A high-strength layered flame-retardant board and its production process

Abstract

The invention relates to the technical field of composite materials, and proposes a high-strength layered flame-retardant board and a production process thereof. The high-strength layered flame-retardant board comprises a substrate layer, a flame-retardant adhesive layer, and a flame-retardant reinforcing layer from bottom to top; the substrate layer comprises the following components in parts by weight: 100 parts of polyolefin, 40-50 parts of SEBS, and 0.5-2 parts of antioxidant; the flame-retardant adhesive layer comprises the following components in parts by weight: 85-95 parts of epoxy resin, 15-25 parts of flame retardant, and 10-15 parts of curing agent; the flame-retardant reinforcing layer comprises the following components in parts by weight: 100 parts of polyolefin, 45-55 parts of SEBS, 20-30 parts of flame retardant, and 0.5-2 parts of antioxidant; the styrene content in the first SEBS is 13wt%-33wt%; and the styrene content in the second SEBS is 20wt%-41wt%. Through the above technical scheme, the problems of low strength and poor aging resistance of flame-retardant plastic sheets in the related art are solved.

Description

Technical Field

[0001] The invention relates to the technical field of composite materials, and in particular to a high-strength layered flame-retardant board and a production process thereof. Background Art

[0002] In recent years, with the rapid development of the automotive industry, the electronic and electrical industry and other industries, there has been a huge market demand for plastic sheets. The layered sheets in plastic sheets are made of two or more layers of sheets through bonding and hot pressing, and have been used in many fields. As multifunctional, portable and thin laminates have become a hot spot in research and application, they are required to have high heat resistance, chemical resistance and excellent mechanical properties. More importantly, it is necessary to solve the problem that plastic sheets are easy to burn and produce a lot of thick smoke, molten droplets or toxic gases. Therefore, in order to meet the flame retardant requirements, flame retardant modification is generally carried out by adding flame retardants. However, adding too much flame retardant will affect the strength of the sheet, and long-term use will lead to a decrease in aging resistance. Therefore, how to improve the strength and aging resistance of flame-retardant plastic sheets is a problem that has yet to be solved. Summary of the invention

[0003] The present invention provides a highly aging-resistant layered flame-retardant board and a production process thereof, which solves the problems of low strength and poor aging resistance of flame-retardant plastic boards in the related art.

[0004] The technical solution of the present invention is as follows:

[0005] The present invention provides a highly aging-resistant layered flame-retardant board, which comprises, from bottom to top, a substrate layer, a flame-retardant adhesive layer, and a flame-retardant reinforcing layer;

[0006] The substrate layer comprises the following components in parts by weight: 100 parts of polyolefin, 40-50 parts of the first SEBS, and 0.5-2 parts of an antioxidant;

[0007] The flame retardant adhesive layer comprises the following components in parts by weight: 85-95 parts of epoxy resin, 15-25 parts of flame retardant, and 10-15 parts of curing agent;

[0008] The flame retardant reinforcement layer comprises the following components in parts by weight: 100 parts of polyolefin, 45-55 parts of the second SEBS, 20-30 parts of flame retardant, and 0.5-2 parts of antioxidant;

[0009] The styrene content in the first SEBS is 13wt%~33wt%;

[0010] The styrene content in the second SEBS is 20wt%~41wt%.

[0011] As a further technical solution, the styrene content in the first SEBS is less than the styrene content in the second SEBS.

[0012] In the present invention, when the styrene content in the first SEBS is less than the styrene content in the second SEBS, the strength and aging resistance of the flame-retardant plastic sheet are further improved.

[0013] As a further technical solution, the polyolefin is one or more of polyethylene, polypropylene, and polyvinyl chloride;

[0014] The flame retardant is a mixture of magnesium aluminum hydrotalcite and an organic phosphorus flame retardant;

[0015] The organophosphorus flame retardant is one or more of tricresyl phosphate, triphenyl phosphate, and tri(xylene) phosphate;

[0016] The antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 1024, antioxidant 264, and antioxidant 1076;

[0017] The curing agent is one or more of triethylenetetramine, tetraethylenepentamine, ethylenediamine and diethylenetriamine.

[0018] As a further technical solution, the mass ratio of the magnesium aluminum hydrotalcite to the organic phosphorus flame retardant is 4:1~4.

[0019] As a further technical solution, the magnesium aluminum hydrotalcite is ASA resin modified magnesium aluminum hydrotalcite.

