High-durability and flame-retardant building template material, preparation method thereof and building template

Abstract

The invention discloses a high-durability and flame-retardant building template material, a preparation method thereof and a building template, and belongs to the technical field of polycarbonate building template materials. The material is prepared from the following components in parts by weight: 100 parts of polycarbonate, 20 to 25 parts of ABS (Acrylonitrile Butadiene Styrene), 8 to 10 parts of a dispersing agent, 12 to 15 parts of epoxidized silicone rubber, 3 to 5 parts of an amino halogen-containing compound, 1 to 2 parts of 4, 4 '-diaminodiphenyl sulfide, 0.5 to 1 part of a flame retardant, 5 to 8 parts of a compatible aid, 0.5 to 0.6 part of an antioxidant, 0.5 to 0.6 part of a light stabilizer and 0.2 to 0.3 part of an anti-dripping agent. By adding the epoxidized silicone rubber, the amino halogen-containing compound and the 4, 4 '-diaminodiphenyl sulfide into the material, the durability, the flame retardance and the performance uniformity can be improved at the same time, the service life of the material is prolonged, and the use safety of the material is improved.

Description

Technical Field

[0001] The present application relates to a highly durable, flame-retardant building template material, a preparation method thereof, and a building template, and belongs to the technical field of polycarbonate building template materials. Background Art

[0002] Polycarbonate is a non-metallic additive material. As an engineering plastic with excellent overall performance, it has a wide range of applications in the construction field. For example, it can be used as temporary roads. After the temporary use ends, it can be recycled and reused. This formwork, which is mainly made of polycarbonate resin, has many advantages, making it a powerful alternative to traditional construction formwork. In terms of performance, polycarbonate construction formwork has outstanding impact resistance and is not easily broken or damaged when subjected to external impact. It can effectively ensure construction safety and reduce the risk of construction delays caused by formwork damage. In addition, in terms of quality, polycarbonate construction formwork has a specific weight of only half that of ordinary glass, which is light and easy to carry and install. It can greatly improve construction efficiency and reduce labor costs.

[0003] However, the polycarbonate building formwork still has the following problems: 1. Poor durability: Polycarbonate is an amorphous plastic with a chaotic and irregular molecular chain arrangement. Under the long-term influence of external factors such as heat, oxygen, and ultraviolet light, it is highly susceptible to molecular chain degradation, oxidation reactions, or minor structural changes, leading to material pulverization. For example, in outdoor construction, formwork is exposed to sunlight and UV radiation for a long time, which can easily break the carbonate bonds in its molecular chains. This, in turn, can cause oxidation reactions, producing quinone compounds, which can cause the formwork to yellow and degrade performance. Furthermore, in some high-humidity environments, even trace amounts of water can accelerate the cleavage of carbonate bonds, causing material aging and shortening the formwork's service life. Furthermore, polycarbonate has poor resistance to environmental stress cracking and high notch sensitivity. In actual use, if the formwork is mechanically damaged and notched, or if internal stress is generated during installation, subsequent use and environmental stresses such as temperature and humidity fluctuations can easily cause cracking at these notches or stress concentrations, further reducing its durability and shortening its service life.

[0004] 2. Poor flame retardancy: Although polycarbonate itself has a certain flame retardant effect and can reach V-2 flame retardancy, it is a self-extinguishing engineering plastic. However, this is far from enough in some construction application scenarios with extremely high fire safety requirements. The current flame retardants for PC mainly include phosphates, silicones and sulfonates, but there are many problems when using them. Phosphate flame retardants need to be added in large quantities and are prone to agglomeration, which reduces the flame retardant uniformity of building formwork materials. Sulfonate flame retardants have high flame retardant efficiency for PC products, but in order to achieve better flame retardant effect, they often need to be compounded with a certain amount of silicone; and the amount of sulfonate flame retardant added is not linearly related to the flame retardant effect. The more you add, the better the flame retardant effect. The amount added needs to be precisely controlled during use. Silicone flame retardants are divided into inorganic silicone and organic silicone. Inorganic silicone flame retardants have a serious impact on the toughness of PC and are less used. Organic silicone flame retardants are mainly polysiloxanes and polysiloxane derivatives, but the amount of silicone flame retardants added is relatively large, and there will be compatibility issues with polycarbonate.

