Polyester composite material, preparation method thereof and polyester product

Abstract

The invention relates to the technical field of polyester composite materials, in particular to a polyester composite material, a preparation method thereof and a polyester product. The polyester composite material disclosed by the invention is prepared from the following components in percentage by mass: 0.001 wt%-0.2 wt% of an inorganic lubricant, 0.001 wt%-0.4 wt% of an organic lubricant, 0.001 wt%-0.1 wt% of a toughening agent and the balance of a polyester matrix, the inorganic lubricant comprises modified silicon dioxide, and the surface of the modified silicon dioxide is modified with a hydroxyl group and a phenyl group; the organic lubricant comprises a distilled monoglyceride lubricant, and the toughening agent comprises a styrene-butadiene block copolymer. According to the invention, the inorganic lubricant, the organic lubricant and the flexibilizer are adopted to modify the polyester matrix, and through mutual cooperation and synergistic effect of all the components, the polyester composite material has excellent fluidity, transparency, lubricity, toughness and antistatic property at the same time.

Description

Technical Field

[0001] The invention relates to the technical field of polyester composite materials, in particular to a polyester composite material and a preparation method thereof and a polyester product. Background Art

[0002] Commonly used polyester materials such as PET, PETG, PCTG, PEN, etc. are widely used in packaging materials, optics, and electrical appliances due to their good transparency and mechanical properties. Highly fluid polyester materials can significantly reduce injection pressure and shorten molding cycles during injection molding, and are widely recognized in the industry.

[0003] High-fluidity polyester materials have low viscosity and good melt fluidity, and can be used in thin-walled parts in the fields of food, daily chemicals, electrical appliances, electronics, etc. However, the reduction in viscosity can easily lead to a decrease in the mechanical properties of polyester materials; therefore, it is not suitable for product parts with high mechanical property requirements.

[0004] At present, the preparation method of high fluidity polyester material includes: 1. Modifying the material with low viscosity polyester with small molecular weight; this method is often accompanied by the reduction of mechanical properties of the material; inserting the preparation of low viscosity polyester on the existing normal production equipment is often accompanied by the increase of production cost. 2. Modifying the polyester with additives that improve fluidity; such additives will migrate to the surface of the product during the molding process and play a role in demolding. When the amount of additives added is high, such additives are easy to cause the transparency of the product to decrease. In severe cases, they are easy to contaminate the mold cavity and the surface of the product, which will have an adverse effect on the subsequent printing and coating of the product surface. In addition, when the polyester is modified by the blending method, the rheological properties of the additives and the polyester matrix are not matched, which is easy to cause the melt flow marks left by the processing and molding inside the product, which will affect the appearance quality of the product. In the process of processing, when the additives are added in the form of masterbatch, they need to be evenly mixed with the polyester raw material in a certain proportion. Static electricity is easy to be generated due to the friction between particles or particles and equipment, which makes the masterbatch easy to adsorb on the inner wall of the processing equipment, resulting in uneven mixing.

[0005] The increase in the fluidity of polyester can easily lead to the loss of mechanical properties of the product and the reduction of the transparency of the polyester product, thus affecting the appearance quality of the product; the use of additives can easily lead to mold cavity contamination, static electricity in the raw materials, and problems such as product appearance quality, which brings a lot of inconvenience to production and processing.

[0006] In view of this, this invention is proposed. Summary of the invention

[0007] The first object of the present invention is to provide a polyester composite material having excellent fluidity, transparency, lubricity, toughness and antistatic properties.

[0008] The second object of the present invention is to provide a method for preparing a polyester composite material with simple steps.

[0009] The third object of the present invention is to provide a polyester product with good quality and high yield.

[0010] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0011] In a first aspect, the present invention provides a polyester composite material, comprising the following components by mass percentage:

[0012] 0.001wt% to 0.2wt% of inorganic lubricant, 0.001wt% to 0.4wt% of organic lubricant, 0.001wt% to 0.1wt% of toughening agent, and the balance is polyester matrix;

[0013] The inorganic lubricant comprises modified silicon dioxide, the surface of which is modified with hydroxyl groups and phenyl groups;

[0014] The organic lubricant includes a distilled glyceride lubricant.

[0015] Furthermore, the organic lubricant includes a distilled glycerol fatty acid ester lubricant.

