Cold-resistant and damp-heat-resistant PETG / PP (polyethylene terephthalate / polypropylene) alloy floor base material, preparation method thereof, floor and preparation method thereof

Abstract

The invention discloses a cold-resistant and damp-heat-resistant PETG / PP alloy floor base material and a preparation method thereof, and a floor and a preparation method thereof. The floor base material comprises the following raw materials in parts by mass: 5-20 parts of PETG resin, 2-8 parts of PP resin, 1-5 parts of a compatilizer, 3-10 parts of a flexibilizer, 20-70 parts of calcium carbonate, 3-10 parts of a modified inorganic fibrous filler, 0.2-2 parts of a chain extender, 1-3 parts of a lubricant, 0.5-2 parts of an antioxidant and 0.5-3 parts of an anti-hydrolysis agent. According to the cold-resistant and damp-heat-resistant PETG / PP alloy floor base material and the preparation method thereof as well as the floor and the preparation method thereof, the dimensional stability, cold resistance and damp-heat resistance of a polyester environment-friendly floor material can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of floor substrates and relates to a floor substrate, in particular to a cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate and a preparation method thereof, a floor and a preparation method thereof. Background Art

[0002] As an indoor floor decoration material, plastic flooring has the characteristics of being waterproof and moisture-proof, lightweight and elastic, and easy to splice and install. At present, plastic flooring is mainly based on PVC resin filled with calcium carbonate system. However, the recycling and separation cost of PVC materials is high, and incineration will produce toxic substances such as dioxins. In recent years, the concept of Non-PVC has received widespread attention in the plastic flooring industry, and the application of halogen-free and environmentally friendly resin systems such as PP, PE, PET, and PS in flooring materials has gradually been explored.

[0003] PET resin has the advantages of safety, environmental protection and recyclability. However, as a floor material, PET materials have the disadvantages of long-term water absorption, moisture and heat aging, poor impact resistance, etc., which limit their wide application and market promotion. There are few reports on the moisture and heat aging of PET floors in the prior art, such as patent documents CN220486992U (PET foaming treatment as an insulation layer, the overall strength is not high) and CN218970512U (PET as a film layer).

[0004] As a non-crystalline copolyester, PETG resin has better impact resistance than PET resin, but when used as floor material, the warping and thermal expansion performance caused by light cannot meet the requirements of daily life. At present, there are a small number of studies on using PETG for floor, such as patent documents CN115139616B (PETG as an anti-scratch layer and using a glass fiber layer), CN219706385U (PETG only as a film layer), CN214329733U (PETG is made together with a carbon fiber sheet layer and a polycarbonate sheet), CN212453480U (PETG only as a wear-resistant layer), CN112064977A (PETG only as a wear-resistant layer and a decorative layer, and the substrate layer is an MDI flame-retardant fiberboard).

[0005] As one of the general-purpose plastics, PP resin has excellent mechanical properties, including tensile strength, compressive strength and hardness, outstanding rigidity and bending fatigue resistance, as well as good chemical stability, water resistance and electrical insulation, and is widely used in different fields. However, PP has poor cold resistance and is prone to embrittlement at low temperatures, resulting in a decrease in impact resistance. In addition, polypropylene is susceptible to aging due to the effects of light, heat and oxygen during use, resulting in a decrease in performance.

[0006] In view of this, there is an urgent need to design a new floor substrate so as to overcome at least part of the above-mentioned defects of the existing floor substrate. Summary of the invention

[0007] The invention provides a cold-resistant and moisture-resistant PETG / PP alloy floor substrate and a preparation method thereof, a floor and a preparation method thereof, which can improve the dimensional stability, cold resistance and moisture-resistant properties of polyester-based environmentally friendly floor materials.

[0008] In order to solve the above technical problems, according to one aspect of the present invention, the following technical solution is adopted:

[0009] A cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate, the floor substrate comprising the following raw materials in parts by weight: 5 to 20 parts of PETG resin, 2 to 8 parts of PP resin, 1 to 5 parts of a compatibilizer, 3 to 10 parts of a toughening agent, 20 to 70 parts of calcium carbonate, 3 to 10 parts of a modified inorganic fibrous filler, 0.2 to 2 parts of a chain extender, 1 to 3 parts of a lubricant, 0.5 to 2 parts of an antioxidant and 0.5 to 3 parts of an anti-hydrolysis agent.

