruments involved in the implementation of the present application are all common reagents and instruments unless otherwise specified. In the present application, the open description of technical features includes both the closed technical scheme consisting of the listed features and the open technical scheme containing the listed features.

[0046] The raw material information used in the following examples and comparative examples is shown below, and unless otherwise specified, all are commercially available raw materials, and in addition, the component raw materials used in each parallel experiment are the same:

[0047] PPS resin 1: viscosity as shown in Table 1, carboxyl weight percentage content of 0, brand PPS 3418, manufacturer Zhejiang Xinhengcheng Co., Ltd.;

[0048] PPS resin 2: viscosity as shown in Table 1, carboxyl weight percentage content of 0, brand PPS 3450, manufacturer Zhejiang Xinhengcheng Co., Ltd.;

[0049] PPS resin 3: viscosity as shown in Table 1, carboxyl weight percentage content of 0, brand PPS 3410, manufacturer Zhejiang Xinhengcheng Co., Ltd.;

[0050] PPS resin 4: viscosity 82 Pa·s, carboxyl weight percentage content of 50 mmol / kg, the preparation method of the PPS resin is as follows: PPS resin 1, p-chlorobenzoic acid and sodium hydroxide are dissolved in N-methylpyrrolidone in proportion, heated and stirred under nitrogen protection to 250℃, after reaction for 3h, cooled to 140℃, white substance precipitates after incubation, filtered and washed with hot water several times, then dried to obtain PPS resin containing carboxyl, i.e. PPS resin 4;

[0051] PPS resin 5: viscosity 80 Pa·s, carboxyl weight percentage content of 250 mmol / kg, the difference between the preparation method of the PPS resin and the preparation method of PPS4 is that the proportion of PPS resin 1 and p-chlorobenzoic acid is different;

[0052] PC resin 1: viscosity as shown in Table 1, brand CH8195, manufacturer Cangzhou Dahua Co., Ltd.;

[0053] PC resin 2: viscosity as shown in Table 1, brand PC 2350, manufacturer Wanhua Chemical;

[0054] PC resin 3: viscosity as shown in Table 1, brand PC 2070, manufacturer Wanhua Chemical;

[0055] PC resin 4: viscosity see Table 1, grade PC 7030PJ, manufacturer TOSHIN CORPORATION;

[0056] Glass fiber: grade ECS10-03-568, manufacturer China Jushi;

[0057] Epoxy resin 1: epoxy equivalent 2500-3100 g / mol, grade YD-019, manufacturer Guodu Chemical;

[0058] Epoxy resin 2: epoxy equivalent 1800-2100 g / mol, grade NPES-909, manufacturer Huianaixincai;

[0059] Epoxy resin 3: epoxy equivalent 3500-4000 g / mol, grade DER669E, manufacturer USA Dow;

[0060] Epoxy resin 4: epoxy equivalent 450-500 g / mol, grade E-20, manufacturer East Asia;

[0061] Antioxidant: antioxidant 1098 and antioxidant 168, mass ratio 1:1, commercially available.

[0062] The viscosity of each of the above PPS resins and PC resins was measured using a capillary rheometer, model RG20, Goettfert, Germany, at 300℃ and shear rate 1000 s -1 .

[0063] Examples 1-4 and Comparative Examples 1-2

[0064] Each provides a polyphenylene sulfide composite material, and a preparation method includes the following steps:

[0065] Mixing and dispersing the raw materials except for the glass fiber to obtain a premix;

[0066] Feeding the obtained premix from the main feeding port of the twin-screw extruder, feeding the glass fiber from the side feeding port of the twin-screw extruder, melt extruding, granulating to obtain a polyphenylene sulfide composite material;

[0067] The length-diameter ratio of the screw of the twin-screw extruder is 48:1, the screw rotation speed is 300 r / min, and the barrel temperature is 270℃,

[0068] The types of PPS resins and PC resins used and the corresponding formulations of the polyphenylene sulfide composite material are shown in Table 1.