[0016] Preferably, the distilled glycerol fatty acid ester lubricant includes at least one of a polyglycerol fatty acid ester lubricant, a distilled glycerol mono-fatty acid ester lubricant and a distilled glycerol di-fatty acid ester lubricant.

[0017] Furthermore, the toughening agent includes a block copolymer of styrene-butadiene.

[0018] Furthermore, the polyester matrix is ​​obtained by polymerizing a dicarboxylic acid compound and a diol compound.

[0019] Further, the dicarboxylic acid compound includes at least one of a C8-C14 aromatic dicarboxylic acid and a C4-C12 aliphatic dicarboxylic acid;

[0020] And / or, the diol compound includes at least one of C2-C21 aliphatic diols.

[0021] Furthermore, the intrinsic viscosity of the polyester matrix is ​​0.5 to 0.9 dL / g.

[0022] In a second aspect, the present invention further provides a method for preparing the polyester composite material as described above, comprising the following steps:

[0023] S1, mixing the polyester matrix, the inorganic lubricant, the organic lubricant and the toughening agent, and extruding and granulating the mixture to obtain an additive masterbatch;

[0024] S2, after the additive masterbatch and the polyester matrix are mixed, the polyester composite material is obtained. Further, in step S1, at least one of the following features (1) to (4) is included;

[0025] (1) The extrusion granulation comprises using a twin-screw extruder;

[0026] (2) The aspect ratio of the screw of the twin-screw extruder is (35-45):1;

[0027] (3) The rotation speed of the twin-screw extruder is 150 to 600 rpm;

[0028] (4) The temperature of the extrusion granulation is 180-270°C.

[0029] In a third aspect, the present invention further provides a polyester product, which is made from the polyester composite material as described above.

[0030] Furthermore, the polyester product includes at least one of an injection molded product, an extruded film-drawing product, an extruded film-blowing product, an extruded sheet and an extruded profile.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] 1. The present invention uses inorganic lubricants, organic lubricants and toughening agents to modify the polyester matrix. Through the mutual cooperation and synergistic effect of each component, the polyester composite material simultaneously has excellent fluidity, transparency, lubricity, toughness and antistatic properties.

[0033] 2. The polyester composite material of the present invention has good fluidity, lubricity and antistatic properties in the melt during the processing and molding process, which can reduce the downtime caused by mold contamination, reduce processing defects, improve the yield of products, and make the processing and molding process more convenient and smooth; at the same time, the polyester composite material has good transparency and good drop resistance.

[0034] 3. During the processing, the polyester composite material of the present invention can avoid parabolic flow marks generated inside the product during the cooling process, and is suitable for products with large volume, thin wall and multiple gates; it can be applied to injection molding products, extrusion film products, extrusion blown film products, extrusion plates and extrusion profiles. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0036] Figure 1 The Danish Palsgaard antistatic agent of the present invention GC-MS test results diagram. DETAILED DESCRIPTION

[0037] The technical scheme of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. If specific conditions are not specified in the embodiments, they are carried out according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not specified in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0038] The polyester composite material, the preparation method thereof and the polyester product of the present invention are described in detail below.

[0039] In some embodiments of the present invention, a polyester composite material is provided, which comprises the following components by mass percentage:

[0040] 0.001wt% to 0.2wt% of inorganic lubricant, 0.001wt% to 0.4wt% of organic lubricant, 0.001wt% to 0.1wt% of toughening agent, and the balance is polyester matrix;

[0041] The inorganic lubricant includes modified silica, the surface of which is modified with hydroxyl groups and phenyl groups;

[0042] Organic lubricants include distilled glyceride-based lubricants.

[0043] The present invention adopts inorganic lubricants, organic lubricants and toughening agents to modify the polyester matrix, wherein silicon dioxide with hydroxyl groups and phenyl groups modified on the surface is used as the inorganic lubricant, and distilled glyceride lubricants are used as the organic lubricant; through the mutual coordination and synergistic effect of the components, the polyester composite material simultaneously has excellent fluidity, transparency, lubricity, toughness and antistatic properties.

[0044] The polyester composite material of the present invention has good fluidity, lubricity and antistatic properties in the melt during the processing and molding process, which can reduce the downtime caused by mold pollution, reduce processing defects, improve the yield of products, and make the processing and molding process more convenient and smooth; at the same time, the polyester composite material has good transparency and good anti-drop performance.