[0010] As an embodiment of the present invention, the PETG is amorphous, and its comonomer includes at least one of 1,4-cyclohexanedimethanol, 1,6-hexanediol, diethylene glycol, butanediol, neopentyl glycol or propylene glycol.

[0011] As an embodiment of the present invention, the compatibilizer includes at least one of polyethylene grafted maleic anhydride, polypropylene grafted maleic anhydride, ethylene-acrylate glycidyl methacrylate, SEBS-g-MAH, and POE-g-GMA;

[0012] The toughening agent includes at least one of TPEE, ACR, TPU, MBS and POE; and the active calcium carbonate is 200-1200 meshes.

[0013] As an embodiment of the present invention, the modified inorganic fibrous filler includes at least one of carbon nanotubes, halloysite nanotubes, calcium carbonate whiskers, alkali-free glass fibers or needle-shaped zinc oxide; the chain extender includes at least one of ADRS, PMDA, epoxies, isocyanates and TGIC.

[0014] As an embodiment of the present invention, the lubricant includes at least one of copolyester wax, OPE wax, calcium stearate, EAA wax, EBS, oleamide, and zinc stearate;

[0015] The antioxidant includes at least one of hindered phenols, aromatic amines, phosphites, and sulfur-containing esters; the anti-hydrolysis agent includes at least one of carbodiimide or polycarbodiimide.

[0016] According to another aspect of the present invention, the following technical solution is adopted: a floor, comprising the above-mentioned cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate.

[0017] According to another aspect of the present invention, the following technical scheme is adopted: a method for preparing the above-mentioned cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate, the preparation method comprising:

[0018] Step S2, weighing a set amount of PETG, PP resin, compatibilizer, chain extender, lubricant, antioxidant, anti-hydrolysis agent and calcium carbonate and blending them in a high-speed mixer;

[0019] Step S3, then adding a set amount of toughening agent to the mixed system obtained in step S2, further stirring for a set time, and then conveying to an extruder;

[0020] Step S4, adding an appropriate amount of modified inorganic fibrous filler, and after the material is extruded through an extruder, it is shaped and thickened by a hot roller to obtain a PETG / PP alloy floor substrate.

[0021] As an embodiment of the present invention, the preparation method further comprises step S1 before step S2, drying the PETG and PP resins at 60 to 80° C. for 6 to 12 hours to remove their own moisture, and setting aside;

[0022] In step S2, the blending temperature is 80°C to 120°C, the mixing time is 10 to 30 minutes, and the rotation speed is 300 r / min to 400 r / min;

[0023] In step S3, the twin-screw extruder has six functional sections, which are the first section feeding section, which can continuously feed the material; the second section melting section, which can heat the material as a whole to form a molten state; the third section plasticizing section, which plasticizes the material, thereby reducing the hardness of the material, improving the toughness of the material, and increasing the ductility and plasticity of the material; the fourth section exhaust section, which can discharge the excess pores in the melt; the fifth section mixing section, which fully mixes the raw materials; and the sixth section extrusion section, which extrude the material inside the twin-screw extruder to form a floor base shape. The temperatures of the screw twin-screw zones are set to be 190-120°C for zone 1, 195-190°C for zone 2, 190-180°C for zone 3, 185-175°C for zone 4, 180-170°C for zone 5, and 170-160°C for zone 6.

[0024] According to another aspect of the present invention, the following technical solution is adopted: a method for preparing the above-mentioned floor, the preparation method comprising:

[0025] Step S2, weighing a set amount of PETG, PP resin, compatibilizer, chain extender, lubricant, antioxidant, anti-hydrolysis agent and calcium carbonate and blending them in a high-speed mixer;

[0026] Step S3, then adding a set amount of toughening agent to the mixed system obtained in step S2, further stirring for a set time, and then conveying to an extruder;

[0027] Step S4, adding an appropriate amount of modified inorganic fibrous filler, after the material is extruded by an extruder, it is shaped and thickened by a hot roller to obtain a PETG / PP alloy floor substrate, and the PETG wear-resistant layer and the PETG transparent layer are composited by online hot lamination, and the texture is pressed, and the surface is coated with UV coating to obtain the final multi-layer composite PETG-based plastic floor.