[0020] In the present invention, ASA resin is used to modify magnesium aluminum hydrotalcite to avoid agglomeration of magnesium aluminum hydrotalcite and improve dispersion in the plate, further improving the strength and aging resistance of the flame retardant plastic plate and the flame retardancy of the plastic plate.

[0021] As a further technical solution, the ASA resin in the ASA resin-modified magnesium-aluminum hydrotalcite is composed of ASA resin XC220 and ASA resin XC200 in a mass ratio of 2:3 to 4:1.

[0022] In the present invention, when the mass ratio of ASA resin XC220 to ASA resin XC200 is adjusted to 2:3-4:1, the aging resistance and flame retardancy of the flame retardant plastic sheet are further improved.

[0023] As a further technical solution, the mass ratio of ASA resin to magnesium-aluminum hydrotalcite in the ASA resin-modified magnesium-aluminum hydrotalcite is 1:1-3.

[0024] As a further technical solution, the preparation method of the ASA resin modified magnesium aluminum hydrotalcite comprises the following steps: melting the ASA resin, mixing it with the magnesium aluminum hydrotalcite, and granulating it to obtain the ASA resin modified magnesium aluminum hydrotalcite with a particle size of 50-60 μm.

[0025] As a further technical solution, the thickness of the substrate layer is 500-600 μm; the thickness of the flame retardant adhesive layer is 80-90 μm; and the thickness of the flame retardant reinforcement layer is 600-700 μm.

[0026] The present invention also proposes a production process of a highly aging-resistant layered flame-retardant board, comprising the following steps:

[0027] S1, mixing the components of the substrate layer, and extruding into a plate to obtain a substrate layer;

[0028] S2, mixing the components of the flame retardant reinforcement layer, and extruding the mixture into a plate to obtain a flame retardant reinforcement layer;

[0029] S3. After mixing the components of the flame retardant adhesive layer, apply the mixture between the substrate layer and the flame retardant reinforcement layer, and cure the mixture to obtain a layered flame retardant board.

[0030] The working principle and beneficial effects of the present invention are:

[0031] In the present invention, the styrene content in the SEBS of the substrate layer is 13% to 33%, and the styrene content in the SEBS of the flame retardant reinforcement layer is 20% to 41%. By using SEBS with different styrene contents in the substrate layer and the flame retardant reinforcement layer of the layered flame retardant board, the two layers cooperate with each other, thereby significantly improving the strength and aging resistance of the flame retardant plastic board. DETAILED DESCRIPTION

[0032] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] In the following embodiments and comparative examples, the particle size of magnesium aluminum hydrotalcite is 0.44 μm, CAS number: 11097-59-9; the model of polyethylene is HDPE-5200B; the model of polypropylene is DL-670M; the model of polyvinyl chloride is HG-700; the model of SEBS with a styrene content of 33wt% is G1641; the model of SEBS with a styrene content of 20wt% is G1642; the model of SEBS with a styrene content of 13wt% is G1657; the model of SEBS with a styrene content of 41wt% is RP6936; the model of SEBS with a styrene content of 30wt% is G1650; the model of SEBS with a styrene content of 18wt% is G1643M.

[0034] Example 1

[0035] The high-strength layered flame-retardant board comprises, from bottom to top, a base material layer with a thickness of 500 μm, a flame-retardant adhesive layer with a thickness of 90 μm, and a flame-retardant reinforcement layer with a thickness of 700 μm;

[0036] The substrate layer includes the following components in parts by weight: 100 parts of polyethylene, 40 parts of the first SEBS, and 0.5 parts of antioxidant 1010;

[0037] The flame retardant adhesive layer comprises the following components in parts by weight: 85 parts of epoxy resin, 16 parts of magnesium aluminum hydrotalcite, 4 parts of tricresyl phosphate, and 10 parts of tetraethylenepentamine;

[0038] The flame retardant reinforcement layer includes the following components in parts by weight: 30 parts of polyethylene, 70 parts of polyvinyl chloride, 45 parts of the second SEBS, 20 parts of magnesium aluminum hydrotalcite, 5 parts of tricresyl phosphate, and 0.5 parts of antioxidant 168;

[0039] The styrene content in the first SEBS is 33wt%, and the styrene content in the second SEBS is 20wt%;

[0040] The production process of high-strength layered flame-retardant panels includes the following steps:

[0041] S1, mixing the components of the substrate layer, and extruding them into a plate to obtain the substrate layer;

[0042] S2, mixing the components of the flame retardant reinforcement layer, and extruding them into a plate to obtain a flame retardant reinforcement layer;

[0043] S3. After mixing the components of the flame retardant adhesive layer, apply it between the base material layer and the flame retardant reinforcement layer, and cure it to obtain a layered flame retardant board.

