Highly durable, fire-retardant building formwork material, method of making and building formwork

Abstract

The application discloses a kind of high durability, flame-retardant building template material and its preparation method and building template, belong to polycarbonate building template material technical field.The material is by weight fraction, including: polycarbonate 100 parts, ABS 20-25 parts, dispersing agent 8-10 parts, epoxidized silicone rubber 12-15 parts, amino halogen-containing compound 3-5 parts, 4, 4 '-diamino diphenyl sulfide 1-2 parts, flame retardant 0.5-1 part, compatible aid 5-8 parts, antioxidant 0.5-0.6 parts, light stabilizer 0.5-0.6 parts, anti-dripping agent 0.2-0.3 parts.The addition of epoxidized silicone rubber, amino halogen-containing compound, 4, 4 '-diamino diphenyl sulfide added in the material can improve durability, flame retardancy and performance uniformity simultaneously, prolong the service life and use safety of material.

Description

Technical Field

[0001] This application relates to a high-durability, flame-retardant building formwork material, its preparation method, and the building formwork itself, belonging to the technical field of polycarbonate building formwork materials. Background Technology

[0002] Polycarbonate is a non-metallic additive material. As an engineering plastic with excellent comprehensive performance, it has wide applications in the construction industry. For example, it can be used as temporary roads, and after temporary use, it can be recycled and reused. This type of formwork, with polycarbonate resin as the main raw material, has many advantages, making it a powerful alternative to traditional construction formwork. In terms of performance, polycarbonate construction formwork has outstanding impact resistance. It is not easily broken or damaged when subjected to external impacts, effectively ensuring construction safety and reducing the risk of construction delays due to formwork damage. In addition, in terms of weight, polycarbonate construction formwork is only half the weight of ordinary glass, making it lightweight, easy to handle and install, which can greatly improve construction efficiency and reduce labor costs.

[0003] However, polycarbonate building formwork still has the following problems:

[0004] 1. Poor Durability: Polycarbonate is a non-crystalline plastic with disordered and irregular molecular chains. 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 microstructural changes, leading to material pulverization. For example, in outdoor construction, formwork exposed to sunlight and ultraviolet radiation for extended periods is prone to the breakage of carbonate bonds in its molecular chains, resulting in oxidation reactions that produce quinone compounds, causing the formwork to yellow and its performance to decline. Furthermore, in high-humidity environments, even trace amounts of water can accelerate the breakage of carbonate bonds, causing material aging and affecting the lifespan of the formwork. Simultaneously, polycarbonate has poor resistance to environmental stress cracking and high notch sensitivity. In actual use, if the formwork suffers mechanical damage resulting in notches, or internal stress is generated during installation, subsequent exposure to environmental stresses such as temperature and humidity changes can easily cause cracking from the notches or stress concentration points, further reducing its durability and shortening its service life.

[0005] 2. Poor Flame Retardancy: Although polycarbonate itself has a certain flame retardant effect, achieving a V-2 flame retardant rating and being a self-extinguishing engineering plastic, this is far from sufficient in some building applications with extremely high fire safety requirements. Currently, flame retardants for PC mainly include phosphate esters, silicone esters, and sulfonates, but their use presents several problems. Phosphate ester flame retardants require large addition amounts and are prone to agglomeration, reducing the uniformity of flame retardancy in building formwork materials. Sulfonate flame retardants have high flame retardant efficiency for PC products, but to achieve better flame retardant effects, they often need to be compounded with siloxanes; furthermore, the amount of sulfonate flame retardant added is not linearly related to the flame retardant effect—more does not necessarily mean better flame retardancy—requiring precise control of the addition amount. Silicon-based flame retardants are divided into inorganic silicon-based and organic silicon-based. Inorganic silicon-based flame retardants have a serious impact on the toughness of PC and are used less frequently. Organic silicon-based flame retardants are mainly polysiloxanes and polysiloxane derivatives, but the amount of siloxane flame retardants added is relatively large, and there are compatibility issues with polycarbonate.

[0006] Currently, patent CN201710469918.4 discloses a hydrolysis-resistant PC-ABS alloy. By adding a ternary random copolymer, cyclic carbodiimide MC-CD, and a coupling agent, the durability and mechanical properties of the material are improved; however, 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. Through the compounding of bromine-based flame retardants and antimony-based flame retardants with toughening agents, a flame-retardant PC / ABS material with good flame retardant and mechanical properties has been developed, broadening the material's application range.