[0045] For example, in different embodiments, the mass percentages of the components in the polyester composite material may be as follows:

[0046] The mass percentage of the inorganic lubricant may be 0.001wt%, 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt% or a range consisting of any two thereof;

[0047] The mass percentage of the organic lubricant may be 0.001wt%, 0.005wt%, 0.01wt%, 0.05wt%, 0.1wt%, 0.15wt%, 0.2wt%, 0.25wt%, 0.3wt%, 0.35wt%, 0.4wt% or a range consisting of any two thereof;

[0048] The mass percentage of the toughening agent may be 0.001 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt% or a range consisting of any two of them.

[0049] In some embodiments of the present invention, the modified silica includes RSN-6018 purchased from DOW CORNING.

[0050] The inorganic lubricant is a modified silica with terminal hydroxyl functional groups and phenyl functional groups on the surface. During the processing, the terminal hydroxyl functional groups on the surface can be linked to the polyester through an esterification reaction, making it more difficult for the chain segments of some molecular chains to move, prolonging the time of the crystallization process, which is beneficial to improving the transparency of the polyester composite material; the phenyl functional group can further destroy the ordered structure of the molecular chain, making crystallization difficult and improving the transparency of the composite material; at the same time, the synergistic effect of the inorganic lubricant and the organic lubricant can further enhance the transparency of the polyester composite material; and the introduction of the inorganic lubricant can be used as a lubricant for the screw during the processing, which is beneficial to reducing the reduction in the characteristic viscosity of the polyester composite material, thereby reducing the loss of mechanical properties of the material.

[0051] In some embodiments of the present invention, the organic lubricant comprises a distilled glycerol fatty acid ester lubricant.

[0052] In some embodiments of the present invention, the distilled glycerol fatty acid ester lubricant includes at least one of a polyglycerol fatty acid ester lubricant, a distilled glycerol mono-fatty acid ester lubricant, and a distilled glycerol di-fatty acid ester lubricant. Preferably, the organic lubricant includes a distilled glycerol mono-fatty acid ester lubricant; more preferably, the organic lubricant includes a distilled glycerol mono-fatty acid ester lubricant made of a mixture of palm oil and rapeseed oil and fatty acids.

[0053] In some embodiments of the present invention, the organic lubricant comprises a distilled monoglyceride lubricant made from a mixture of palm oil and rapeseed oil and fatty acids; preferably a Danish Palsgaard antistatic agent.

[0054] Organic lubricants include distilled glyceride lubricants. During the injection molding and extrusion processes, organic lubricants can make the polyester composite material melt have better fluidity; during the molding process, as the melt solidifies into a solid, the melt temperature decreases, and the organic lubricant can migrate to the surface of the product; the surface of the processed product (including injection molded products, film products, sheets, profiles, etc.) has good gloss and a low static friction coefficient, thereby playing a role in demolding and anti-overlapping. During the cooling and crystallization process of the composite material melt, due to the addition of organic lubricants, the organic lubricant that has no time to migrate or has not migrated to the surface of the product plays the role of a heterogeneous nucleating agent in the melt system, so that the melt is heterogeneously nucleated and crystallized during the cooling process, and cooperates with the inorganic lubricant to reduce the size of the crystal grains, which is beneficial to the penetration of light and the improvement of light flux, thereby playing a role in enhancing the transparency of the composite material product, which is beneficial to the improvement of the overall transparency of the composite material product.

[0055] When polyolefin polymers and polyester polymers are melt-blended, there is an incompatibility phenomenon, which easily causes the blended products to turn white and then opaque. The organic lubricant used in the present invention is a fine-grained powdered polymer. Through research and analysis of distilled glycerol mono-fatty acid ester compositions, it can be mutually fusible with polyester and can maintain a certain degree of transparency; specifically, it can be a distilled glycerol mono-ester lubricant made from a mixture of palm oil and rapeseed oil and fatty acids. For example, through gas chromatography-mass spectrometry (GC-MS) testing and analysis, Danish Palsgaard antistatic agent The main components of Figure 1 As shown, the component structure has sufficient ester structure composition, so the polyester polymers can be melt-blended and fused with each other.

[0056] The organic lubricant of the present invention is a distilled monoglyceride lubricant made from a mixture of palm oil and rapeseed oil and fatty acids, and has a certain antistatic property, thereby making the polyester composite material have antistatic performance.