[0028] As an embodiment of the present invention, the preparation method further comprises step S1 before step S2, drying the PETG and PP resins at 60-80° C. for 6-12 hours to remove their own moisture for standby use; in step S2, the blending temperature is 80° C.-120° C., the mixing is 10-30 minutes, and the rotation speed is 300 r / min-400 r / min;

[0029] In step S3, the twin-screw extruder has six functional sections, which are the first section feeding section, which can continuously feed the material; the second section melting section, which can heat the material as a whole to form a molten state; the third section plasticizing section, which plasticizes the material, thereby reducing the hardness of the material, improving the toughness of the material, and increasing the ductility and plasticity of the material; the fourth section exhaust section, which can discharge the excess pores in the melt; the fifth section mixing section, which fully mixes the raw materials; and the sixth section extrusion section, which extrude the material inside the twin-screw extruder to form a floor base shape. The temperatures of the screw twin-screw zones are set to be 120-190°C for zone 1, 195-190°C for zone 2, 190-180°C for zone 3, 185-175°C for zone 4, 180-170°C for zone 5, and 170-160°C for zone 6.

[0030] The beneficial effects of the present invention are as follows: the cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate and its preparation method, the floor and its preparation method proposed in the present invention can improve the dimensional stability, cold resistance and moisture-resistant and heat-resistant of polyester-based environmentally friendly floor materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Schematic diagram of the structure of the floor in one embodiment of the present invention.

[0032] Figure 2 The figure is a flow chart of a method for preparing a floor substrate in one embodiment of the present invention.

[0033] Figure 3 The figure is a flow chart of a floor preparation method according to an embodiment of the present invention. DETAILED DESCRIPTION

[0034] The preferred embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0035] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0036] The description in this section is only for several typical embodiments, and the present invention is not limited to the scope of the embodiments. The same or similar prior art means and some technical features in the embodiments are mutually replaced within the scope of the present invention.

[0037] Unless otherwise indicated, implied from the context, or customary in the prior art, all parts and percentages in this application are based on weight, and the test and characterization methods used are all current as of the filing date of this application. Where applicable, the contents of any patent, patent application or publication referred to in this application are fully incorporated herein by reference, and their equivalent patent families are also incorporated by reference, especially the definitions of synthesis techniques, product and processing designs, polymers, comonomers, initiators or catalysts disclosed in these documents in the art. If the definition of a specific term disclosed in the prior art is inconsistent with any definition provided in this application, the definition of the term provided in this application shall prevail.

[0038] Numerical ranges in this application are approximate values, so unless otherwise specified, they may include numerical values ​​outside the range. Numerical ranges include all numerical values ​​from the lower limit to the upper limit increased by 1 unit, provided that there is an interval of at least 2 units between any lower value and any higher value. For example, if the recorded component, physical or other properties (such as molecular weight, melt index, etc.) are 100 to 1000, it means that all single values ​​are clearly listed, such as 100, 101, 102, etc., and all sub-ranges, such as 100 to 166, 155 to 170, 198 to 200, etc. For a range containing a numerical value less than 1 or containing a fraction greater than 1 (such as 1.1, 1.5, etc.), 1 unit is appropriately regarded as 0.0001, 0.001, 0.01 or 0.1. For a range containing a single digit less than 10 (such as 1 to 5), 1 unit is usually regarded as 0.1. These are only specific examples of what is intended to be expressed, and all possible combinations of values ​​between the lowest and highest values ​​listed are considered to be clearly recorded in this application. It should also be noted that the terms "first", "second", etc. in this article do not limit the order of precedence, but are only used to distinguish substances with different structures.

[0039] When used with respect to chemical compounds, unless expressly specified otherwise, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively). In addition, nouns using "a," "an," or "the" also include their plural forms unless expressly specified otherwise.

[0040] The terms "comprising", "including", "having" and their derivatives do not exclude the presence of any other components, steps or processes, and are irrelevant to whether these other components, steps or processes are disclosed in this application. To eliminate any doubt, unless explicitly stated, all compositions using the terms "comprising", "including", or "having" in this application may include any additional additives, adjuvants or compounds. On the contrary, except for those necessary for operating performance, the term "essentially consisting of..." excludes any other components, steps or processes from the scope of any description of the term below. The term "consisting of..." does not include any components, steps or processes that are not specifically described or listed. Unless explicitly stated, the term "or" refers to the listed individual members or any combination thereof.

[0041] The description of the steps in each embodiment in the specification is only for the convenience of explanation, and the implementation method of the present application is not limited by the order of implementation of the steps.