[0007] While the aforementioned existing technologies have addressed the issues of poor hydrolysis resistance and flame retardancy of polycarbonate, no technology currently achieves a dual improvement in both durability and flame retardancy. The applicant has found that combining existing formulations for improving durability and flame retardancy presents two problems: first, compatibility issues arise, leading to a decrease in the uniformity of performance in the prepared building formwork; second, because it is a combination of two formulations, it is difficult to achieve a balance between durability and flame retardancy. Building formwork prepared with the combination of durability and flame retardancy formulations often exhibits a trend of decreased durability and flame retardancy compared to formwork prepared with a single formulation. 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

[0008] To address the aforementioned issues, a highly durable and flame-retardant building formwork material is provided. The addition of epoxy silicone rubber, amino halogenated compounds, and 4,4'-diaminodiphenyl sulfide to this material can simultaneously improve durability, flame retardancy, and performance uniformity, thereby extending the material's service life and safety.

[0009] According to one aspect of this application, a highly durable, flame-retardant building formwork material is provided, comprising, by weight parts:

[0010] 100 parts polycarbonate, 20-25 parts ABS, 8-10 parts dispersant, 12-15 parts epoxidized silicone rubber, 3-5 parts amino halogenated compound, 1-2 parts 4,4'-diaminodiphenyl sulfide, 0.5-1 part flame retardant, 5-8 parts compatibilizer, 0.5-0.6 parts antioxidant, 0.5-0.6 parts light stabilizer, and 0.2-0.3 parts anti-dripping agent;

[0011] The structural formula of the amino-containing halogenated compound is as follows:

[0012] , where X is selected from Br, Cl, I, F, and n is selected from any integer from 2 to 4.

[0013] The building formwork material of this application uses polycarbonate and ABS as the matrix. The addition of 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, this application adds compatibility additives to improve the compatibility between the two, thereby obtaining a composite material with good compatibility and more uniform performance.

[0014] Furthermore, the addition of epoxy silicone rubber can lead to a decrease in the material's resistance to environmental stress cracking, making it prone to chipping under external forces during installation or use. Therefore, although its addition improves temperature resistance, the decrease in resistance to environmental stress cracking results in poor material durability. Based on this, the present application incorporates an amino halogenated compound and 4,4'-diaminodiphenyl sulfide. The amino groups in these two substances can react with the epoxy groups in the epoxy silicone rubber to form branched segments in the matrix, which can dissipate stress and impact, reduce the risk of environmental stress cracking, and thus improve the durability of the material.

[0015] In addition to the above-mentioned effects, amino-containing halogenated compounds also possess the following properties:

[0016] 1. Improved flame retardancy: This compound contains a large number of halogen groups, which can reduce the amount of flame retardant used while improving the flame retardant effect of the material;

[0017] 2. Improved performance uniformity: The ester groups it contains can improve its compatibility with polycarbonate, thereby improving the performance uniformity of the material;

[0018] 3. Improved mechanical properties: The benzene ring structure of the material can impart rigidity to the chain segments, making the molecules less prone to chain breakage or degradation at high temperatures, thereby improving wear resistance and fatigue resistance.

[0019] Optionally, the structural formula of the amino-containing halogenated compound is as follows:

[0020] .

[0021] The value of n is 2 here, which can reduce the alkyl chain length of the amino halogenated compound, further increasing the rigidity of the substance and thus improving the durability of the material.

[0022] Optionally, the preparation method of the amino-containing halogenated compound is as follows:

[0023] 3,5-Dihalobenzoic acid and an alcoholic amine compound in a molar ratio of (2.1-2.4):1 are added to a solvent and reacted under the action of a catalyst. After the reaction is completed, the mixture is filtered and washed to obtain the final product.

[0024] The preparation method uses readily available raw materials, has a controllable reaction process, and produces high product yields. It can significantly reduce the preparation cost of building formwork materials and improve the performance consistency of mass-produced building formwork materials.

[0025] 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;

[0026] The alkanolamine compound is selected from at least one of diethanolamine, dipropanolamine, and dibutanolamine.

[0027] Optionally, the reaction temperature of 3,5-dihalobenzoic acid and the alcohol amine compound is 70-95℃, and the reaction time is 4-6h.

