Polyphenylene sulfide composite material as well as preparation method and application thereof

Abstract

The invention discloses a polyphenylene sulfide composite material as well as a preparation method and application thereof, and belongs to the field of high polymer materials. The polyphenylene sulfide composite material comprises the following components in parts by weight: 49-91 parts of PPS resin, 2-15 parts of PC resin, 10-50 parts of glass fibers and 0.1-3 parts of epoxy resin. Wherein the viscosity ratio of the PC resin to the PPS resin is (2-11): 1. According to the glass fiber reinforced polyphenylene sulfide composite material, the PC resin and the epoxy resin are added into the glass fiber reinforced polyphenylene sulfide composite material, the viscosity ratio of the PPS resin to the PC resin is controlled to be within a proper range, and the use amount of the components is controlled to be within a specific range, so that the material is short in flash length after injection molding, not prone to floating fibers and good in appearance; the method is suitable for products such as automobiles, electronic appliances and mechanical parts.

Description

Technical Field

[0001] This application relates to the field of polymer materials, and specifically relates to a polyphenylene sulfide composite material, a preparation method thereof, and an application thereof. Background Art

[0002] Polyphenylene sulfide (PPS) is a semi-crystalline polymer with symmetry and regularity in which benzene rings and sulfur atoms are alternately connected on the main chain. Due to the presence of benzene rings in the chain segments, this material is insensitive to shear, has low viscosity, high shear fluidity, and slow chain segment movement, resulting in slow crystallization during the injection molding process and large flash in injection molding. The presence of flash affects the appearance and assembly use of products, so the flash has to be removed, which will increase the labor and material costs. Currently, mainly by adding silane coupling agents, polyphenylene ether resins, etc. to improve the flash problem of PPS, but these methods are not applicable to glass fiber-reinforced systems, and the resulting materials are prone to the appearance problem of floating fibers.

[0003] Therefore, it is urgent to develop a solution to the flash problem applicable to glass fiber-reinforced PPS composite materials. Summary of the Invention

[0004] Based on the defects existing in the prior art, the purpose of this application is to provide a polyphenylene sulfide composite material, a preparation method thereof, and an application thereof. The obtained polyphenylene sulfide composite material has less flash after injection molding, is not prone to floating fibers, has good appearance, and high toughness.

[0005] To achieve the above purpose, in the first aspect, this application provides a polyphenylene sulfide composite material, which comprises the following components in parts by weight:

[0006]

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

[0008] Adding PC resin and epoxy resin to the glass fiber-reinforced polyphenylene sulfide composite material can improve its processing performance and reduce the flash length. Among them, the PC resin can promote the crystallization of the PPS resin during the processing and improve the flash problem; the epoxy resin can react with the PPS resin and the PC resin, and can act as a bridge to connect the PPS molecules and the PC molecules, increasing the shear strain of the PPS resin and improving the flash problem. In addition, the inventors found that too large or too small viscosity ratio of the PC resin to the PPS resin will lead to the deterioration of the flash problem, and it is necessary to control the viscosity ratio of the PPS resin and the PC resin within the above suitable range to effectively improve the flash problem.

[0009] In this application, by adding PC resin and epoxy resin to the glass fiber reinforced polyphenylene sulfide composite material, and controlling the viscosity ratio of PPS resin and PC resin within an appropriate range and the dosages of the above components within a specific range, the material has a short flash length after injection molding, is not prone to fiber floating, has a 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 the range formed by any two of the above values. Preferably, the weight percentage of the polyphenylene sulfide resin in the polyphenylene sulfide composite material is above 35%, such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 88.3%, or the 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 the 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 the 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 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, or the 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 the 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 the range formed by any two of the above values. When the viscosity of the PPS resin is within the above range, it is more conducive to processing.

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

[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 the range formed by any two of the above values. When the viscosity of the PC resin is within the above range, it is more conducive to processing.

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

[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 the range formed by any two of the above values.

[0020] The content of carboxyl groups in the PPS resin is measured as follows: Use a hot press to hot-press PPS resin particles into an amorphous film at 315 °C, and then use a Thermo Scientific Nicolet iN10 type microscopic infrared spectrometer to perform infrared spectroscopy tests on the amorphous film by the transmission method, measure the peak heights of the absorption peaks at 1704 cm -1 and 3065 cm -1 , and correct them to H 1704 and H 3065 . Calculate 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, and the shear strain property of the PPS resin is better, resulting in a shorter flash length after injection molding of the obtained polyphenylene sulfide composite material.

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

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

[0024] Preferably, the glass fiber includes at least one of circular glass fiber or flat glass fiber.

[0025] Preferably, the average diameter of the circular glass fiber is 9 - 15 μm, and the average length is 2 - 4 mm. For example, the average diameter of the circular glass fiber is 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm or the range formed by any two of the above values; 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 the range formed by any two of the above values.

[0026] The average diameter and average length of the circular glass fiber are obtained by the following method: observing the glass fiber sample with a scanning electron microscope, measuring the sizes of 300 glass fibers, and taking the average value.