[0042] The invention discloses a cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate, which comprises the following raw materials in parts by weight: 5 to 20 parts of PETG resin, 2 to 8 parts of PP resin, 1 to 5 parts of a compatibilizer, 3 to 10 parts of a toughening agent, 20 to 70 parts of calcium carbonate, 3 to 10 parts of a modified inorganic fibrous filler, 0.2 to 2 parts of a chain extender, 1 to 3 parts of a lubricant, 0.5 to 2 parts of an antioxidant and 0.5 to 3 parts of an anti-hydrolysis agent.

[0043] In one embodiment of the present invention, the PETG may be amorphous, and its comonomer may include at least one of 1,4-cyclohexanedimethanol, 1,6-hexanediol, diethylene glycol, butanediol, neopentyl glycol or propylene glycol. The compatibilizer may include at least one of polyethylene grafted maleic anhydride, polypropylene grafted maleic anhydride, ethylene-acrylate glycidyl methacrylate, SEBS-g-MAH, POE-g-GMA; the toughening agent may include at least one of TPEE, ACR, TPU, MBS, POE; the activated calcium carbonate is 200-1200 mesh.

[0044] The modified inorganic fibrous filler may include at least one of carbon nanotubes, halloysite nanotubes, calcium carbonate whiskers, alkali-free glass fibers, or needle-shaped zinc oxide; the chain extender may include at least one of ADRS, PMDA, epoxies, isocyanates, and TGIC. The lubricant may include at least one of copolyester wax, OPE wax, calcium stearate, EAA wax, EBS, oleamide, and zinc stearate; the antioxidant may include at least one of hindered phenols, aromatic amines, phosphites, and sulfur-containing esters; the anti-hydrolysis agent may include at least one of carbodiimide or polycarbodiimide.

[0045] The present invention further discloses a method for preparing the above-mentioned cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate. Figure 2 is a flow chart of a method for preparing a floor substrate according to an embodiment of the present invention; Figure 2 , the preparation method comprises:

[0046] [Step S1] Drying the PETG and PP resins at 60-80° C. for 6-12 hours to remove their own moisture for later use;

[0047] [Step S2] Weigh a set amount of PETG, PP resin, compatibilizer, chain extender, lubricant, antioxidant, anti-hydrolysis agent and calcium carbonate and blend them in a high-speed mixer; in one embodiment, the blending temperature is 80°C to 120°C, the mixing time is 10 to 30 minutes, and the rotation speed is 300 r / min to 400 r / min.

[0048] [Step S3] Add a set amount of toughening agent to the mixed system obtained in step S2, further stir for a set time (such as 10 to 20 minutes), and then feed it into a twin-screw extruder through a main feeder; in one embodiment, the twin-screw extruder has six functional sections, which are, in sequence, a feeding section in the first zone, which can continuously feed the material; a melting section in the second zone, which can heat the entire material to form a molten state; a plasticizing section in the third zone, which plasticizes the material, thereby reducing the hardness of the material, improving the toughness of the material, and increasing the ductility and plasticity of the material; a venting section in the fourth zone, which can discharge excess pores in the melt; a mixing section in the fifth zone, which fully mixes the raw materials; and an extrusion section in the sixth zone, which extrude the material inside the twin-screw extruder to form a floor base shape. The temperatures of each zone of the screw are set at 190-120°C for zone 1, 195-190°C for zone 2, 190-180°C for zone 3, 185-175°C for zone 4, 180-170°C for zone 5, and 170-160°C for zone 6.

[0049] [Step S4] An appropriate amount of modified inorganic fibrous filler is added through the first side feeding, and after the material is extruded by a twin-screw, it is shaped and thickened by a hot roller to obtain a PETG / PP alloy floor substrate.

[0050] The present invention also discloses a floor, which comprises the above-mentioned cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate. Figure 1 This is a schematic diagram of the structure of the floor in one embodiment of the present invention; please refer to Figure 1 In one embodiment of the present invention, the floor comprises a coating layer 1, a PETG transparent film layer 2, a PETG color film layer 3, a PETG / PP substrate layer 4, a coating layer 1, and a sound-absorbing layer 5, which are arranged in sequence. The substrate used in the PETG / PP substrate layer 4 is the above-mentioned PETG / PP alloy floor substrate.