[0028] At the above reaction temperature, product efficiency can be improved while product decomposition can be avoided, thereby increasing the overall reaction yield.

[0029] Optionally, the catalyst is selected from concentrated sulfuric acid, and the amount of catalyst added is 0.5-1 wt% of the total weight of 3,5-dihalobenzoic acid and the alcohol amine compound.

[0030] Optionally, during the reaction of 3,5-dihalobenzoic acid and alkanolamine compounds, water is removed promptly by vacuum distillation or by adding an external dehydrating agent.

[0031] Since the above reaction is reversible, water will be removed in the presence of concentrated sulfuric acid as a catalyst. Adding a dehydrating agent or vacuum distillation can further ensure that the reaction proceeds in the forward direction, thereby increasing the yield of amino halogenated compounds.

[0032] Optionally, the weight ratio of the amino-containing halogenated compound to 4,4'-diaminodiphenyl sulfide is 2:1.

[0033] Both the amino groups in amino-containing halogen compounds and the amino groups in 4,4'-diaminodiphenyl sulfide can react with the epoxy groups in epoxide silicone rubber. Therefore, they are in a competitive relationship in terms of reaction. If there is too much amino-containing halogen compound, it will improve the flame retardancy of the material, but the temperature resistance will decrease. The addition of 4,4'-diaminodiphenyl sulfide can improve the temperature resistance, but if too much is added, it will lead to poor toughness and decreased resistance to environmental stress cracking.

[0034] Optionally, the dispersant is selected from at least one of sodium silicate, sodium hexaphosphate, and triethanolamine;

[0035] The antioxidant is selected from at least one of antioxidant 168, antioxidant 1010, and antioxidant 1076;

[0036] The light stabilizer is selected from poly[1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine 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-hexamethylenediyl-[(2,2,6,6-tetramethyl-4-piperidinyl)imino] (CAS No.: 71878-19-8);

[0037] The anti-dripping agent is selected from polytetrafluoroethylene or anti-dripping agent SN3310.

[0038] Optionally, the epoxidized silicone rubber is epoxidized phenyl silicone rubber.

[0039] The addition of epoxidized phenyl silicone rubber in this application has the following advantages:

[0040] 1. Does not significantly reduce heat distortion temperature:

[0041] Because the main chain of epoxy phenyl silicone rubber contains silicon-oxygen bonds and the side chains contain epoxy groups and phenyl groups, the bond energy of its main chain silicon-oxygen bonds is higher than that of C-C bonds, and the phenyl groups contained in its side chains endow the molecular chains with high rigidity and cohesive energy, which can effectively inhibit the movement of molecular chains at high temperatures. Therefore, the addition of this epoxy phenyl silicone rubber will not significantly reduce the heat distortion temperature of the material, thus maintaining good heat distortion resistance of the material.

[0042] 2. Improve flame retardancy:

[0043] In the initial stages of combustion, the silicon element in epoxidized phenyl silicone rubber migrates to the material surface, reacts with oxygen in the air to generate silicon dioxide, and together with the phenyl oxidation products, forms a silicon-carbon ceramic-like char layer. This char layer has a dense structure and excellent heat insulation and oxygen barrier properties, effectively preventing heat transfer to the matrix, reducing the release of flammable gases, and inhibiting the combustion reaction. Furthermore, blending epoxidized phenyl silicone rubber with polycarbonate alters the thermal decomposition pathway of polycarbonate, causing it to produce more char residue during thermal decomposition, further enhancing the flame-retardant effect.

[0044] 3. Improve corrosion resistance:

[0045] Epoxidized phenyl silicone rubber exhibits strong chemical stability due to its silicon-oxygen bonds, making it resistant to reactions with corrosive media such as acids, alkalis, oxygen, and moisture. When blended with polycarbonate, it forms a multi-layered, continuous, and dense silicone rubber film on the surface and within the material. This film possesses low surface energy and hydrophobicity, effectively preventing moisture, corrosive gases, and chemical reagents from penetrating into the polycarbonate, thus acting as a physical barrier. Furthermore, the phenyl groups in the side chains possess excellent chemical inertness, resisting the erosion of most chemical substances and synergistically enhancing the corrosion resistance of polycarbonate.

[0046] Optionally, the vinyl content of the epoxidized phenyl silicone rubber is 20-25%, and the epoxy content is 15-20%.