[0005] Patent CN201710469918.4 currently discloses a hydrolysis-resistant PC-ABS alloy. By adding a ternary random copolymer, cyclic carbodiimide MC-CD, and a coupling agent, the material's durability and mechanical properties are improved, but no attention is paid to improving the material's flame retardancy. Patent CN201510735824.8 discloses a novel bromine-antimony composite flame retardant system for flame-retardant PC / ABS materials. By combining bromine-based and antimony-based flame retardants with a toughening agent, the resulting flame-retardant PC / ABS material exhibits excellent flame retardancy and mechanical properties, broadening the material's application range.

[0006] Although the above-mentioned existing technologies have only solved the problems of poor hydrolysis resistance and flame retardancy of polycarbonate, there is currently no technology that can achieve dual improvement in durability and flame retardancy. The applicant has found that if the existing formulas for improving durability and improving flame retardancy are combined, firstly, there will be compatibility issues, resulting in a decrease in the performance uniformity of the building formwork prepared by the materials; secondly, due to the combination of two formulas, it is difficult to achieve both durability and flame retardancy. The building formwork prepared by combining durable and flame retardant formulas often shows a trend of lower durability and flame retardancy than the building formwork prepared by a single formula. Therefore, there is an urgent need for a building formwork material that can simultaneously improve durability, flame retardancy and performance uniformity. Summary of the Invention

[0007] In order to solve the above problems, a highly durable and flame-retardant building formwork material is provided. The addition of epoxidized silicone rubber, amino halogen-containing compounds, and 4,4'-diaminodiphenyl sulfide to the material can simultaneously improve durability, flame retardancy, and performance uniformity, thereby extending the service life and safety of the material.

[0008] According to one aspect of the present application, a highly durable, flame-retardant building formwork material is provided, comprising, by weight: 100 parts of polycarbonate, 20-25 parts of ABS, 8-10 parts of dispersant, 12-15 parts of epoxidized silicone rubber, 3-5 parts of amino halogen-containing compound, 1-2 parts of 4,4'-diaminodiphenyl sulfide, 0.5-1 part of flame retardant, 5-8 parts of compatibilizer, 0.5-0.6 part of antioxidant, 0.5-0.6 part of light stabilizer, 0.2-0.3 part of anti-dripping agent; The structural formula of the amino halogen-containing compound is as follows: , wherein X is selected from one of Br, Cl, I, and F, and n is selected from any integer between 2 and 4.

[0009] The building formwork material of the present application is based on polycarbonate and ABS. The added epoxidized silicone rubber can improve the overall temperature resistance, flame retardancy and corrosion resistance of the material. However, there is a compatibility problem between epoxidized silicone rubber and polycarbonate. Therefore, the present application further adds a compatibility aid to improve the compatibility between the two, thereby obtaining a composite material with good compatibility and more uniform performance.

[0010] In addition, the addition of epoxidized silicone rubber will also cause the material's resistance to environmental stress cracking to deteriorate, and it is easy to produce gaps under external forces during installation or use. Therefore, although its addition makes the temperature resistance acceptable, the resistance to environmental stress cracking decreases, making the durability of the material still poor. Based on this, the amino halogen-containing compound and 4,4'-diaminodiphenyl sulfide are compounded and added in this application. The amino groups contained in these two substances can react with the epoxy groups in the epoxidized silicone rubber, thereby forming branched chain segments in the matrix, which can dissipate stress and impact force, reduce the risk of environmental stress cracking, and thus improve the durability of the material.

[0011] In addition to the above functions, amino halogen compounds also have: 1. Improve flame retardancy: The compound contains more halogen groups, which can reduce the amount of flame retardant used while improving the flame retardant effect of the material; 2. Improve performance uniformity: The ester group it contains can improve compatibility with polycarbonate, thereby improving the performance uniformity of the material; 3. Improve mechanical properties: Contains benzene ring structure to improve the material, which can give the chain segment rigidity, making the molecule less likely to break or degrade at high temperatures, thereby improving wear resistance and fatigue resistance.

[0012] Optionally, the amino halogen-containing compound has the following structural formula: .

[0013] Here, n is 2, which can reduce the alkyl chain length of the amino halogen-containing compound, further increase the rigidity of the substance, and thus improve the durability of the material.

[0014] Optionally, the preparation method of the amino halogen-containing compound is: Add 3,5-dihalobenzoic acid and an alcoholamine compound in a molar ratio of (2.1-2.4):1 to a solvent, react under the action of a catalyst, filter and wash after the reaction to obtain the product.

[0015] The preparation method has readily available raw materials, a controllable reaction process, and a high product yield, and can significantly reduce the preparation cost of building template materials and improve the performance consistency of mass-produced building template materials.