[0057] In some embodiments of the present invention, the toughening agent comprises a block copolymer of styrene-butadiene; preferably, the toughening agent comprises a block copolymer of styrene-butadiene from BASF Corporation.

[0058]

[0059] The toughening agent is a block copolymer of styrene-butadiene, which belongs to the polyolefin polymer and has poor compatibility with polyester. After mutual melting, the product is easily whitened due to the incompatibility of the system. The organic lubricant has good compatibility with the toughening agent because it contains polyolefin and / or alkane components. With the assistance of the organic lubricant, the introduction of the toughening agent can play a toughening role on the polyester composite material without losing transparency.

[0060] In some embodiments of the present invention, the polyester matrix is ​​obtained by polymerizing a dicarboxylic acid compound and a diol compound.

[0061] In some embodiments of the present invention, the carboxylic acid compound includes at least one of an aromatic dicarboxylic acid of C8 to C14 and an aliphatic dicarboxylic acid of C4 to C12; preferably, the dicarboxylic acid compound includes at least one of terephthalic acid, phthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and cyclohexane diacetic acid; more preferably, the dicarboxylic acid compound includes terephthalic acid.

[0062] In some embodiments of the present invention, the diol compound includes at least one of C2 to C21 aliphatic diols; preferably, the diol compound includes at least one of ethylene glycol, diethylene glycol, 1,3-propylene glycol, 2-ethyl-1,3-propylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-diethyl-1,3-propylene glycol and 2,5-hexanediol; more preferably, it is at least one of ethylene glycol, 1,4-cyclohexanedimethanol and neopentyl glycol; more preferably, it is ethylene glycol.

[0063] In some embodiments of the present invention, the polyester matrix comprises PET (polyethylene terephthalate).

[0064] In some embodiments of the present invention, the intrinsic viscosity of the polyester matrix is ​​0.5 to 0.9 dL / g; typically but not limitatively, for example, the intrinsic viscosity of the polyester matrix can be 0.5 dL / g, 0.6 dL / g, 0.7 dL / g, 0.8 dL / g, 0.9 dL / g or a range consisting of any two thereof; preferably, the intrinsic viscosity of the polyester matrix is ​​0.5 to 0.8 dL / g; more preferably 0.5 to 0.7 dL / g; more preferably 0.5 to 0.6 dL / g.

[0065] The test method for the intrinsic viscosity is: at 25.0±0.1°C, using a solvent composed of phenol and tetrachloroethane in a ratio of 3 / 2 (wt / wt), and measuring at a concentration of 0.25 g / 50 mL.

[0066] In some embodiments of the present invention, a method for preparing the above polyester composite material is also provided, comprising the following steps:

[0067] S1, mixing the polyester matrix, the inorganic lubricant, the organic lubricant and the toughening agent, and extruding and granulating the mixture to obtain an additive masterbatch;

[0068] S2. Mix the additive masterbatch and the polyester matrix to obtain a polyester composite material.

[0069] The preparation method of the polyester composite material of the present invention comprises the following steps: preparing additive master batches in advance, and then mixing the additive master batches with a polyester matrix to prepare the polyester composite material.

[0070] In some embodiments of the present invention, in step S1, the extrusion granulation comprises using a twin-screw extruder.

[0071] In some embodiments of the present invention, in step S1, the aspect ratio of the screw of the twin-screw extruder is (35-45):1; typically but not limitatively, for example, the aspect ratio of the screw of the twin-screw extruder can be 35:1, 38:1, 40:1, 42:1, 45:1 or a range of any two thereof; preferably 40:1.

[0072] In some embodiments of the present invention, in step S1, the rotation speed of the twin-screw extruder is 150-600 rpm; typically but not limitatively, for example, the rotation speed of the twin-screw extruder can be 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm or a range of any two thereof.

[0073] In some embodiments of the present invention, the temperature of extrusion granulation is 180-270°C; preferably, the temperatures of each working zone are: 220°C for zone 1, 255°C for zone 2, 260°C for zone 3, 260°C for zone 4, 265°C for zone 5, 265°C for zone 6, 265°C for zone 7, 265°C for zone 8, 265°C for zone 9, and 265°C for die head.

[0074] In some embodiments of the present invention, in step S1, the mixed material is fed into an automatic feeder, and the automatic feeder automatically discharges the material into the screw of the twin-screw extruder according to the set feeding parameters.