[0069] Table 1

[0070] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 PPS resin No. PPS resin 1 PPS resin 2 PPS resin 2 PPS resin 3 PPS resin 1 PPS resin 2 PPS resin viscosity / Pa-s 82 53.8 53.8 100 82 53.8 PPS resin amount / parts by weight 70 70 70 70 70 70 PC resin No. PC resin 1 PC resin 2 PC resin 3 PC resin 4 PC resin 2 PC resin 4 PC resin viscosity / Pa-s 304.6 128 556 821 128 821 PC resin amount / parts by weight 8 8 8 8 8 8 Glass fiber amount / parts by weight 30 30 30 30 30 30 Epoxy resin 1 amount / parts by weight 1.5 1.5 1.5 1.5 1.5 1.5 Antioxidant amount / parts by weight 0.5 0.5 0.5 0.5 0.5 0.5 PC viscosity / PPS viscosity 3.7 2.4 10.3 8.2 1.6 15.3

[0071] Examples 5-11

[0072] Each provides a polyphenylene sulfide composite material, the formulations of which are shown in Table 2, wherein the preparation methods of Examples 5-11 are the same as those of Example 1.

[0073] Table 2

[0074]

[0075] The polyphenylene sulfide composite materials of the above examples and comparative examples were subjected to the following performance tests:

[0076] Flash length: a flash evaluation mold was used, a 20x0.04mm opening was opened on one side, a 150mmx15mmx1mm sample was injection molded, the sample would form a flash at the opening of the mold, and the size of the flash was measured by an optical image measuring instrument (YVM30200, Dongguan Yuanxing Optical Instrument Co., Ltd.), the flash length of 15 samples was tested, and the average flash length was taken as the flash length;

[0077] Appearance: a 15cmx10cm color plate (without opening) was injection molded, a two-dimensional optical microscope (two-dimensional image measuring instrument, YVM30200, Dongguan Yuanxing Optical Instrument Co., Ltd.) was used to observe the floating fibers on the surface of the color plate, the number of floating fibers ≤10 was A grade, the number of floating fibers 10-50 (not including 10 but including 50) was B grade, and the number of floating fibers >50 was C grade;

[0078] Charpy notched impact strength: A type notch, tested according to standard ISO 180-2019.

[0079] The test results are shown in Table 3.

[0080] Table 3

[0081]

[0082]

[0083] From the above data, it can be seen that the polyphenylene sulfide composite materials of the embodiments of the present application have less flash after injection molding, are not prone to floating fibers, have good appearance, and have high toughness, wherein the flash length is below 100μm, the impact strength is above 8.5kJ / m 2 The appearance grade is A or B.

[0084] As can be seen from the comparison of Examples 1-8 and Comparative Examples 1-2, the viscosity ratio of the PPS resin to the PC resin affects the flash length, when the viscosity ratio is in the range of (2-11):1, the flash length is significantly shorter and the toughness is better.

[0085] As can be seen from the comparison of Examples 1, 5-6, when the content of carboxyl groups in the PPS resin is ≥40mmol / kg, the flash length is shorter.

[0086] As can be seen from Examples 1, 9-11, when the epoxy equivalent weight of the epoxy resin is 1700-5000 g / mol, the flash length is shorter.

[0087] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A polyphenylene sulfide composite material, characterized in that, It contains the following components by weight: 49-91 parts PPS resin, 2-15 parts PC resin, 10-50 parts glass fiber, and 0.1-3 parts epoxy resin; The viscosity ratio of the PC resin to the PPS resin is (2~11):1; The viscosity of the PPS resin is 50~110 Pa·s; The viscosity of the PC resin is 100~1000 Pa·s.

2. The polyphenylene sulfide composite material as described in claim 1, characterized in that, The carboxyl content in the PPS resin is ≥40 mmol / kg.

3. The polyphenylene sulfide composite material as described in claim 2, characterized in that, The carboxyl content in the PPS resin is 45~260 mmol / kg.

4. The polyphenylene sulfide composite material as described in claim 1, characterized in that, The epoxy equivalent of the epoxy resin is above 100 g / mol.

5. The polyphenylene sulfide composite material as described in claim 4, characterized in that, The epoxy equivalent of the epoxy resin is 1700~5000 g / mol.

6. The polyphenylene sulfide composite material as described in claim 1, characterized in that, The epoxy resin includes at least one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, and epoxidized olefin compound; and / or the PC resin includes bisphenol A type aromatic polycarbonate.

7. The method for preparing the polyphenylene sulfide composite material according to claim 1, characterized in that, Includes the following steps: The raw materials, excluding glass fiber, are mixed and dispersed to obtain a premix; The premixed material is fed into the main feed port of the screw extruder, and the glass fiber is fed into the side feed port of the screw extruder. The mixture is melt-extruded and granulated to obtain a polyphenylene sulfide composite material.

8. The application of the polyphenylene sulfide composite material as described in any one of claims 1 to 6 in automotive, electronic, electrical, or mechanical parts.

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