[0051] The present invention further discloses a method for preparing the above-mentioned floor. Figure 3 is a flow chart of a floor preparation method according to an embodiment of the present invention; please refer to Figure 3 , the preparation method comprises:

[0052] [Step S1] Drying the PETG and PP resins at 60-80° C. for 6-12 hours to remove their own moisture for later use;

[0053] [Step S2] Weigh a set amount of PETG, PP resin, compatibilizer, chain extender, lubricant, antioxidant, anti-hydrolysis agent and calcium carbonate and blend them in a high-speed mixer; in one embodiment, the blending temperature is 80°C to 120°C, the mixing time is 10 to 30 minutes, and the rotation speed is 300 r / min to 400 r / min.

[0054] [Step S3] Then, a set amount of toughening agent is added to the mixed system obtained in step S2, and after further stirring for 10 to 20 minutes, it is fed into the twin-screw extruder through the main feed. In one embodiment, the twin-screw extruder has six functional sections, which are the first zone feeding section, which can continuously feed; the second zone melting section, which can heat the material as a whole to form a molten state; the third zone plasticizing section, which plasticizes the material, thereby reducing the hardness of the material, improving the toughness of the material, and increasing the ductility and plasticity of the material; the fourth zone exhaust section, which can discharge the excess pores in the melt; the fifth zone mixing section, which fully mixes the raw materials; the sixth zone extrusion section, which extrude the material inside the twin-screw extruder to form a floor base shape. The temperatures of the screw zones are set to be 190 to 120°C for zone 1, 195 to 190°C for zone 2, 190 to 180°C for zone 3, 185 to 175°C for zone 4, 180 to 170°C for zone 5, and 170 to 160°C for zone 6.

[0055] [Step S4] An appropriate amount of modified inorganic fibrous filler is added through the first side feeding. After the material is extruded by a twin-screw, it is shaped and thickened by a hot roller to obtain a PETG / PP alloy floor substrate. The PETG wear-resistant layer and the PETG transparent layer are composited by online hot lamination, and the texture is pressed. After the surface is coated with UV coating, the final multi-layer composite PETG-based plastic floor is obtained.

[0056] The following examples and comparative examples prepare PETG / PP floor substrates and products by the following method, and weigh the components as shown in Table 1. The specific steps are as follows:

[0057] S1. Dry the PETG and PP resins at 60-80°C for 6-12 hours to remove their own moisture and set aside.

[0058] S2. Weigh a certain amount of PETG, PP resin, compatibilizer, chain extender, lubricant, antioxidant, anti-hydrolysis agent and calcium carbonate and blend them in a high-speed mixer at a temperature of 80°C to 120°C for 10 to 30 minutes at a speed of 300 r / min to 400 r / min.

[0059] S3. Then add a certain amount of toughening agent to the mixed system obtained in S2, further stir for 10 to 20 minutes, and then feed it into the twin-screw extruder through the main feed. The twin-screw extruder has six functional sections, which are the first zone feeding section, which can continuously feed; the second zone melting section, which can heat the material as a whole to form a molten state; the third zone plasticizing section, which plasticizes the material, thereby reducing the hardness of the material, improving the toughness of the material, and increasing the ductility and plasticity of the material; the fourth zone exhaust section, which can discharge the excess pores in the melt; the fifth zone mixing section, which fully mixes the raw materials; the sixth zone extrusion section, which extrudes the material inside the twin-screw extruder equipment to form a floor base shape. Set the temperature of each zone of the screw: the temperature of the first zone is 190 to 120°C, the temperature of the second zone is 195 to 190°C, the temperature of the third zone is 190 to 180°C, the temperature of the fourth zone is 185 to 175°C, the temperature of the fifth zone is 180 to 170°C, and the temperature of the sixth zone is 170 to 160°C.

[0060] S4. Add an appropriate amount of modified inorganic fibrous filler through the first side feeding, and after the material is extruded by a twin-screw, it is shaped and thickened by a hot roller to obtain a PETG / PP substrate, and then the PETG wear-resistant layer and the PETG transparent layer are composited by online hot lamination, and the texture is pressed. After the surface is coated with UV coating, the final multi-layer composite PETG-based plastic floor product is obtained.