[0075] In some embodiments of the present invention, in step S1 and step S2, mixing includes stirring; preferably, mixing is performed using a high-speed mixer.

[0076] The present invention does not strictly limit the amount of polyester matrix added in step S1 and the amount of polyester matrix added in step S2, and can be adjusted according to the actual equipment. The total amount of polyester matrix added in step S1 and step S2 can make the polyester composite material meet the ratio of each component of the above polyester composite material. In some embodiments of the present invention, a polyester product is also provided, which is made of the above polyester composite material.

[0077] In some embodiments of the present invention, the polyester product comprises at least one of an injection molded product, an extruded film product, an extruded blown film product, an extruded sheet, and an extruded profile.

[0078] During the processing, the polyester composite material of the present invention can avoid parabolic flow marks generated inside the product during the cooling process, and is suitable for products with large volume, thin wall and multiple gates; it can be applied to injection molding products, extrusion film products, extrusion blown film products, extrusion plates and extrusion profiles.

[0079] The features and properties of the present invention are further described in detail below in conjunction with examples and comparative examples.

[0080] Example 1

[0081] The polyester composite material provided in this embodiment includes the following components in terms of mass percentage:

[0082] Inorganic lubricant 0.001wt%, organic lubricant 0.2wt%, toughening agent 0.05wt%, the balance is polyester matrix;

[0083] The inorganic lubricant was modified silica, RSN-6018 purchased from DOW CORNING Company;

[0084] The organic lubricant is Palsgaard antistatic agent from Denmark

[0085] The toughening agent is a styrene-butadiene block copolymer from BASF

[0086] The polyester matrix is ​​a polyethylene terephthalate copolymer obtained by polymerization of terephthalic acid and ethylene glycol; specifically, Hualei brand PET polyester of China Resources Chemical Materials, model CR-7739, with an intrinsic viscosity of 0.60 dL / g.

[0087] The method for preparing the polyester composite material provided in this embodiment comprises the following steps:

[0088] S1, mixing the polyester matrix, inorganic lubricant, organic lubricant and toughening agent by a high-speed mixer, and then extruding and granulating by a twin-screw extruder to obtain an additive masterbatch;

[0089] The length-to-diameter ratio of the screw of the twin-screw extruder is 40:1, the speed is 250rpm, and the temperature is 220-265°C; the temperatures of the working sections are: zone 1 220°C, zone 2 255°C, zone 3 260°C, zone 4 260°C, zone 5 265°C, zone 6 265°C, zone 7 265°C, zone 8 265°C, zone 9 265°C, and die head 265°C;

[0090] S2. The additive masterbatch and the polyester matrix are mixed evenly by a high-speed mixer to obtain a polyester composite material.

[0091] Example 2

[0092] The polyester composite material and the preparation method thereof provided in this embodiment refer to Example 1, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.2 wt% inorganic lubricant, 0.2 wt% organic lubricant, 0.05 wt% toughening agent, and the remainder is polyester matrix.

[0093] Example 3

[0094] The polyester composite material and the preparation method thereof provided in this embodiment refer to Example 1, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.1 wt% inorganic lubricant, 0.2 wt% organic lubricant, 0.05 wt% toughening agent, and the remainder is polyester matrix.

[0095] Example 4

[0096] The polyester composite material and preparation method thereof provided in this embodiment refer to Example 1, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.1 wt% inorganic lubricant, 0.001 wt% organic lubricant, 0.05 wt% toughening agent, and the remainder is polyester matrix.

[0097] Example 5

[0098] The polyester composite material and the preparation method thereof provided in this embodiment refer to Example 1, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.1 wt% inorganic lubricant, 0.4 wt% organic lubricant, 0.05 wt% toughening agent, and the remainder is polyester matrix.

[0099] Example 6

[0100] The polyester composite material and the preparation method thereof provided in this embodiment refer to Example 1, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.1wt% inorganic lubricant, 0.2wt% organic lubricant, 0.001wt% toughening agent, and the remainder is polyester matrix.

[0101] Example 7

[0102] The polyester composite material and preparation method thereof provided in this embodiment refer to Example 1, except that the polyester composite material includes the following components, by mass percentage: 0.1 wt% inorganic lubricant, 0.2 wt% organic lubricant, 0.1 wt% toughening agent, and the remainder is polyester matrix.