[0016] Optionally, the 3,5-dihalobenzoic acid is selected from at least one of 3,5-dichlorobenzoic acid, 3,5-dibromobenzoic acid, 3,5-diiodobenzoic acid, and 3,5-difluorobenzoic acid; The alcoholamine compound is selected from at least one of diethanolamine, dipropanolamine and dibutanolamine.

[0017] Optionally, the reaction temperature of the 3,5-dihalobenzoic acid and the alcoholamine compound is 70-95° C., and the reaction time is 4-6 hours.

[0018] At the above reaction temperature, the product efficiency can be improved, and the product decomposition can be avoided, thereby improving the overall reaction yield.

[0019] Optionally, the catalyst is selected from concentrated sulfuric acid, and the added amount of the catalyst is 0.5-1 wt % of the total weight of the 3,5-dihalobenzoic acid and the olamine compound.

[0020] Optionally, during the reaction of 3,5-dihalobenzoic acid and the olamine compound, water is removed in time by vacuum distillation or by adding an external water absorbent.

[0021] Since the above reaction is a reversible reaction, water will be removed in the presence of concentrated sulfuric acid as a catalyst. Adding a water absorbent or removing water by reduced pressure distillation can further ensure that the reaction proceeds in the forward direction, thereby increasing the yield of the amino halogen-containing compound.

[0022] Optionally, the weight ratio of the amino halogen-containing compound to 4,4'-diaminodiphenyl sulfide is 2:1.

[0023] The amino groups in amino halogen compounds and the amino groups in 4,4'-diaminodiphenyl sulfide can both react with the epoxy groups in epoxidized silicone rubber. Therefore, the two are in a competitive relationship in terms of reaction. If there are too many amino halogen compounds, the flame retardancy of the material will be improved, but the temperature resistance will decrease. The addition of 4,4'-diaminodiphenyl sulfide can improve the temperature resistance, but if it is added too much, the toughness will deteriorate and the resistance to environmental stress cracking will decrease.

[0024] Optionally, the dispersant is selected from at least one of sodium silicate, sodium metasodium hexaphosphate and triethanolamine; The antioxidant is selected from at least one of antioxidant 168, antioxidant 1010, and antioxidant 1076; The light stabilizer is selected from poly[1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidinyl succinate] or poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-S-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino] (CAS No.: 71878-19-8); The anti-dripping agent is selected from polytetrafluoroethylene or anti-dripping agent SN3310.

[0025] Optionally, the epoxidized silicone rubber is epoxidized phenyl silicone rubber.

[0026] The addition of the epoxidized phenyl silicone rubber of the present application has the following advantages: 1. Does not significantly reduce heat deformation temperature: Since the main chain of epoxidized phenyl silicone rubber contains a silicon-oxygen bond and the side chain contains an epoxy group and a phenyl group, the bond energy of the main chain silicon-oxygen bond is higher than that of the CC bond, and the phenyl group contained in the side chain gives the molecular chain higher rigidity and cohesive energy, which can effectively inhibit the movement of the molecular chain at high temperatures. Therefore, the addition of the epoxidized phenyl silicone rubber will not significantly reduce the heat deformation temperature of the material, so that the material maintains good heat deformation resistance.

[0027] 2. Improve flame retardancy: During the initial combustion phase, the silicon in epoxidized phenyl silicone rubber migrates to the surface of the material, reacting with oxygen in the air to form silicon dioxide. This silicon dioxide, combined with the phenyl oxidation products, forms a ceramic-like char layer containing silicon and carbon. This dense char layer offers excellent thermal and oxygen insulation properties, effectively preventing heat transfer to the substrate, reducing the release of combustible gases and inhibiting the combustion reaction. Furthermore, when epoxidized phenyl silicone rubber is blended with polycarbonate, it alters the thermal decomposition pathway of the polycarbonate, causing it to produce more carbonaceous residue, further enhancing its flame retardancy.

[0028] 3. Improve corrosion resistance: The silicon-oxygen bonds of epoxidized phenyl silicone rubber are chemically stable and resistant to reactions with corrosive media such as acids, bases, oxygen, and moisture. When blended with polycarbonate, it forms a continuous, dense multi-layer silicone rubber film on and within the material. This film, with its low surface energy and hydrophobicity, effectively prevents moisture, corrosive gases, and chemicals from penetrating the polycarbonate, acting as a physical barrier. Furthermore, the phenyl groups in the side chains exhibit excellent chemical inertness, resisting attack by most chemicals and synergistically enhancing the corrosion resistance of polycarbonate.