[0044] Example 2

[0045] The high-strength layered flame-retardant board comprises, from bottom to top, a base material layer with a thickness of 600 μm, a flame-retardant adhesive layer with a thickness of 80 μm, and a flame-retardant reinforcing layer with a thickness of 600 μm;

[0046] The substrate layer includes the following components in parts by weight: 80 parts of polyethylene, 20 parts of polypropylene, 50 parts of the first SEBS, 1 part of antioxidant 168, and 1 part of antioxidant 1076;

[0047] The flame retardant adhesive layer comprises the following components in parts by weight: 95 parts of epoxy resin, 12.5 parts of magnesium aluminum hydrotalcite, 12.5 parts of tri(xylene) phosphate, and 15 parts of diethylenetriamine;

[0048] The flame retardant reinforcement layer includes the following components in parts by weight: 100 parts of polyvinyl chloride, 55 parts of the second SEBS, 15 parts of magnesium aluminum hydrotalcite, 15 parts of tri(xylene) phosphate, and 2 parts of antioxidant 264;

[0049] The styrene content in the first SEBS is 13wt%, and the styrene content in the second SEBS is 41wt%;

[0050] The production process of high-strength layered flame-retardant panels includes the following steps:

[0051] S1, mixing the components of the substrate layer, and extruding them into a plate to obtain the substrate layer;

[0052] S2, mixing the components of the flame retardant reinforcement layer, and extruding them into a plate to obtain a flame retardant reinforcement layer;

[0053] S3. After mixing the components of the flame retardant adhesive layer, apply it between the base material layer and the flame retardant reinforcement layer, and cure it to obtain a layered flame retardant board.

[0054] Example 3

[0055] The high-strength layered flame-retardant board comprises, from bottom to top, a base material layer with a thickness of 500 μm, a flame-retardant adhesive layer with a thickness of 80 μm, and a flame-retardant reinforcement layer with a thickness of 700 μm;

[0056] The substrate layer includes the following components in parts by weight: 100 parts of polyethylene, 45 parts of the first SEBS, 0.5 parts of antioxidant 264, and 1 part of antioxidant 1010;

[0057] The flame retardant adhesive layer comprises the following components in parts by weight: 90 parts of epoxy resin, 7.5 parts of magnesium aluminum hydrotalcite, 7.5 parts of tricresyl phosphate, and 12 parts of triethylenetetramine;

[0058] The flame retardant reinforcement layer includes the following components in parts by weight: 60 parts of polyvinyl chloride, 40 parts of polyethylene, 52 parts of the second SEBS, 10 parts of magnesium aluminum hydrotalcite, 10 parts of tri(xylene) phosphate, and 1 part of antioxidant 1010;

[0059] The styrene content in the first SEBS is 33wt%, and the styrene content in the second SEBS is 30wt%;

[0060] The production process of high-strength layered flame-retardant panels includes the following steps:

[0061] S1, mixing the components of the substrate layer, and extruding them into a plate to obtain the substrate layer;

[0062] S2, mixing the components of the flame retardant reinforcement layer, and extruding them into a plate to obtain a flame retardant reinforcement layer;

[0063] S3. After mixing the components of the flame retardant adhesive layer, apply it between the base material layer and the flame retardant reinforcement layer, and cure it to obtain a layered flame retardant board.

[0064] Example 4

[0065] The only difference between this embodiment and embodiment 3 is that the styrene content in the first SEBS is 30 wt %.

[0066] Example 5

[0067] The only difference between this embodiment and embodiment 3 is that the styrene content in the first SEBS is 18 wt %.

[0068] Example 6

[0069] The difference between this embodiment and embodiment 5 is that the magnesium aluminum hydrotalcite is replaced by ASA resin modified magnesium aluminum hydrotalcite;

[0070] The preparation method of ASA resin modified magnesium aluminum hydrotalcite in the flame retardant adhesive layer comprises the following steps: 10g of ASA resin is melted and mixed with 10g of magnesium aluminum hydrotalcite, and granulated to obtain ASA resin modified magnesium aluminum hydrotalcite with a particle size of 55μm; wherein the ASA resin is composed of ASA resin XC220 and ASA resin XC200 with a mass ratio of 5:1.