[0027] Preferably, the average flat ratio of the flat glass fiber 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. Among them, 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 fiber is 3, 3.2, 3.4, 3.6, 4 or the 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 the 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 the range formed by any two of the above values; 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 the range formed by any two of the above values.

[0029] The average flat ratio, the average long side length and the average short side length of the cross-section, and the average length of the flat glass fiber are measured by the following method: observing the glass fiber sample using a scanning electron microscope, measuring the sizes of 300 glass fibers, and taking the average value.

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

[0031] Preferably, the epoxy equivalent of the epoxy resin is 100 g / mol or more, 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 the range formed by any two of the above values.

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

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

[0034] The epoxy equivalent of the epoxy resin is measured by the potentiometric titration method in Standard GB / T 4612 - 2008. Weigh 1 - 2 g of the sample and completely dissolve it in 30 mL of chloroform, and measure it specifically according to the method in the standard.

[0035] Preferably, the polyphenylene sulfide composite material further includes 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 part by weight, 0.2 part by weight, 0.5 part by weight, 0.7 part by weight, 1 part by weight, 1.2 part by weight, 1.5 part by weight, 1.7 part by weight, 2 parts by weight, or the range formed by any two of the above values. Exemplarily, the coupling agent includes a silane coupling agent, and the silane coupling agent can be selected to include at least one of an amino silane coupling agent, an epoxy group silane coupling agent, a vinyl silane coupling agent, etc.

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

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

[0039] In a second aspect, the present application provides a method for preparing the polyphenylene sulfide composite material, comprising the following steps:

[0040] Mix and disperse the raw materials except glass fiber to obtain a premix;

[0041] Feed the premix into the main feed port of a screw extruder, and feed glass fiber into the side feed port of the screw extruder, and then melt extrude and pelletize to obtain the polyphenylene sulfide composite material.

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

[0043] In a third aspect, the present application further provides the application of the polyphenylene sulfide composite material in automobiles, electronic and electrical appliances, or mechanical parts. For example, the polyphenylene sulfide composite material is suitable as the housing material for mobile phones and watches.

[0044] Compared with the prior art, the beneficial effects of the present application are as follows: By adding PC resin and epoxy resin to the glass fiber-reinforced polyphenylene sulfide composite material, and controlling the viscosity ratio of PPS resin and PC resin within an appropriate range and the dosage of each of the above components within a specific range, the flash length of the material after injection molding is short, it is not easy to float fibers, the appearance is good, and the toughness is high, making it suitable for products such as automobiles, electronic and electrical appliances, and mechanical parts. Specific embodiments

[0045] To better illustrate the purpose, technical solution, and advantages of this application, the following will further explain this application in combination with specific examples and comparative examples. The purpose is to understand the content of this application in detail, rather than a limitation to this application. All other examples obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of this application. The experimental reagents and instruments involved in the implementation of this application are all common ordinary reagents and instruments unless otherwise specified. In this application, among the technically characterized described in an open-ended manner, it includes a closed technical solution composed of the listed characteristics, as well as an open technical solution containing the listed characteristics.

[0046] The raw material information of the following examples and comparative examples is as follows, and unless otherwise specified, they are all commercially available raw materials. In addition, the component raw materials used in each parallel experiment are all of the same type:

[0047] PPS Resin 1: The viscosity is shown in Table 1, the carboxyl weight percentage is 0, the grade is PPS 3418, and the manufacturer is Zhejiang NHU Company Limited;

[0048] PPS Resin 2: The viscosity is shown in Table 1, the carboxyl weight percentage is 0, the grade is PPS 3450, and the manufacturer is Zhejiang NHU Company Limited;

[0049] PPS Resin 3: The viscosity is shown in Table 1, the carboxyl weight percentage is 0, the grade is PPS 3410, and the manufacturer is Zhejiang NHU Company Limited;

[0050] PPS Resin 4: The viscosity is 82 Pa·s, the carboxyl weight percentage is 50 mmol / kg. The preparation method of this PPS resin is as follows: Dissolve PPS Resin 1, p-chlorobenzoic acid, and sodium hydroxide in N-methylpyrrolidone in proportion, heat and stir under nitrogen protection to 250 °C, react for 3 h, then cool down to 140 °C for heat preservation. After white substances precipitate, filter, wash with hot water multiple times, and then dry to obtain a PPS resin containing carboxyl, that is, PPS Resin 4;

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

[0052] PC Resin 1: The viscosity is shown in Table 1, the grade is CH8195, and the manufacturer is Cangzhou Dahua Co., Ltd.;

[0053] PC Resin 2: The viscosity is shown in Table 1, the grade is PC 2350, and the manufacturer is Wanhua Chemical;

[0054] PC Resin 3: The viscosity is shown in Table 1, the grade is PC 2070, and the manufacturer is Wanhua Chemical;

[0055] PC resin 4: The viscosity is shown in Table 1, grade PC 7030PJ, manufacturer TOSHIN CORPORATION;

[0056] Glass fiber: grade ECS10-03-568, manufacturer China National Bluestar (Group) Co., Ltd.;

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

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

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

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

[0061] Antioxidant: Antioxidant 1098 and Antioxidant 168, with a mass ratio of 1:1, commercially available.