[0029] Optionally, the epoxidized phenyl silicone rubber has a vinyl content of 20-25% and an epoxy content of 15-20%.

[0030] The above-mentioned vinyl content and epoxy content can optimize the durability, flame retardancy and mechanical properties of the composite material. If the vinyl content is too high, it will have little effect on the flame retardancy, but will cause a decrease in temperature resistance; if the phenyl content is too high, it will cause the composite material to become more brittle and reduce the mechanical properties of the material at high temperatures.

[0031] Optionally, the preparation method of the epoxidized silicone rubber refers to patent CN110358091B.

[0032] Optionally, the compatibilizing agent is obtained by copolymerizing acrylamide, styrene and propenyltrichlorosilane in a weight ratio of (3-5): (3-4): 1.

[0033] The compatibilizer disclosed herein is obtained by copolymerizing the three aforementioned substances. This compatibilizer effectively improves the compatibility of polycarbonate and epoxidized silicone rubber, resulting in a composite material with superior overall performance. Furthermore, the compatibilizer contains amide groups that react with the epoxidized silicone rubber to form a cross-linked network. Under high-temperature conditions, this network restricts the movement of polycarbonate molecular chains, increasing the polycarbonate's glass transition temperature and heat distortion temperature, enabling it to maintain good mechanical properties and dimensional stability at higher temperatures. It also improves the overall density of the material, further enhancing flame retardancy and imparting corrosion resistance.

[0034] Optionally, the propenyltrichlorosilane is at least one selected from allyldimethylsilane, propenyltrichlorosilane, allyl(chloromethyl)dimethylsilane, and trimethylallyloxysilane.

[0035] The raw material of the acryltrichlorosilane is easily available, which is conducive to the industrial production of the compatibilizing agent.

[0036] Preferably, the propenyltrichlorosilane is selected from propenyltrichlorosilane or allyl(chloromethyl)dimethylsilane, both of which contain halogen atoms, which can further improve the flame retardancy of the composite material and improve the compatibility with the flame retardant, so that the flame retardant can be uniformly dispersed in the composite material.

[0037] Optionally, the preparation method of the compatibility aid is: S1: 1 / 3 acrylamide and 1 / 2 styrene are added to a solvent, followed by the addition of an initiator and sodium dodecylbenzenesulfonate, and reacted at 60-80°C for 1-3h to obtain a prepolymer; S2: the remaining acrylamide, styrene and propenyltrichlorosilane are added to the prepolymer, and the reaction is continued at the temperature for 3-5h, and then the temperature is raised to 95°C for 0.5-1h, and then the product is discharged, filtered, washed and dried to obtain the compatibility aid.

[0038] The propenyltrichlorosilane has low radical activity under the action of the free radical initiator, so the copolymerization of this substance is limited and cannot effectively form a high molecular weight polymer. The pre-polymerization in step S1 in the present preparation method can make the pre-polymer initiate the reaction of propenyltrichlorosilane, improve the reaction efficiency of the copolymer, and obtain an ideal compatibility aid.

[0039] The initiator is selected from benzoyl peroxide and / or azobisisobutyronitrile, and the amount of the initiator added is 1-3% of the total weight of acrylamide, styrene and propenyltrichlorosilane.

[0040] The amount of initiator added in the present application is larger than that in the conventional copolymerization of styrene and acrylamide, because the reaction activity of propenyltrichlorosilane in polymerization is low, so more initiator is needed to initiate the reaction to improve the reaction efficiency.

[0041] Preferably, the initiator is selected from benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1, because the reaction activity of propenyltrichlorosilane is low, the present application can improve the reaction efficiency of propenyltrichlorosilane and reduce the reaction time by co-initiation of the two initiators.

[0042] The amount of sodium dodecylbenzenesulfonate added is 1-3% of the total weight of acrylamide, styrene and propenyltrichlorosilane.

[0043] Optionally, the flame retardant is selected from nitrogen-containing flame retardants or phosphorus-containing flame retardants.

[0044] Preferably, the flame retardant is selected from melamine or [(6-oxo-6H-dibenzo[C,E][1,2]oxaphosphorin-6-yl)methyl] butanedioic acid.

