Preparation method and application of flame-retardant anti-dripping polymer composite material
By leveraging the synergistic effect of halogen-free flame retardants and crosslinking agents, a crosslinked network structure is constructed, which solves the problem of dripping during combustion of polymer materials, improves flame retardancy and mechanical properties, and ensures the safety and mechanical properties of materials under high-temperature environments.
Patent Information
- Application Number
- CN202511546163.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-28
- Publication Date
- 2026-01-23
AI Technical Summary
Existing polymer materials are prone to producing molten droplets during combustion, which reduces safety, and traditional flame retardants can damage the mechanical properties of the substrate.
By employing halogen-free flame retardants in conjunction with crosslinking agents and co-crosslinking agents, a crosslinked network structure is constructed to enhance the flame retardant properties and anti-dripping properties of the polymer.
It significantly suppresses melt flow and dripping during combustion, improves the thermal stability and mechanical properties of the material, and enhances its safety in high-temperature environments.
Smart Images
Figure CN121379072A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of functional materials technology, and in particular to a method for preparing and applying a flame-retardant and anti-dripping polymer composite material. Background Technology
[0002] In today's world where humans are inextricably linked to plastic products, polymers have a vast market application across various fields. However, the flammability of polymers and their tendency to produce molten droplets during intense combustion significantly compromise their safety in everyday use. Therefore, improving the flame retardancy and anti-dripping properties of polymer materials is crucial and imperative. Currently, the optimal choice for improving the flame retardancy of polymers is to add flame retardants to the matrix, making flame retardants the second most consumed polymer additive. However, with the development of flame retardant technology, higher demands are being placed on flame-retardant polymer composites. In addition to halogen-free flame retardancy and high flame retardancy, it is also necessary to avoid significant damage to the mechanical properties of the substrate caused by the addition of flame retardants. Summary of the Invention
[0003] To address the aforementioned problems in existing technologies, this invention provides a method for preparing and applying a flame-retardant and anti-dripping polymer composite material. This invention enhances the flame-retardant properties of the polymer by introducing a halogen-free flame retardant; simultaneously, the combined action of a crosslinking agent and a co-crosslinking agent constructs an effective crosslinked network structure within the polymer matrix, significantly suppressing melt flow and dripping during combustion. Therefore, the synergistic effect of halogen-free flame retardancy and the crosslinked network structure achieves high flame retardancy and anti-dripping properties. Furthermore, this synergistic effect also endows the composite material with good thermal stability and excellent mechanical properties.
[0004] The technical solution of the present invention is as follows: The first objective of this invention is to provide a flame-retardant and anti-dripping polymer composite material, wherein the raw material composition of the flame-retardant and anti-dripping polymer is as follows: by weight, each raw material is: 88-90 parts of polymer material, 10-12 parts of halogen-free flame retardant, 0.02-0.1 parts of crosslinking agent, and 0.02-0.1 parts of co-crosslinking agent; Halogen-free flame retardants have the structure shown in the following general formula (1):
[0005] General formula (1) R1-R4 are independently represented as one or more of H, carboxyl, carbonyl, methylene alcohol, cyclohexyl, methyl, cyanomethyl, and aminomethyl; the molecular weight of the halogen-free flame retardant is 1000–5000 g / mol.
[0006] In one embodiment of the present invention, the polymeric material is one or more of polylactide, polyethylene terephthalate, polybutylene terephthalate, and polyglycolic acid.
[0007] In one embodiment of the present invention, the preparation method of the halogen-free flame retardant includes the following steps: (1) Dissolve tris(2-chloropropyl) phosphate in an organic solvent to obtain a tris(2-chloropropyl) phosphate solution; (2) Dissolve piperazine monomers in an organic solvent to prepare an organic solution containing piperazine monomers; (3) Add an organic solution containing piperazine monomers dropwise to a tris(2-chloropropyl) phosphate solution at 0-5℃, react for a period of time, raise the temperature to react, and then lower the temperature to 0-5℃ after the reaction is completed; (4) Add an organic solution containing phosphoric acid dropwise, and add triethylamine dropwise at the same time. Keep the pH of the reaction system at 7.5-8.5. After reacting for a period of time, extract, wash and dry to obtain the halogen-free flame retardant.
[0008] In one embodiment of the present invention, in step (2), the structure of the piperazine monomer is shown in any of the following structures: , , , , , , , .
[0009] In one embodiment of the present invention, in steps (1) and (2), the organic solvent is one or more of dichloromethane, trichloromethane, tetrahydrofuran, and aqueous ethanol solution.
[0010] In one embodiment of the present invention, in step (3), the molar ratio of tris(2-chloropropyl) phosphate to piperazine monomer is 1:3-5; the reaction conditions are: stirring at 0-5℃ for 3-5 h, then heating to 25-30℃, and stirring for another 5-8 h.