[0103] Example 8

[0104] The polyester composite material and the preparation method thereof provided in this embodiment refer to Example 1, except that the toughening agent is methyl methacrylate-butadiene-styrene copolymer (MBS).

[0105] Comparative Example 1

[0106] The polyester composite material and its preparation method provided in this comparative example refer to Example 3, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.2wt% organic lubricant, 0.05wt% toughening agent, and the remainder is polyester matrix; no inorganic lubricant is added to the polyester composite material.

[0107] Comparative Example 2

[0108] The polyester composite material and its preparation method provided in this comparative example refer to Example 3, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.3wt% inorganic lubricant, 0.2wt% organic lubricant, 0.05wt% toughening agent, and the remainder is polyester matrix.

[0109] Comparative Example 3

[0110] The polyester composite material and its preparation method provided in this comparative example refer to Example 6, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.1wt% inorganic lubricant, 0.05wt% toughening agent, and the remainder is polyester matrix; no organic lubricant is added to the polyester composite material.

[0111] Comparative Example 4

[0112] The polyester composite material and its preparation method provided in this comparative example refer to Example 6, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.1wt% inorganic lubricant, 0.5wt% organic lubricant, 0.05wt% toughening agent, and the remainder is polyester matrix.

[0113] Comparative Example 5

[0114] The polyester composite material and its preparation method provided in this comparative example refer to Example 6, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.1wt% inorganic lubricant, 0.2wt% organic lubricant, and the remainder is polyester matrix; no toughening agent is added to the polyester composite material.

[0115] Comparative Example 6

[0116] The polyester composite material and its preparation method provided in this comparative example refer to Example 6, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.1wt% inorganic lubricant, 0.2wt% organic lubricant, 0.2wt% toughening agent, and the balance is polyester matrix.

[0117] Comparative Example 7

[0118] The polyester composite material and the preparation method thereof provided in this comparative example refer to Example 3, except that the polyester composite material, in terms of mass percentage, comprises the following components: 0.1 wt % inorganic lubricant, and the balance is polyester matrix.

[0119] Comparative Example 8

[0120] The polyester composite material and the preparation method thereof provided in this embodiment refer to Example 3, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.2 wt % organic lubricant, and the remainder is polyester matrix.

[0121] Comparative Example 9

[0122] The polyester composite material and the preparation method thereof provided in this embodiment refer to Example 3, except that the polyester composite material, in terms of mass percentage, includes the following components: 0.05 wt % toughening agent, and the balance is polyester matrix.

[0123] Comparative Example 10

[0124] The polyester composite material and the preparation method thereof provided in this embodiment refer to Example 3, except that the inorganic lubricant is zinc stearate.

[0125] Comparative Example 11

[0126] The polyester composite material and the preparation method thereof provided in this embodiment refer to Example 3, except that the organic lubricant is glyceryl tristearate.

[0127] Test Example 1

[0128] The properties of the polyester composite materials prepared in Examples 1 to 8 and Comparative Examples 1 to 11 were tested, and the results are shown in Table 1.

[0129] The testing method of injection speed is as follows: use Zhende CJ150M3V injection molding machine to carry out injection molding experiments on the samples respectively, the barrel temperature of the injection molding machine is 260±2℃, 270±2℃, 270±2℃, 265±2℃, the first-stage injection pressure is 55%, the speed is 50%, and the position is 65mm; the second-stage injection pressure is 30%, the speed is 40%, and the position is 35mm; the first-stage holding pressure is 15%, and the time is 5s; the second-stage holding pressure is 10%, and the time is 3s; the hot runner 1 temperature is 285±2℃, and the hot runner 2 temperature is 285±2℃; the mold is a 29g preform mold with 1 out of 4, and the blowing mold is a 500mL bottle mold with 1 out of 1. The injection speed of different samples is recorded during the injection molding process as an evaluation of the flow performance.

[0130] The test method for drop resistance is as follows: during the processing of polyester, due to the existence of degradation, the intrinsic viscosity is easily reduced, which leads to an increase in the brittleness of the material and a decrease in the toughness and drop resistance of the product; the toughness of the material is evaluated by the number of broken bottles of the product in the drop test. Before the test, the bottles are filled with water and sealed, and free fall is allowed. The test height is 2m, and there are 10 samples in each group. The number of unbroken bottles is recorded.