[0045] According to another aspect of the present application, there is provided a method for preparing the highly durable, flame-retardant building formwork material described in any one of the above items, comprising the following steps: (1) mixing the polycarbonate, ABS, epoxidized silicone rubber, amino halogen-containing compound, 4,4'-diaminodiphenyl sulfide, dispersant, compatibilizer, antioxidant, light stabilizer, flame retardant, and anti-dripping agent to obtain a mixture; (2) adding the mixed material into an extruder, extruding and granulating to obtain the highly durable and flame-retardant building formwork material.

[0046] Optionally, in step (2), the extrusion temperature of the extruder is 250-290° C., and the rotation speed is 200-500 rpm.

[0047] According to another aspect of the present application, a highly durable, flame-retardant building formwork is provided, which is prepared by injection molding or 3D printing using any of the highly durable, flame-retardant building formwork materials described above.

[0048] The beneficial effects of this application include but are not limited to: 1. According to the highly durable, flame-retardant building formwork material of the present application, the amino group contained in the amino halogen-containing compound, 4,4'-diaminodiphenyl sulfide, can react with the epoxidized silicone rubber to form a chemical bond, thereby forming a rigid, stable structure in the polycarbonate substrate to improve the durability of the material.

[0049] 2. In the highly durable, flame-retardant building formwork material of this application, the amino halogen-containing compound contains halogen elements at both ends, which can impart good flame retardancy to the polycarbonate matrix. The ester group contained in the middle can improve compatibility with polycarbonate, thereby enabling the compound to be evenly dispersed in the polycarbonate matrix and improving the overall performance uniformity of the material.

[0050] 3. In the highly durable, flame-retardant building formwork material of this application, both the amino halogen-containing compound and 4,4'-diaminodiphenyl sulfide can form a chemical bond with the epoxidized silicone rubber, and the combination of the two in a specific ratio can achieve optimal durability and flame retardancy.

[0051] 4. The method for preparing the highly durable, flame-retardant building formwork material of the present application has a simple preparation process, is easy to operate, does not require additional post-processing steps, and is conducive to industrial promotion and use.

[0052] 5. The highly durable and flame-retardant building formwork according to the present application is prepared by injection molding or 3D printing of granulated materials. The process is simple and meets the requirements of non-metallic additive 3D printing, which can improve the processing efficiency and construction efficiency of the building formwork. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings: Figure 1 This is a reaction process diagram of the amino halogen-containing compound involved in Examples 1-3 of the present application. DETAILED DESCRIPTION

[0054] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0055] Unless otherwise specified, the raw materials used in the examples and comparative examples of this application were purchased from commercial sources. The epoxidized silicone rubber used in the following examples and comparative examples was obtained using the method described in Example 1 of CN110358091B. The melt index (MI) of the polycarbonate at 300°C and a load of 1.2 kg was 10 g / 10 min. The light stabilizer used was poly[1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidinylsuccinate], the flame retardant was melamine, the antioxidant was antioxidant 168, and the anti-drip agent was anti-drip agent SN3310.

[0056] Unless otherwise specified, the methods used in the examples and comparative examples of the present application are conventional methods in the prior art. In the preparation of the compatibilizer and amino halogen-containing compound in the following examples and comparative examples, the selected solvent is not specifically limited, as long as it can ensure that the raw materials have good solubility and are convenient for the discharge of subsequent products. The temperature of the extruder in the following examples and comparative examples is 250-290°C, which specifically means that the extruder is divided into five temperature sections, the temperature of the conveying section is 250-260°C, the temperature of the melting section is 255-265°C, the temperature of the mixing section is 265-270°C, the temperature of the exhaust section is 265-275°C, the temperature of the homogenizing section is 275-280°C, and the temperature of the extrusion die head is 280-290°C.

[0057] Example 1 This embodiment relates to a highly durable, flame-retardant building formwork material, which comprises, by weight: 100 parts of polycarbonate, 20 parts of ABS, 8 parts of sodium silicate, 12 parts of epoxidized silicone rubber, 3 parts of amino halogen-containing compound, 2 parts of 4,4'-diaminodiphenyl sulfide, 0.5 parts of flame retardant, 5 parts of compatibilizer, 0.5 parts of antioxidant, 0.5 parts of light stabilizer, and 0.2 parts of anti-dripping agent.

[0058] The preparation method of the material comprises the following steps: (1) mixing the polycarbonate, ABS, epoxidized silicone rubber, amino halogen-containing compound, 4,4'-diaminodiphenyl sulfide, sodium silicate, compatibilizer, antioxidant, light stabilizer, flame retardant, and anti-dripping agent to obtain a mixture; (2) Adding the mixed material into an extruder, extruding and granulating at 250-290° C. and 200 rpm to obtain the highly durable and flame-retardant building formwork material.