[0071] Example 7

[0072] The difference between this embodiment and embodiment 6 is that the magnesium aluminum hydrotalcite is replaced by ASA resin modified magnesium aluminum hydrotalcite;

[0073] The preparation method of ASA resin modified magnesium aluminum hydrotalcite in the flame retardant adhesive layer comprises the following steps: 10g ASA resin is melted and mixed with 30g magnesium aluminum hydrotalcite, and granulated to obtain ASA resin modified magnesium aluminum hydrotalcite with a particle size of 55μm.

[0074] Example 8

[0075] The only difference between this embodiment and embodiment 7 is that the ASA resin is composed of ASA resin XC220 and ASA resin XC200 in a mass ratio of 1:4.

[0076] Example 9

[0077] The only difference between this embodiment and embodiment 7 is that the ASA resin is composed of ASA resin XC220 and ASA resin XC200 in a mass ratio of 2:3.

[0078] Example 10

[0079] The only difference between this embodiment and embodiment 7 is that the ASA resin is composed of ASA resin XC220 and ASA resin XC200 in a mass ratio of 4:1.

[0080] Comparative Example 1

[0081] High-strength layered flame-retardant board, including only a substrate layer with a thickness of 1280 μm;

[0082] The substrate layer includes the following components in parts by weight: 100 parts of polyethylene, 45 parts of SEBS with a styrene content of 33 wt%, 0.5 parts of antioxidant 264, and 1 part of antioxidant 1010;

[0083] The production process of high-strength flame-retardant panels includes the following steps:

[0084] The components of the substrate layer are mixed and extruded into a board to obtain a flame retardant board.

[0085] Comparative Example 2

[0086] High-strength layered flame-retardant board, including only a flame-retardant reinforcement layer with a thickness of 1280 μm;

[0087] The flame retardant reinforcement layer includes the following components in parts by weight: 60 parts of polyvinyl chloride, 40 parts of polyethylene, 52 parts of SEBS with a styrene content of 30wt%, 10 parts of magnesium aluminum hydrotalcite, 10 parts of tri(xylene) phosphate, and 1 part of antioxidant 1010;

[0088] The production process of high-strength flame-retardant panels includes the following steps:

[0089] The components of the flame retardant reinforcement layer are mixed and extruded into a board to obtain a flame retardant board.

[0090] Aging test

[0091] According to the standard GB / T 1040.1-2018 "Determination of tensile properties of plastics Part 1: General", the flame retardant board samples prepared in Examples 1 to 10 and Comparative Examples 1 to 2 were tested for tensile strength, which was recorded as the initial tensile strength;

[0092] Then, each sample was subjected to an ultraviolet accelerated aging test. 2 The tensile strength of the test sample after aging for 1200h at a temperature of 50℃ is recorded as the tensile strength after aging, and the change rate of tensile strength is calculated (the result is rounded to two decimal places), tensile strength change rate = [(initial tensile strength-tensile strength after aging) / initial tensile strength] × 100%. The results are shown in Table 1.

[0093] Table 1 Test results of initial tensile strength and tensile strength change rate

[0094]

[0095] By comparing the data of Examples 1 to 10 and Comparative Examples 1 to 2, it can be seen that compared with Comparative Examples 1 to 2, the layered flame retardant boards prepared in Examples 1 to 10 have higher initial tensile strength and smaller tensile strength change rate, indicating that by using SEBS with different styrene contents in the base material layer and the flame retardant reinforcement layer of the layered flame retardant board, the two layers work together to significantly improve the strength and aging resistance of the flame retardant plastic sheet.

[0096] By comparing the data of Examples 3 to 5, it can be seen that compared with Examples 3 to 4, the layered flame retardant board prepared in Example 5 has a higher initial tensile strength and a smaller tensile strength change rate, indicating that when the styrene content in the first SEBS is less than the styrene content in the second SEBS, the strength and aging resistance of the flame retardant plastic sheet can be further improved.

[0097] By comparing the data of Examples 5 to 10, it can be seen that compared with Example 5, the layered flame retardant boards prepared in Examples 6 to 7 have higher initial tensile strength and smaller tensile strength change rate than those in Example 5, indicating that the use of ASA resin to modify magnesium-aluminum hydrotalcite can further improve the strength and aging resistance of the flame retardant plastic sheet; compared with Examples 7 to 8, the layered flame retardant boards prepared in Examples 9 to 10 have a smaller tensile strength change rate, indicating that when the mass ratio of ASA resin XC220 and ASA resin XC200 is adjusted to 2:3 to 4:1, the aging resistance of the flame retardant plastic sheet is further improved.