[0061] Examples 1 to 7 and Comparative Examples 1 to 7

[0062] Table 1 Examples 1 to 7 (parts)

[0063]

[0064]

[0065] Table 2 Comparative Examples 1 to 7 (parts)

[0066] raw material Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 PETG 22 \ 20 20 20 20 20 PP \ 22 2 2 2 2 2 PE-g-MAH 2 2 \ 2 2 2 2 ACR 5 5 5 \ 5 5 5 Activated calcium carbonate 60 60 60 60 60 60 60 Alkali-free glass fiber 5 5 5 5 \ 5 5 ADRS 1 1 1 1 1 \ 1 Copolyester wax 2 2 2 2 2 2 2 Phosphites 1 1 1 1 1 1 1 Carbodiimide 2 2 2 2 2 2 \

[0067] The PETG / PP floor products prepared in the above examples and comparative examples were subjected to the following performance tests, and the test reference standards and methods are as follows:

[0068] Warpage: Tested in accordance with ISO24342 standard. Cut the sample into a 250mm×250mm square, place it on a flat table, and use a feeler gauge to test the four corners of the sample one by one. The test result is the maximum value of the four corners. The warpage is required to be ≤1.2mm.

[0069] Thermal shrinkage: Tested in accordance with ISO24342 standard. Cut the sample into a 250mm×250mm square, measure the length and width of the sample (all four sides need to be measured and recorded, length is L10, L20, width is W10, W20), place the sample in an 80℃ oven, take it out after 6 hours and place it in the laboratory for 3 hours, and then test the length and width of the sample after standing (length is L11, L21, width is W11, W21). Calculate, length: [(L11+L21) / 2-(L10+L20) / 2] / [(L10+L20) / 2]; width: [(W11+W21) / 2-(W10+W20) / 2] / [(W10+W20) / 2], and select the maximum value of the test result. The thermal shrinkage rate is required to be ≤0.12%.

[0070] Wheelchair test: Tested in accordance with EN425 standard. The sample is slotted into a U-shaped buckle or vertical buckle, cut into a specific shape for splicing, and the spliced ​​sample is fixed on the wheelchair tester, and different rotations are set for testing. The wheelchair test is required to be ≥25,000 rotations.

[0071] Thermal expansion: Cut a 180mm×1220mm sample, measure the length and width of the sample, record the length as L10 and L20, record the width as W10 and W20, place it in the drying room, set the drying room temperature to 1℃, and record the time when it reaches the set temperature. After keeping warm for 24 hours, measure the length and width, record the length as L11 and L21, and the width as W11 and W21. After the drying room temperature reaches room temperature, place the sample in the laboratory for 24 hours, measure the length and width, record the length as L12 and L22, and the width as W12 and W22. Place the sample in the drying room, set the temperature to 38℃, reach the set temperature, and record the time. After keeping warm for 24 hours, measure the length and width, record the length as L13 and L23, and the width as W13 and W23. After the drying room cools to room temperature, place the sample in the laboratory for 24 hours, measure the length and width, record the length as L14 and L24, and the width as W14 and W24. Calculate the experimental data, the thermal expansion coefficient of length is: [(L13+L23) / 2-(L10+L20) / 2] / [(L10+L20) / 2]; the thermal expansion coefficient of width is: [(W13+W23) / 2-(W10+W20) / 2] / [(W10+W20) / 2], and select the maximum value from the test results. The thermal expansion coefficient is required to be ≤6.

[0072] Drop ball impact: Tested in accordance with EN13329 standard. Place a 300mm×250mm sample on the bottom of the drop ball impact tester and fix it with screws. Use a 2280g ball to drop from a height of 1500mm for impact testing. No cracking is required by the drop ball impact.

[0073] Lighting test: Cut a sample of 180mm×1220mm, place it in a lighting laboratory, set the lighting temperature to 70℃, and light for 3 hours. It is required that there is no arching phenomenon after lighting.

[0074] Elastic modulus and static bending strength: Tested according to GB17657 standard. Cut 50mm×150mm samples, measure the sample thickness, place the samples on the support rollers of the universal mechanical testing machine, input the sample thickness and then test. The elastic modulus is required to be ≥3500MPa and the static bending strength is ≥18MPa.