[0047] The above-mentioned vinyl and epoxy contents enable the composite material to achieve optimal durability, flame retardancy, and mechanical properties. If the vinyl content is too high, it will not have a significant impact on the flame retardancy, but it will cause a decrease in temperature resistance. If the phenyl content is too high, it will lead to an increase in the brittleness of the composite material and reduce the mechanical properties of the material at high temperatures.

[0048] Optionally, the preparation method of the epoxy silicone rubber is referenced in patent CN110358091B.

[0049] Optionally, the compatibility aid is obtained by copolymerizing acrylamide, styrene and propylene trichlorosilane in a weight ratio of (3-5):(3-4):1.

[0050] The compatibility additive of this application is obtained by copolymerizing the above three substances. This compatibility additive can effectively improve the compatibility between polycarbonate and epoxidized silicone rubber, thereby obtaining a composite material with better overall performance. In addition, the compatibility additive contains amide groups, which can react with epoxidized silicone rubber to form a cross-linked network. Under high temperature conditions, this network structure can restrict the movement of polycarbonate molecular chains, increase the glass transition temperature and heat distortion temperature of polycarbonate, and enable polycarbonate to maintain good mechanical properties and dimensional stability at higher temperatures; at the same time, it can improve the overall density of the material, further enhance flame retardancy, and impart corrosion resistance to the material.

[0051] Optionally, the propenyltrichlorosilane is selected from at least one of allyl dimethylsilane, propenyltrichlorosilane, allyl (chloromethyl) dimethylsilane, and trimethylallyloxysilane.

[0052] The raw materials for the aforementioned propylene-based trichlorosilane are readily available, which facilitates the industrial production of compatibility additives.

[0053] Preferably, the propylene trichlorosilane is selected from propylene trichlorosilane or allyl (chloromethyl) dimethylsilane. Both of these propylene trichlorosilanes contain halogen atoms, which can further improve the flame retardancy of the composite material and improve its compatibility with the flame retardant, so that the flame retardant can be uniformly dispersed in the composite material.

[0054] Optionally, the compatibility agent is prepared by:

[0055] S1: Add 1 / 3 acrylamide and 1 / 2 styrene to the solvent, then add the initiator and sodium dodecylbenzenesulfonate, and react at 60-80℃ for 1-3 hours to obtain the prepolymer;

[0056] S2: Add the remaining acrylamide, styrene and propylene trichlorosilane to the prepolymer, continue the reaction at this temperature for 3-5 hours, then raise the temperature to 95°C and react for 0.5-1 hours. Discharge, filter, wash and dry to obtain the compatibility additive.

[0057] Propylene trichlorosilane exhibits low free radical activity under the action of free radical initiators, thus limiting its copolymerization and preventing the effective formation of high molecular weight polymers. In this preparation method, prepolymerization in step S1 allows the prepolymer to initiate the reaction of propylene trichlorosilane, improving the reaction efficiency of the copolymer and yielding an ideal compatibility aid.

[0058] The initiator is selected from benzoyl peroxide and / or azobisisobutyronitrile, and the amount of the initiator added accounts for 1-3% of the total weight of acrylamide, styrene, and propylene trichlorosilane.

[0059] The amount of initiator added in this application is larger than that in conventional styrene-acrylamide copolymerization because propylene trichlorosilane has low reactivity in polymerization, thus requiring more initiator to initiate the reaction and improve reaction efficiency.

[0060] Preferably, the initiator is selected from benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1. Since propylene trichlorosilane has low reactivity in the reaction, this application can improve the reaction efficiency of propylene trichlorosilane and reduce the reaction time by using two initiators together.

[0061] The amount of sodium dodecylbenzenesulfonate added is 1-3% of the total weight of acrylamide, styrene, and propylene trichlorosilane.

[0062] Optionally, the flame retardant is selected from nitrogen-containing flame retardants or phosphorus-containing flame retardants.

[0063] Preferably, the flame retardant is selected from melamine or [(6-oxo-6H-dibenzo[C,E][1,2]oxophosphorylhexane-6-yl)methyl]succinic acid.