[0098] Flame retardancy test

[0099] According to the standard GB / T 2406.2-2009 "Determination of Combustion Behavior of Plastics by Oxygen Index Method", the oxygen index test was performed on the samples prepared in Examples 5 to 10, wherein the sample size was set to III in the standard. b The oxygen index test results are shown in Table 2.

[0100] Table 2 Oxygen index test results

[0101]

[0102] By comparing the data of Examples 5 to 10, it can be seen that compared with Example 5, the oxygen index of the layered flame retardant boards prepared in Examples 6 to 7 is higher, indicating that the modification of magnesium-aluminum hydrotalcite with ASA resin can improve the flame retardancy of the flame retardant plastic sheet; compared with Examples 7 to 8, the oxygen index of the layered flame retardant boards prepared in Examples 9 to 10 is higher, indicating that when the mass ratio of ASA resin XC220 and ASA resin XC200 is adjusted to 2:3 to 4:1, the flame retardancy of the flame retardant plastic sheet can be further improved.

[0103] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A high-strength layered flame-retardant board, characterized in that: From bottom to top, it includes a base material layer, a flame retardant adhesive layer, and a flame retardant reinforcement layer; The substrate layer comprises the following components in parts by weight: 100 parts of polyolefin, 40-50 parts of the first SEBS, and 0.5-2 parts of an antioxidant; The flame retardant adhesive layer comprises the following components in parts by weight: 85-95 parts of epoxy resin, 15-25 parts of flame retardant, and 10-15 parts of curing agent; The flame retardant reinforcement layer comprises the following components in parts by weight: 100 parts of polyolefin, 45-55 parts of the second SEBS, 20-30 parts of flame retardant, and 0.5-2 parts of antioxidant; The styrene content in the first SEBS is 13wt%~33wt%; The styrene content in the second SEBS is 20wt%~41wt%; The styrene content in the first SEBS is less than the styrene content in the second SEBS; The flame retardant is a mixture of magnesium aluminum hydrotalcite and an organic phosphorus flame retardant; The magnesium aluminum hydrotalcite is ASA resin modified magnesium aluminum hydrotalcite.

2. A high-strength layered flame-retardant board according to claim 1, characterized in that: The polyolefin is one or more of polyethylene, polypropylene, and polyvinyl chloride; The organophosphorus flame retardant is one or more of tricresyl phosphate, triphenyl phosphate, and tri(xylene) phosphate; The antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 1024, antioxidant 264, and antioxidant 1076; The curing agent is one or more of triethylenetetramine, tetraethylenepentamine, ethylenediamine and diethylenetriamine.

3. A high-strength layered flame-retardant board according to claim 2, characterized in that: The mass ratio of the magnesium aluminum hydrotalcite to the organic phosphorus flame retardant is 4:1-4.

4. A high-strength layered flame-retardant board according to claim 3, characterized in that: The ASA resin in the ASA resin-modified magnesium-aluminum hydrotalcite is composed of ASA resin XC220 and ASA resin XC200 in a mass ratio of 2:3 to 4:

1.

5. A high-strength layered flame-retardant board according to claim 4, characterized in that: The mass ratio of the ASA resin to the magnesium-aluminum hydrotalcite in the ASA resin-modified magnesium-aluminum hydrotalcite is 1:1-3.

6. A high-strength layered flame-retardant board according to claim 5, characterized in that: The preparation method of the ASA resin modified magnesium aluminum hydrotalcite comprises the following steps: melting the ASA resin, mixing it with the magnesium aluminum hydrotalcite, and granulating to obtain the ASA resin modified magnesium aluminum hydrotalcite with a particle size of 50-60 μm.

7. The high-strength layered flame-retardant board according to claim 1, characterized in that: The thickness of the substrate layer is 500-600 μm; the thickness of the flame retardant adhesive layer is 80-90 μm; and the thickness of the flame retardant reinforcement layer is 600-700 μm.

8. The production process of a high-strength layered flame-retardant board according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1, mixing the components of the substrate layer, and extruding into a plate to obtain a substrate layer; S2, mixing the components of the flame retardant reinforcement layer, and extruding the mixture into a plate to obtain a flame retardant reinforcement layer; S3. After mixing the components of the flame retardant adhesive layer, apply the mixture between the substrate layer and the flame retardant reinforcement layer, and cure the mixture to obtain a layered flame retardant board.

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