[0062] The viscosities of the above-mentioned PPS resins and PC resins were measured using a capillary rheometer, model RG20, from Goettfert Company, Germany, at 300 °C and a shear rate of 1000 s -1 -1.

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

[0064] All provided a polyphenylene sulfide composite material, and the preparation method included the following steps:

[0065] Mix and disperse the raw materials except glass fiber to obtain a premix;

[0066] Feed the obtained premix into the main feeding port of a twin-screw extruder, and feed glass fiber into the side feeding port of the twin-screw extruder, melt and extrude, and pelletize to obtain a polyphenylene sulfide composite material;

[0067] Among them, the length-diameter ratio of the screws of the twin-screw extruder was 48:1, the screw rotation speed was 300 r / min, and the barrel temperature was 270 °C,

[0068] The types of PPS resins and PC resins used and the corresponding formulations of the polyphenylene sulfide composite materials 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 Number 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 Dosage / parts by weight 70 70 70 70 70 70 PC Resin Number 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 Dosage / parts by weight 8 8 8 8 8 8 Glass Fiber Dosage / parts by weight 30 30 30 30 30 30 Epoxy Resin 1 Dosage / parts by weight 1.5 1.5 1.5 1.5 1.5 1.5 Antioxidant Dosage / 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 to 11

[0072] A polyphenylene sulfide composite material is provided, and their formulas are shown in Table 2, wherein the preparation methods of Examples 5 to 11 are the same as those of Example 1.

[0073] Table 2

[0074]

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

[0076] Flash length: Use a flash evaluation mold, open a 20×0.04mm opening on one side, and inject a 150mm×15mm×1mm spline. The spline will form a flash at the mold opening. Use an optical image measuring instrument (YVM30200, Dongguan Yuanxing Optical Instrument Co., Ltd.) to measure the flash size. Test the flash length of 15 samples and take the average flash length as the flash length;

[0077] Appearance: A 15cm×10cm color plate (without opening) was injected, and the floating fibers on the surface of the color plate were observed using a two-dimensional optical microscope (two-dimensional image measuring instrument, YVM30200, Dongguan Yuanxing Optical Instrument Co., Ltd.). The number of floating fibers ≤ 10 was grade A, the number of floating fibers 10-50 (excluding 10, but including 50) was grade B, and the number of floating fibers > 50 was grade C.

[0078] Izod notched impact strength: A-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 each embodiment of the present application have less flash after injection molding, are not easy to float fibers, have good appearance, and have high toughness. The flash length is less than 100 μm, and the impact strength is 8.5 kJ / m 2 Above, the appearance grade is A or B.

[0084] From the comparison between Examples 1 to 8 and Comparative Examples 1 to 2, it can be seen that the viscosity ratio of PPS resin to PC resin affects the flash length. When the viscosity ratio of the two is in the range of (2 to 11):1, the flash length is significantly shorter and the toughness is better.

[0085] Comparison of Examples 1 and 5 to 6 shows that when the content of carboxyl groups in the PPS resin is ≥40 mmol / kg, the length of the flash is shorter.

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

[0087] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application rather than 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 of ordinary skill 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: Contains the following components by weight: The viscosity ratio of the PC resin to the PPS resin is (2-11):

1.

2. The polyphenylene sulfide composite material according to claim 1, characterized in that: The viscosity of the PPS resin is 50-110 Pa·s.

3. The polyphenylene sulfide composite material according to claim 1, characterized in that: The viscosity of the PC resin is 100-1000 Pa·s.

4. The polyphenylene sulfide composite material according to claim 1, characterized in that: The content of carboxyl groups in the PPS resin is ≥40 mmol / kg.

5. The polyphenylene sulfide composite material according to claim 4, characterized in that: The content of carboxyl groups in the PPS resin is 45 to 260 mmol / kg.

6. The polyphenylene sulfide composite material according to claim 1, characterized in that: The epoxy equivalent of the epoxy resin is above 100 g / mol.

7. The polyphenylene sulfide composite material according to claim 6, characterized in that: The epoxy equivalent of the epoxy resin is 1700 to 5000 g / mol.

8. The polyphenylene sulfide composite material according to claim 1, characterized in that: The epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, and epoxidized olefin compounds; and / or the PC resin includes bisphenol A aromatic polycarbonate.

9. The method for preparing the polyphenylene sulfide composite material according to claim 1, characterized in that: The following steps are involved: Mixing and dispersing raw materials except glass fiber to obtain a premix; The premix is ​​fed from the main feeding port of the screw extruder, and the glass fiber is fed from the side feeding port of the screw extruder, and the mixture is melt-extruded and granulated to obtain a polyphenylene sulfide composite material.

10. Use of the polyphenylene sulfide composite material according to any one of claims 1 to 8 in automobiles, electronic appliances or mechanical parts.

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