[0064] According to another aspect of this application, a method for preparing the high-durability, flame-retardant building formwork material described in any of the above claims is provided, comprising the following steps:

[0065] (1) The polycarbonate, ABS, epoxidized silicone rubber, amino halogenated compound, 4,4'-diaminodiphenyl sulfide, dispersant, compatibilizer, antioxidant, light stabilizer, flame retardant and anti-dripping agent are mixed to obtain a mixture;

[0066] (2) The mixture is added to an extruder, extruded and granulated to obtain the high-durability, flame-retardant building template material.

[0067] Optionally, in step (2), the extrusion temperature of the extruder is 250-290℃ and the rotation speed is 200-500 rpm.

[0068] According to another aspect of this application, a high-durability, flame-retardant building template is provided, which is prepared by injection molding or 3D printing using the high-durability, flame-retardant building template material described in any one of the above claims.

[0069] The beneficial effects of this application include, but are not limited to:

[0070] 1. According to the high-durability, flame-retardant building formwork material of this application, the amino groups contained in the amino-containing halogenated compounds and 4,4'-diaminodiphenyl sulfide can react with epoxidized silicone rubber to form a chemical bond, thereby forming a rigid and stable structure in the polycarbonate substrate to improve the durability of the material.

[0071] 2. According to the high-durability, flame-retardant building template material of this application, the amino-containing halogen compound contains halogen elements at both ends, which can impart good flame retardancy to the polycarbonate matrix, and the ester group contained in the middle can improve the compatibility with polycarbonate, thereby making it uniformly dispersed in the polycarbonate matrix and improving the overall performance uniformity of the material.

[0072] 3. According to the high-durability, flame-retardant building formwork material of this application, amino halogenated compounds and 4,4'-diaminodiphenyl sulfide can both form a chemical bond with epoxide silicone rubber, and the two can achieve the best durability and flame-retardant effect of the material under a specific ratio.

[0073] 4. The preparation method of the high-durability, flame-retardant building formwork material according to this application has a simple preparation process, is easy to operate, requires no additional post-processing steps, and is conducive to industrial promotion and use.

[0074] 5. The high-durability, flame-retardant building template according to this application is prepared by injection molding or 3D printing of granulated materials. The process is simple, meets the requirements of non-metallic additive 3D printing, and can improve the processing efficiency and construction efficiency of building templates. Attached Figure Description

[0075] The accompanying drawings, which are included to provide a further understanding of this application and form part of this application, illustrate exemplary embodiments and are used to explain this application, but do not constitute an undue limitation of this application. In the drawings:

[0076] Figure 1 This is a reaction process diagram of the amino-containing halogenated compounds involved in Examples 1-3 of this application. Detailed Implementation

[0077] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0078] Unless otherwise specified, all raw materials used in the embodiments and comparative examples of this application were purchased commercially. The epoxy silicone rubber used in the following embodiments and comparative examples was obtained by the preparation method of 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 was poly[1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine succinate], the flame retardant was selected from melamine, the antioxidant was selected from antioxidant 168, and the anti-dripping agent was selected from anti-dripping agent SN3310.

[0079] Unless otherwise specified, the methods used in the embodiments and comparative examples of this application are conventional methods in the prior art. In the preparation of the compatibility aids and amino-containing halogenated compounds in the following embodiments and comparative examples, the solvents used are not specifically limited, as long as they can ensure good solubility of the raw materials and facilitate the subsequent discharge of the products. In the following embodiments and comparative examples, the extruder temperature is 250-290℃, specifically referring to the extruder being divided into five temperature sections: conveying section temperature 250-260℃, melting section temperature 255-265℃, mixing section temperature 265-270℃, venting section temperature 265-275℃, homogenizing section temperature 275-280℃, and extrusion die temperature 280-290℃.

[0080] Example 1

[0081] This embodiment relates to a highly durable, flame-retardant building formwork material, which, by weight, comprises:

[0082] 100 parts polycarbonate, 20 parts ABS, 8 parts sodium silicate, 12 parts epoxidized silicone rubber, 3 parts amino halogenated compound, 2 parts 4,4'-diaminodiphenyl sulfide, 0.5 parts flame retardant, 5 parts compatibility agent, 0.5 parts antioxidant, 0.5 parts light stabilizer, and 0.2 parts anti-dripping agent.

[0083] The preparation method of this material includes the following steps:

[0084] (1) The polycarbonate, ABS, epoxidized silicone rubber, amino halogenated compound, 4,4'-diaminodiphenyl sulfide, sodium silicate, compatibilizer, antioxidant, light stabilizer, flame retardant and anti-dripping agent are mixed to obtain a mixture;

[0085] (2) The mixture is added to an extruder and extruded and granulated at 250-290℃ and 200 rpm to obtain the high-durability, flame-retardant building template material.