[0131] The transparency test method is: use the WGZ turbidity meter of Shanghai Xinrui Instrument Co., Ltd. to conduct turbidity test on different sample bottle embryos obtained by injection molding to evaluate the transparency of the material.

[0132] Antistatic performance test method: Schrader SL-030 digital surface resistance tester tests the surface resistivity of the sample.

[0133] Table 1

[0134]

[0135]

[0136] As can be seen from Table 1, the polyester composite materials of Examples 1 to 8 of the present invention modify the polyester matrix by using an inorganic lubricant, an organic lubricant and a toughening agent, and through the mutual cooperation and synergistic effect of each component, the polyester composite materials simultaneously have excellent fluidity, transparency, antistatic and anti-drop performance. However, the polyester composite materials of Comparative Examples 1 to 11 cannot simultaneously have excellent fluidity, transparency, antistatic and anti-drop performance.

[0137] Comparison of Example 2, Example 3, Comparative Example 1 and Comparative Example 2 shows that the addition of inorganic lubricant in the polyester composite material can improve the flow of the melt, but excessive addition reduces the transparency.

[0138] From the comparison of Example 3, Example 4, Example 5, Comparative Example 3 and Comparative Example 4, it can be seen that when an inorganic lubricant is used together with an organic lubricant, the fluidity and transparency can be improved due to the synergistic effect, but when used in excess, the melt viscosity will be seriously reduced, affecting the toughness, and the transparency will also be reduced; the internal olefins of the organic lubricant can promote the compatibility of the toughening agent with the polyester system, increasing the toughness without reducing the transparency.

[0139] Comparison of Example 3, Example 6, Example 7, Comparative Example 5 and Comparative Example 6 shows that the addition of toughening agent improves the fluidity and toughness of the polyester composite material; however, when the toughening agent is excessive, the transparency decreases.

[0140] 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 it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A polyester composite material, characterized in that: According to mass percentage, it includes the following components: 0.001wt% to 0.2wt% of inorganic lubricant, 0.001wt% to 0.4wt% of organic lubricant, 0.001wt% to 0.1wt% of toughening agent, and the balance is polyester matrix; The inorganic lubricant comprises modified silicon dioxide, the surface of which is modified with hydroxyl groups and phenyl groups; The organic lubricant includes a distilled glyceride lubricant.

2. The polyester composite material according to claim 1, characterized in that: The organic lubricant includes a distilled glycerol fatty acid ester lubricant; Preferably, the distilled glycerol fatty acid ester lubricant includes at least one of a polyglycerol fatty acid ester lubricant, a distilled glycerol mono-fatty acid ester lubricant and a distilled glycerol di-fatty acid ester lubricant.

3. The polyester composite material according to claim 2, characterized in that: The toughening agent includes a block copolymer of styrene-butadiene.

4. The polyester composite material according to claim 3, characterized in that: The polyester matrix is ​​obtained by polymerizing a dicarboxylic acid compound and a diol compound.

5. The polyester composite material according to claim 4, characterized in that: The dicarboxylic acid compound includes at least one of a C8-C14 aromatic dicarboxylic acid and a C4-C12 aliphatic dicarboxylic acid; And / or, the diol compound includes at least one of C2-C21 aliphatic diols.

6. The polyester composite material according to claim 4, characterized in that: The intrinsic viscosity of the polyester matrix is ​​0.5 to 0.9 dL / g.

7. The method for preparing the polyester composite material according to any one of claims 1 to 6, characterized in that: The steps include: S1, mixing the polyester matrix, the inorganic lubricant, the organic lubricant and the toughening agent, and extruding and granulating the mixture to obtain an additive masterbatch; S2. Mixing the additive masterbatch and the polyester matrix to obtain the polyester composite material.

8. The method for preparing the polyester composite material according to claim 7, characterized in that: In step S1, at least one of the following features (1) to (4) is included; (1) The extrusion granulation comprises using a twin-screw extruder; (2) The aspect ratio of the screw of the twin-screw extruder is (35-45):1; (3) The rotation speed of the twin-screw extruder is 150 to 600 rpm; (4) The temperature of the extrusion granulation is 180-270°C.

9. A polyester product, characterized in that: The polyester composite material is prepared by using the polyester composite material described in any one of claims 1 to 6.

10. The polyester product according to claim 9, characterized in that: The polyester product comprises at least one of an injection molded product, an extruded film-drawing product, an extruded film-blowing product, an extruded plate and an extruded profile.

Images