[0059] The compatibilizer is obtained by copolymerizing acrylamide, styrene and allyldimethylsilane in a weight ratio of 3:3:1. The preparation method of the compatibilizer is as follows: S1: 1 / 3 acrylamide and 1 / 2 styrene are added to a solvent, followed by the addition of an initiator (benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1) at a concentration of 3% based on the total weight of acrylamide, styrene, and allyldimethylsilane, and sodium dodecylbenzenesulfonate at a concentration of 3% based on the total weight of acrylamide, styrene, and allyldimethylsilane, and the reaction is carried out at 60°C for 3 hours to obtain a prepolymer; S2: Add the remaining acrylamide, styrene and allyldimethylsilane to the prepolymer, continue to react at the same temperature for 5 hours, then raise the temperature to 95° C. and react for 0.5 hours. Discharge, filter, wash and dry the material to obtain the compatibilizer.

[0060] The preparation method of the amino halogen compound is as follows: 3,5-dibromobenzoic acid and dibutanolamine with a molar ratio of 2.1:1 are added to a solvent, followed by adding concentrated sulfuric acid accounting for 0.5wt% of the total weight of 3,5-dibromobenzoic acid and dibutanolamine, and adding molecular sieves to absorb water, reacting at 95°C for 4h, filtering and washing after the reaction is completed, and obtaining the obtained compound. Figure 1 , X is Br, n is 4, the specific reaction equation is as follows: .

[0061] Example 2 This embodiment relates to a highly durable, flame-retardant building formwork material, which comprises, by weight: 100 parts of polycarbonate, 25 parts of ABS, 10 parts of sodium hexaphosphate, 15 parts of epoxidized silicone rubber, 5 parts of amino halogen-containing compound, 1 part of 4,4'-diaminodiphenyl sulfide, 1 part of flame retardant, 8 parts of compatibilizer, 0.6 part of antioxidant, 0.6 part of light stabilizer, and 0.3 part of anti-dripping agent.

[0062] The preparation method of the material comprises the following steps: (1) mixing the polycarbonate, ABS, epoxidized silicone rubber, amino halogen-containing compound, 4,4'-diaminodiphenyl sulfide, sodium hexaphosphate, compatibilizer, antioxidant, light stabilizer, flame retardant, and anti-dripping agent to obtain a mixture; (2) Adding the mixed material into an extruder, extruding and granulating at 250-290° C. and 500 rpm to obtain the highly durable and flame-retardant building formwork material.

[0063] The compatibilizer is obtained by copolymerizing acrylamide, styrene and allyl (chloromethyl) disilane in a weight ratio of 5:3:1. The preparation method of the compatibilizer is as follows: S1: 1 / 3 acrylamide and 1 / 2 styrene are added to a solvent, followed by the addition of an initiator (benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1) based on the total weight of acrylamide, styrene, and allyl(chloromethyl)dimethylsilane, and sodium dodecylbenzenesulfonate in a weight ratio of 1% based on the total weight of acrylamide, styrene, and allyl(chloromethyl)dimethylsilane, and the reaction is carried out at 80°C for 1 hour to obtain a prepolymer; S2: Add the remaining acrylamide, styrene and allyl (chloromethyl) disilane to the prepolymer, continue to react at the same temperature for 3 hours, then raise the temperature to 95° C. and react for 1 hour. Discharge, filter, wash and dry to obtain the compatibilizer.

[0064] The preparation method of the amino halogen compound is as follows: 3,5-difluorobenzoic acid and dipropanolamine with a molar ratio of 2.4:1 are added to a solvent, followed by adding concentrated sulfuric acid accounting for 1wt% of the total weight of 3,5-difluorobenzoic acid and dipropanolamine, and adding molecular sieves to absorb water, reacting at 70°C for 6h, filtering and washing after the reaction is completed, and obtaining the obtained compound. Figure 1 , X is F, n is 3, and the specific reaction equation is as follows: .

[0065] Example 3 This embodiment relates to a highly durable, flame-retardant building formwork material, which comprises, by weight: 100 parts of polycarbonate, 22 parts of ABS, 8 parts of dispersant, 13 parts of epoxidized silicone rubber, 4 parts of amino halogen-containing compound, 2 parts of 4,4'-diaminodiphenyl sulfide, 0.8 parts of flame retardant, 6 parts of compatibilizer, 0.6 parts of antioxidant, 0.6 parts of light stabilizer, and 0.3 parts of anti-dripping agent.