[0086] The compatibility agent is obtained by copolymerization of acrylamide, styrene, and allyl dimethylsilane in a weight ratio of 3:3:1. The preparation method of the compatibility agent is as follows:

[0087] S1: Add 1 / 3 acrylamide and 1 / 2 styrene to the solvent, then add an initiator (benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1) accounting for 3% of the total weight of acrylamide, styrene and allyl dimethylsilane, and sodium dodecylbenzenesulfonate accounting for 3% of the total weight of acrylamide, styrene and allyl dimethylsilane, and react at 60°C for 3 hours to obtain the prepolymer;

[0088] S2: Add the remaining acrylamide, styrene and allyl dimethylsilane to the prepolymer, continue the reaction at this temperature for 5 hours, then raise the temperature to 95°C and react for 0.5 hours. Discharge, filter, wash and dry to obtain the compatibility additive.

[0089] The preparation method of the amino-containing halogen compound is as follows: 3,5-dibromobenzoic acid and dibutanolamine in a molar ratio of 2.1:1 are added to a solvent, followed by the addition of concentrated sulfuric acid (0.5 wt% of the total weight of 3,5-dibromobenzoic acid and dibutanolamine), and the addition of molecular sieves for water absorption. The reaction is carried out at 95°C for 4 hours. After the reaction is completed, the mixture is filtered and washed to obtain the final product. The preparation process is described in [reference needed]. Figure 1 X is Br, n is 4, and the specific reaction equation is as follows:

[0090] .

[0091] Example 2

[0092] This embodiment relates to a highly durable, flame-retardant building formwork material, which, by weight, comprises:

[0093] 100 parts polycarbonate, 25 parts ABS, 10 parts sodium hexaphosphate, 15 parts epoxidized silicone rubber, 5 parts amino halogenated compound, 1 part 4,4'-diaminodiphenyl sulfide, 1 part flame retardant, 8 parts compatibility agent, 0.6 parts antioxidant, 0.6 parts light stabilizer, and 0.3 parts anti-dripping agent.

[0094] The preparation method of this material includes the following steps:

[0095] (1) The polycarbonate, ABS, epoxidized silicone rubber, amino halogenated compound, 4,4'-diaminodiphenyl sulfide, sodium hexaphosphate, compatibilizer, antioxidant, light stabilizer, flame retardant and anti-dripping agent are mixed to obtain a mixture;

[0096] (2) The mixture is added to an extruder and extruded and granulated at 250-290℃ and 500 rpm to obtain the high-durability, flame-retardant building template material.

[0097] The compatibility agent is obtained by copolymerization of acrylamide, styrene, and allyl (chloromethyl)dimethylsilane in a weight ratio of 5:3:1. The preparation method of the compatibility agent is as follows:

[0098] S1: Add 1 / 3 acrylamide and 1 / 2 styrene to the solvent, then add an initiator (benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1) accounting for 1% of the total weight of acrylamide, styrene and allyl (chloromethyl) dimethylsilane, and sodium dodecylbenzenesulfonate accounting for 1% of the total weight of acrylamide, styrene and allyl (chloromethyl) dimethylsilane, and react at 80°C for 1 hour to obtain the prepolymer;

[0099] S2: Add the remaining acrylamide, styrene and allyl (chloromethyl)dimethylsilane to the prepolymer, continue to react at this temperature for 3 hours, then raise the temperature to 95°C and react for 1 hour. Discharge, filter, wash and dry to obtain the compatibility additive.

[0100] The preparation method of the amino-containing halogenated compound is as follows: 3,5-difluorobenzoic acid and dipropanolamine in a molar ratio of 2.4:1 are added to a solvent, followed by the addition of concentrated sulfuric acid (1 wt% of the total weight of 3,5-difluorobenzoic acid and dipropanolamine), and the addition of molecular sieves for water absorption. The reaction is carried out at 70°C for 6 hours. After the reaction is completed, the mixture is filtered and washed to obtain the final product. The preparation process is described in [reference needed]. Figure 1 X is F, n is 3, and the specific reaction equation is as follows:

[0101] .