[0075] Performance test

[0076] The PETG / PP floor substrates obtained in Examples 1 to 7 and Comparative Examples 1 to 7 were tested

[0077] Table 3 Performance test data of Examples 1 to 7

[0078] performance Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Warpage(mm) 0.15 1.9 1.4 0.20 1.5 0.20 1.60 Shrinkage rate (%) 0.05 0.19 0.15 0.12 0.21 0.29 0.25 Wheelchair test(r) 30000 24000 23000 26000 22000 25000 25000 Coefficient of thermal expansion 2.2 5.6 5.9 3.8 5.7 6.1 5.3 Low temperature drop ball impact No cracking No cracking There is cracking There is cracking No cracking No cracking No cracking Lighting test No arching No arching No arching No arching No arching There is arching There is arching Elastic modulus (MPa) 4036 3869 3904 3623 2642 3361 3856 Static bending strength (MPa) 28.2 23.2 23.7 23.1 20.4 22.2 23.9

[0079] Table 4 Performance test data of comparative examples 1 to 7

[0080]

[0081]

[0082] From Examples 1, 2, 3 and Comparative Examples 1, 2, 3, it can be seen that PETG has a benzene ring and a regular structure, so it has good flatness and dimensional stability, but insufficient toughness; the molecular chain structure of PP is relatively stable and is not easy to decompose or degrade in a hot and humid environment. Only when the ratio of PETG and PP is appropriate can good dimensional stability and toughness be taken into account; in addition, the lack of a compatibilizer easily leads to phase separation and the sample is prone to cracking.

[0083] From Example 4 and Comparative Example 4, no toughening agent or too little toughening agent will lead to poor cold resistance of the material and decreased low-temperature impact performance. From Example 5 and Comparative Example 5, using alkali-free glass fiber and calcium carbonate as fillers together can avoid thermal expansion and contraction, and has better thermal stability than when a high amount of calcium carbonate is filled alone; in addition, alkali-free glass fiber also has a rigidity-enhancing effect, and a reduced filling amount will lead to a decrease in elastic modulus and flexural strength.

[0084] From Example 6 and Comparative Example 6, the absence of chain extender or too little chain extender will lead to insufficient melt strength and imperfect dimensional stability during processing, resulting in increased shrinkage and thermal expansion coefficient. From Example 7 and Comparative Example 7, the absence of anti-hydrolysis agent or insufficient anti-hydrolysis agent will lead to poor moisture and heat resistance of the material, causing increased shrinkage and warpage of the material.

[0085] In summary, the cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate and its preparation method, the floor and its preparation method proposed in the present invention can improve the dimensional stability, cold resistance and moisture-resistant and heat-resistant of polyester-based environmentally friendly floor materials.

[0086] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0087] The description and application of the present invention here are illustrative, and it is not intended to limit the scope of the present invention to the above-mentioned embodiments. The effects or advantages involved in the embodiments may not be embodied in the embodiments due to interference from various factors, and the description of the effects or advantages is not used to limit the embodiments. The deformation and change of the embodiments disclosed here are possible, and the replacement of the embodiments and the various equivalent parts are well known to those of ordinary skill in the art. It should be clear to those skilled in the art that the present invention can be implemented in other forms, structures, arrangements, proportions, and with other components, materials and parts without departing from the spirit or essential features of the present invention. Other deformations and changes can be made to the embodiments disclosed here without departing from the scope and spirit of the present invention.

Claims

1. A cold-resistant, heat-resistant PETG / PP alloy floor substrate, characterized in that: The floor substrate comprises the following raw materials in parts by weight: 5 to 20 parts of PETG resin, 2 to 8 parts of PP resin, 1 to 5 parts of compatibilizer, 3 to 10 parts of toughening agent, 20 to 70 parts of calcium carbonate, 3 to 10 parts of modified inorganic fibrous filler, 0.2 to 2 parts of chain extender, 1 to 3 parts of lubricant, 0.5 to 2 parts of antioxidant and 0.5 to 3 parts of anti-hydrolysis agent.

2. The cold-resistant and heat-resistant PETG / PP alloy floor substrate according to claim 1, characterized in that: The PETG is amorphous, and its comonomer includes at least one of 1,4-cyclohexanedimethanol, 1,6-hexanediol, diethylene glycol, butanediol, neopentyl glycol or propylene glycol.

3. The cold-resistant and heat-resistant PETG / PP alloy floor substrate according to claim 1, characterized in that: The compatibilizer includes at least one of polyethylene grafted maleic anhydride, polypropylene grafted maleic anhydride, ethylene-acrylate glycidyl methacrylate, SEBS-g-MAH, and POE-g-GMA; The toughening agent includes at least one of TPEE, ACR, TPU, MBS and POE; and the active calcium carbonate is 200-1200 meshes.

4. The cold-resistant and heat-resistant PETG / PP alloy floor substrate according to claim 1, characterized in that: The modified inorganic fibrous filler includes at least one of carbon nanotubes, halloysite nanotubes, calcium carbonate whiskers, alkali-free glass fibers or needle-shaped zinc oxide; the chain extender includes at least one of ADRS, PMDA, epoxies, isocyanates and TGIC.