[0066] The preparation method of the material comprises the following steps: (1) mixing the polycarbonate, ABS, epoxidized silicone rubber, amino halogen-containing compound, 4,4'-diaminodiphenyl sulfide, dispersant, compatibilizer, antioxidant, light stabilizer, flame retardant, and anti-dripping agent to obtain a mixture; (2) Adding the mixed material into an extruder, extruding and granulating at 250-290° C. and 300 rpm to obtain the highly durable and flame-retardant building formwork material.

[0067] The compatibilizer is obtained by copolymerizing acrylamide, styrene and propenyltrichlorosilane in a weight ratio of 5:4:1. The preparation method of the compatibilizer is as follows: S1: 1 / 3 acrylamide and 1 / 2 styrene are added to a solvent, followed by the addition of an initiator (benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1) at 2.5% of the total weight of acrylamide, styrene, and allyltrichlorosilane, and sodium dodecylbenzenesulfonate at 2% of the total weight of acrylamide, styrene, and allyltrichlorosilane, and the reaction is carried out at 70°C for 2.5 hours to obtain a prepolymer; S2: adding the remaining acrylamide, styrene and propenyltrichlorosilane to the prepolymer, continuing the reaction at the same temperature for 4 hours, then raising the temperature to 95° C. to react for 1 hour, discharging, filtering, washing and drying to obtain the compatibilizing agent.

[0068] The preparation method of the amino halogen compound is as follows: 3,5-dichlorobenzoic acid and diethanolamine compounds with a molar ratio of 2.2:1 are added to a solvent, followed by adding concentrated sulfuric acid accounting for 1wt% of the total weight of 3,5-dichlorobenzoic acid and diethanolamine, and adding molecular sieves to absorb water, reacting at 90°C for 5h, filtering and washing after the reaction is completed, and obtaining the obtained compound. Figure 1 , X is Cl, n is 2, the specific reaction equation is as follows: .

[0069] Example 4 The difference between this embodiment and embodiment 3 is that the amino halogen-containing compound is 5 parts and the 4,4'-diaminodiphenyl sulfide is 1 part.

[0070] Example 5 The difference between this embodiment and embodiment 3 is that the amino halogen-containing compound is 3 parts and the 4,4'-diaminodiphenyl sulfide is 2 parts.

[0071] Example 6 The difference between this embodiment and embodiment 3 is that dibutanolamine is used instead of diethanolamine in the preparation of the amino halogen-containing compound.

[0072] Example 7 The difference between this embodiment and embodiment 3 is that the compatibilizer is obtained by copolymerizing acrylamide, styrene and propenyltrichlorosilane in a weight ratio of 1:4:1.

[0073] Example 8 The difference between this embodiment and embodiment 3 is that the compatibilizing agent is obtained by copolymerizing acrylamide and styrene in a weight ratio of 5:4.

[0074] Example 9 The difference between this embodiment and embodiment 3 is that allyldimethylsilane is used instead of propenyltrichlorosilane.

[0075] Comparative Example 1 The difference between the present comparative example and Example 3 is that the un-epoxidized phenyl silicone rubber is prepared by the preparation method of paragraphs

[0041] -

[0045] of CN110358091B.

[0076] Comparative Example 2 The difference between the present comparative example and Example 3 is that the 3,5-dichloroaniline is used instead of the amino halogen-containing compound.

[0077] Comparative Example 3 The difference between the present comparative example and Example 3 is that the 4,4'-diamino diphenyl sulfide is not added.

[0078] Test Example 1 The high-durability and flame-retardant building template material of the above examples and comparative examples is prepared into a test strip by an injection molding machine, and the test strip is tested as follows, and the test results are shown in Table 1.

[0079] 1. Tensile strength: tested according to GB / T 1040; 2. Impact strength: tested according to ISO 179-1; 3. Heat distortion temperature: tested according to GB 1634; 4. Oxygen index: tested according to GB / T 2406.2-2009.

[0080] Table 1

[0081] According to the test data of Examples 1-3, the high-durability and flame-retardant building template material prepared by the present application has good tensile strength and impact strength, and the heat distortion temperature is above 113℃ and the oxygen index is above 30.4%, which can improve the durability and flame retardancy of the material.

[0082] Test Example 2 The high-durability and flame-retardant building template material of the above examples and comparative examples is prepared into a test strip by an injection molding machine, and the test strip is tested as follows, and the test results are shown in Table 1.