[0102] Example 3

[0103] This embodiment relates to a highly durable, flame-retardant building formwork material, which, by weight, comprises:

[0104] 100 parts polycarbonate, 22 parts ABS, 8 parts dispersant, 13 parts epoxidized silicone rubber, 4 parts amino halogenated compound, 2 parts 4,4'-diaminodiphenyl sulfide, 0.8 parts flame retardant, 6 parts compatibility agent, 0.6 parts antioxidant, 0.6 parts light stabilizer, and 0.3 parts anti-dripping agent.

[0105] The preparation method of this material includes the following steps:

[0106] (1) The polycarbonate, ABS, epoxidized silicone rubber, amino halogenated compound, 4,4'-diaminodiphenyl sulfide, dispersant, compatibilizer, antioxidant, light stabilizer, flame retardant and anti-dripping agent are mixed to obtain a mixture;

[0107] (2) The mixture is added to an extruder and extruded and granulated at 250-290℃ and 300 rpm to obtain the high-durability, flame-retardant building template material.

[0108] The compatibility agent is obtained by copolymerization of acrylamide, styrene, and propylene trichlorosilane in a weight ratio of 5:4:1. The preparation method of the compatibility agent is as follows:

[0109] S1: Add 1 / 3 acrylamide and 1 / 2 styrene to the solvent, then add an initiator (benzoyl peroxide and azobisisobutyronitrile in a weight ratio of 1:1) accounting for 2.5% of the total weight of acrylamide, styrene and propylenetrichlorosilane, and sodium dodecylbenzenesulfonate accounting for 2% of the total weight of acrylamide, styrene and propylenetrichlorosilane, and react at 70°C for 2.5 h to obtain the prepolymer;

[0110] S2: Add the remaining acrylamide, styrene and propylene trichlorosilane to the prepolymer, continue to react at this temperature for 4 hours, then raise the temperature to 95°C and react for 1 hour. Discharge, filter, wash and dry to obtain the compatibility additive.

[0111] The preparation method of the amino-containing halogenated compound is as follows: 3,5-dichlorobenzoic acid and diethanolamine compound in a molar ratio of 2.2:1 are added to a solvent, followed by the addition of concentrated sulfuric acid (1 wt% of the total weight of 3,5-dichlorobenzoic acid and diethanolamine), and the addition of molecular sieves for water absorption. The reaction is carried out at 90℃ for 5 hours. After the reaction is completed, the mixture is filtered and washed to obtain the final product. The preparation process is described in [reference needed]. Figure 1 X is Cl, n is 2, and the specific reaction equation is as follows:

[0112] .

[0113] Example 4

[0114] The difference between this embodiment and Example 3 is that the amino-containing halogen compound is 5 parts and 4,4'-diaminodiphenyl sulfide is 1 part.

[0115] Example 5

[0116] The difference between this embodiment and Example 3 is that the amino-containing halogen compound is 3 parts and 4,4'-diaminodiphenyl sulfide is 2 parts.

[0117] Example 6

[0118] The difference between this embodiment and Example 3 is that dibutanolamine is used instead of diethanolamine in the preparation of the amino-containing halogenated compound.

[0119] Example 7

[0120] The difference between this embodiment and Embodiment 3 is that the compatibility additive is obtained by copolymerization of acrylamide, styrene and propylene trichlorosilane in a weight ratio of 1:4:1.

[0121] Example 8

[0122] The difference between this embodiment and Embodiment 3 is that the compatibility additive is obtained by copolymerizing acrylamide and styrene in a weight ratio of 5:4.

[0123] Example 9

[0124] The difference between this embodiment and Embodiment 3 is that allyl dimethylsilane is used instead of propenyl trichlorosilane.

[0125] Comparative Example 1

[0126] The difference between this comparative example and Example 3 is that unepoxidized phenyl silicone rubber is used, which is prepared by the preparation method described in Sections

[0041] -

[0045] of Example 1 of CN110358091B.

[0127] Comparative Example 2

[0128] The difference between this comparative example and Example 3 is that 3,5-dichloroaniline is used instead of the amino-containing halogenated compound.

[0129] Comparative Example 3

[0130] The difference between this comparative example and Example 3 is that 4,4'-diaminodiphenyl sulfide is not added.

[0131] Test Example 1

[0132] The high-durability, flame-retardant building template materials of the above embodiments and comparative examples were used to prepare test strips using an injection molding machine. The test strips were subjected to the following tests, and the test results are shown in Table 1.