5. The cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate according to claim 1, characterized in that: The lubricant comprises at least one of copolyester wax, OPE wax, calcium stearate, EAA wax, EBS, oleamide, and zinc stearate; The antioxidant includes at least one of hindered phenols, aromatic amines, phosphites, and sulfur-containing esters; the anti-hydrolysis agent includes at least one of carbodiimide or polycarbodiimide.

6. A floor, characterized in that: The floor comprises the cold-resistant, moisture-resistant and heat-resistant PETG / PP alloy floor substrate as described in any one of claims 1 to 5.

7. A method for preparing the cold-resistant and heat-resistant PETG / PP alloy floor substrate according to any one of claims 1 to 5, characterized in that: The preparation method comprises: Step S2, weighing a set amount of PETG, PP resin, compatibilizer, chain extender, lubricant, antioxidant, anti-hydrolysis agent and calcium carbonate and blending them in a high-speed mixer; Step S3, then adding a set amount of toughening agent to the mixed system obtained in step S2, further stirring for a set time, and then conveying to an extruder; Step S4, adding an appropriate amount of modified inorganic fibrous filler, and after the material is extruded by an extruder, it is shaped and thickened by a hot roller to obtain a PETG / PP alloy floor substrate.

8. The preparation method according to claim 7, characterized in that: The preparation method further comprises, before step S2: step S1, drying the PETG and PP resins at 60-80° C. for 6-12 hours to remove their own moisture for standby use; In step S2, the blending temperature is 80°C to 120°C, the mixing time is 10 to 30 minutes, and the rotation speed is 300 r / min to 400 r / min; In the step S3, the twin-screw extruder has six functional sections, which are: a feeding section in the first zone for continuous feeding; a melting section in the second zone for heating the material as a whole to form a molten state; a plasticizing section in the third zone for plasticizing the material, thereby reducing the hardness of the material, improving the toughness of the material, and increasing the ductility and plasticity of the material; a venting section in the fourth zone for discharging excess pores in the melt; a mixing section in the fifth zone for fully mixing the raw materials; an extrusion section in the sixth zone for extruding the material inside the twin-screw extruder to form a floor base shape; the temperatures of the screw and twin-screw zones are set to be 190-120°C for zone one, 195-190°C for zone two, 190-180°C for zone three, 185-175°C for zone four, 180-170°C for zone five, and 170-160°C for zone six.

9. A method for preparing the floor according to claim 6, characterized in that: The preparation method comprises: Step S2, weighing a set amount of PETG, PP resin, compatibilizer, chain extender, lubricant, antioxidant, anti-hydrolysis agent and calcium carbonate and blending them in a high-speed mixer; Step S3, then adding a set amount of toughening agent to the mixed system obtained in step S2, further stirring for a set time, and then conveying to an extruder; Step S4, adding an appropriate amount of modified inorganic fibrous filler, after the material is extruded by an extruder, it is shaped and thickened by a hot roller to obtain a PETG / PP alloy floor substrate, and the PETG wear-resistant layer and the PETG transparent layer are composited by online hot lamination, and the texture is pressed, and the surface is coated with UV coating to obtain the final multi-layer composite PETG-based plastic floor.

10. The preparation method according to claim 9, characterized in that: The preparation method further comprises, before step S2: step S1, drying the PETG and PP resins at 60-80° C. for 6-12 hours to remove their own moisture for standby use; In step S2, the blending temperature is 80°C to 120°C, the mixing time is 10 to 30 minutes, and the rotation speed is 300 r / min to 400 r / min; In the step S3, the twin-screw extruder has six functional sections, which are, in order, a feeding section in the first zone for continuous feeding; a melting section in the second zone for heating the material as a whole to form a molten state; a plasticizing section in the third zone for plasticizing the material, thereby reducing the hardness of the material, improving the toughness of the material, and increasing the ductility and plasticity of the material; a venting section in the fourth zone for exhausting excess pores in the melt; a mixing section in the fifth zone for fully mixing the raw materials; an extrusion section in the sixth zone for extruding the material inside the twin-screw extruder to form a floor base shape; the temperatures of the screw and twin-screw zones are set to be 190-120°C for zone one, 195-190°C for zone two, 190-180°C for zone three, 185-175°C for zone four, 180-170°C for zone five, and 170-160°C for zone six.

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