[0083] Table 2

[0084] According to the above test data, after the sample made of the highly durable and flame-retardant building formwork material of the present application is subjected to ultra-low temperature and high temperature treatment, the combination of epoxidized silicone rubber, amino halogen-containing compounds, and 4,4'-diaminodiphenyl sulfide can reduce the tensile strength and oxygen index decrease rate, thereby improving the durability and flame retardancy of the material, making it less likely to powder during use, and extending the service life and safety of the material.

[0085] The high-durability, flame-retardant building formwork materials prepared in the above embodiments and comparative examples are prepared by injection molding or 3D printing to obtain a high-durability, flame-retardant building formwork, which can be used as a temporary road, thereby increasing the number of times the temporary road can be recycled.

[0086] The foregoing is merely an embodiment of the present application, and the scope of protection of the present application is not limited by these specific embodiments, but is determined by the claims of the present application. For those skilled in the art, the present application may have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc. made within the technical ideas and principles of the present application should be included in the scope of protection of the present application.

Claims

1. A highly durable, flame-retardant building formwork material, characterized in that: Calculated by weight, including: 100 parts of polycarbonate, 20-25 parts of ABS, 8-10 parts of dispersant, 12-15 parts of epoxidized silicone rubber, 3-5 parts of amino halogen-containing compound, 1-2 parts of 4,4'-diaminodiphenyl sulfide, 0.5-1 part of flame retardant, 5-8 parts of compatibilizer, 0.5-0.6 part of antioxidant, 0.5-0.6 part of light stabilizer, 0.2-0.3 part of anti-dripping agent; The structural formula of the amino halogen-containing compound is as follows: , wherein X is selected from one of Br, Cl, I, and F, and n is selected from any integer between 2 and 4.

2. The highly durable, flame-retardant building formwork material according to claim 1, characterized in that: The structural formula of the amino halogen-containing compound is as follows: 。 3. The highly durable, flame-retardant building formwork material according to claim 1, characterized in that: The preparation method of the amino halogen-containing compound is: Add 3,5-dihalobenzoic acid and an alcoholamine compound in a molar ratio of (2.1-2.4):1 to a solvent, react under the action of a catalyst, filter and wash after the reaction to obtain the product.

4. The highly durable, flame-retardant building formwork material according to claim 3, characterized in that: The 3,5-dihalobenzoic acid is selected from at least one of 3,5-dichlorobenzoic acid, 3,5-dibromobenzoic acid, 3,5-diiodobenzoic acid, and 3,5-difluorobenzoic acid; The alcoholamine compound is selected from at least one of diethanolamine, dipropanolamine and dibutanolamine.

5. The highly durable, flame-retardant building formwork material according to claim 3, characterized in that: The reaction temperature of 3,5-dihalobenzoic acid and the alcoholamine compound is 70-95° C., and the reaction time is 4-6 hours.

6. The highly durable, flame-retardant building formwork material according to claim 1, characterized in that: The weight ratio of the amino halogen-containing compound to 4,4'-diaminodiphenyl sulfide is 2:

1.

7. The highly durable, flame-retardant building formwork material according to claim 1, characterized in that: The dispersant is selected from at least one of sodium silicate, sodium metasodium hexaphosphate and triethanolamine; The antioxidant is selected from at least one of antioxidant 168, antioxidant 1010, and antioxidant 1076; The light stabilizer is selected from poly[1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidinyl succinate] or poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-S-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino]; The anti-dripping agent is selected from polytetrafluoroethylene or anti-dripping agent SN3310.

8. The method for preparing a highly durable, flame-retardant building formwork material according to any one of claims 1 to 7, characterized in that: The steps include: (1) mixing the polycarbonate, ABS, epoxidized silicone rubber, amino halogen-containing compound, 4,4'-diaminodiphenyl sulfide, dispersant, compatibilizer, antioxidant, light stabilizer, flame retardant, and anti-dripping agent to obtain a mixture; (2) adding the mixed material into an extruder, extruding and granulating to obtain the highly durable and flame-retardant building formwork material.

9. The preparation method according to claim 8, characterized in that In step (2), the extrusion temperature of the extruder is 250-290° C., and the rotation speed is 200-500 rpm.

10. A highly durable, flame-retardant building formwork, characterized in that: The highly durable and flame-retardant building template material is prepared by injection molding or 3D printing technology using the highly durable and flame-retardant building template material described in any one of claims 1 to 7.

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