[0133] 1. Tensile strength: Tested according to GB / T 1040;

[0134] 2. Impact strength: Tested according to ISO 179-1;

[0135] 3. Heat distortion temperature: Tested according to GB1634;

[0136] 4. Oxygen index: Tested in accordance with GB / T 2406.2-2009.

[0137] Table 1

[0138]

[0139] According to the test data of Examples 1-3, the high-durability and flame-retardant building template material prepared in this application has good tensile strength and impact strength, and its heat distortion temperature is above 113°C and its oxygen index is above 30.4%, which can improve the durability and flame retardancy of the material.

[0140] Test Example 2

[0141] The high-durability, flame-retardant building template materials of the above embodiments and comparative examples were used to prepare test strips using an injection molding machine. After the test strips were placed at -50℃ and 100℃ for 10 hours respectively, the tensile strength and oxygen index after treatment were tested using the tensile strength and oxygen index test method of Test Example 1. The tensile strength reduction rate and oxygen index were calculated. The test results are shown in Table 2.

[0142] Table 2

[0143]

[0144] According to the test data above, after the samples made of the high-durability and flame-retardant building template material of this application are subjected to ultra-low temperature and high temperature treatment, the combination of epoxy silicone rubber, amino halogenated compound 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 prone to pulverization during use, extending the service life and safety of the material.

[0145] The high-durability, flame-retardant building templates prepared by the above embodiments and comparative examples can be used as temporary roads by injection molding or 3D printing, thereby increasing the number of times temporary roads can be reused.

[0146] The above description is merely an embodiment of this application, and the scope of protection of this application is not limited to these specific embodiments, but is determined by the claims of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the technical concept and principles of this application should be included within the scope of protection of this application.

Claims

1. A highly durable, flame-retardant building formwork material, characterized in that, By weight, including: The composition includes 100 parts polycarbonate, 20-25 parts ABS, 8-10 parts dispersant, 12-15 parts epoxidized silicone rubber, 3-5 parts amino halogenated compound, 1-2 parts 4,4'-diaminodiphenyl sulfide, 0.5-1 part flame retardant, 5-8 parts compatibilizer, 0.5-0.6 parts antioxidant, 0.5-0.6 parts light stabilizer, and 0.2-0.3 parts anti-dripping agent. The epoxidized silicone rubber is epoxidized phenyl silicone rubber, and the compatibilizer is obtained by copolymerizing acrylamide, styrene, and propylene trichlorosilane in a weight ratio of (3-5):(3-4):

1. The structural formula of the amino-containing halogenated compound is as follows: , where X is selected from Br, Cl, I, F, and n is selected from any integer from 2 to 4.

2. The high-durability, flame-retardant building formwork material according to claim 1, characterized in that, The structural formula of the amino-containing halogenated compound is as follows: 。 3. The high-durability, flame-retardant building formwork material according to claim 1, characterized in that, The preparation method of the amino-containing halogenated compound is as follows: 3,5-Dihalobenzoic acid and an alcoholic amine compound in a molar ratio of (2.1-2.4):1 are added to a solvent and reacted under the action of a catalyst. After the reaction is completed, the mixture is filtered and washed to obtain the final product.

4. The high-durability, 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 alkanolamine compound is selected from at least one of diethanolamine, dipropanolamine, and dibutanolamine.

5. The high-durability, flame-retardant building formwork material according to claim 3, characterized in that, The reaction temperature of 3,5-dihalobenzoic acid and alkanolamine compounds is 70-95℃, and the reaction time is 4-6h.

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

1.

7. The high-durability, flame-retardant building formwork material according to claim 1, characterized in that, The dispersant is selected from at least one of sodium silicate, sodium 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-hydroxypiperidine 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-hexamethylenediyl-[(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 the high-durability, flame-retardant building formwork material according to any one of claims 1-7, characterized in that, Includes the following steps: (1) The polycarbonate, ABS, epoxidized silicone rubber, amino halogenated compound, 4,4'-diaminodiphenyl sulfide, dispersant, compatibilizer, antioxidant, light stabilizer, flame retardant and anti-dripping agent are mixed to obtain a mixture; (2) The mixture is added to an extruder, extruded and granulated to obtain the high-durability, flame-retardant building template material.

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

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

Images