[0011] In one embodiment of the present invention, in step (4), the organic solution containing phosphoric acid is an organic solution of orthophosphoric acid or polyphosphoric acid, and the concentration is prepared to be 10-20wt%; the reaction conditions are: the pH of the system is maintained at 6.5-7.5 with triethylamine, the temperature is 20-25℃, and the time is 5-8 h.
[0012] In one embodiment of the present invention, the crosslinking agent is one or more of dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and di(2,4-dichlorobenzoyl)peroxide.
[0013] In one embodiment of the present invention, the co-crosslinking agent is one or more of triallyl isonitrile urate and epoxyallyl phosphate.
[0014] A second objective of this invention is to provide a method for preparing the above-mentioned flame-retardant and anti-dripping polymer composite material, comprising the following steps: First, dry the halogen-free flame retardant and polymer masterbatch in a vacuum oven at 80℃. Then, weigh 10-12 parts of halogen-free flame retardant, 0.02-0.1 parts of crosslinking agent, 0.02-0.1 parts of co-crosslinking agent, and 88-90 parts of polymer material according to the ratio. After premixing, add the mixture to a torque rheometer or screw extruder and melt-blend at 180-190℃. Then, obtain the flame-retardant and anti-dripping polymer composite material through a molding process.
[0015] A third objective of this invention is to provide an application of the above-mentioned flame-retardant and anti-dripping polymer composite material in the fields of medical device manufacturing, textiles, construction, or transportation.
[0016] The beneficial technical effects of this invention are as follows: The halogen-free flame retardant of this invention significantly improves the flame retardant performance of materials. The formation of the cross-linked network and the synergistic effect of the flame retardant macromolecular structure effectively bind the molten polymer, fundamentally suppressing the phenomenon of melt dripping during combustion and avoiding the risk of secondary fire.
[0017] The flame-retardant polymer composite material of this invention exhibits superior mechanical properties and thermal stability. The cross-linking network and flame retardant work together to significantly increase the thermal decomposition initiation temperature of the composite material and substantially increase the high-temperature char residue, thereby enhancing the material's safety in high-temperature environments while maintaining or even improving the mechanical properties of the matrix polymer. Attached Figure Description
[0018] Figure 1 The 1H NMR spectrum of TCPA, the halogen-free flame retardant obtained in Example 1; Figure 2 The stress-strain curves of the composite materials obtained in Examples 3-8 are shown. Figure 3 The stress-strain curves of the composite materials obtained in Examples 9 and 10 are shown. Figure 4 The TGA curves of the composite materials obtained in Examples 3-10 are shown. Detailed Implementation
[0019] The present invention will now be described in detail with reference to embodiments and comparative examples.
[0020] Polylactide, sourced from TotalCoppen Energy, model number LX575.
[0021] Polyhydroxy fatty acid ester (PHA), derived from CJ Group in South Korea, model number S1000P.
[0022] Example 1 0.1 mol of tris(2-chloropropyl) phosphate (TCPP) was dissolved in 100 mL of dichloromethane to obtain a tris(2-chloropropyl) phosphate dichloromethane solution; 0.3 mol of piperazine monomers was dissolved in 100 mL of dichloromethane to prepare a dichloromethane solution containing piperazine monomers; the dichloromethane solution containing piperazine monomers was added dropwise to the tris(2-chloropropyl) phosphate dichloromethane solution at 0 °C, while triethylamine was added dropwise, maintaining the pH of the reaction system at 7.5-8.5, and reacting for 3 h. The system temperature was then raised to 25 °C and reacted for 5 h; finally, 50 mL of 20% thiocyanate solution was added dropwise. A solution of wt% phosphoric acid in dichloromethane was prepared, and triethylamine was added dropwise. The pH of the reaction system was maintained at 6.5-7.5. After reacting for 3 hours, the solution was removed and extracted with excess water-carrying agent. A white precipitate was precipitated. The precipitate was then washed with deionized water 5-8 times and finally dried in a vacuum oven at 60°C for 12 hours to obtain the halogen-free flame retardant TCPA. The structural formula of piperazine monomers is In this context, R1, R2, R3, and R4 are all hydrogen atoms.
[0023] Example 2 0.1 mol of tris(2-chloropropyl) phosphate (TCPP) was dissolved in 100 mL of dichloromethane to obtain a tris(2-chloropropyl) phosphate dichloromethane solution; 0.3 mol of piperazine monomers was dissolved in 100 mL of dichloromethane to prepare a dichloromethane solution containing piperazine monomers; the dichloromethane solution containing piperazine monomers was added dropwise to the tris(2-chloropropyl) phosphate dichloromethane solution at 0 °C, while triethylamine was added dropwise, maintaining the pH of the reaction system at 7.5-8.5, and reacting for 3 h. The system temperature was then raised to 25 °C and reacted for 5 h; finally, 50 mL of 20% thiocyanate solution was added dropwise. A solution of wt% phosphoric acid in dichloromethane was prepared, and triethylamine was added dropwise. The pH of the reaction system was maintained at 6.5-7.5. After reacting for 3 hours, the solution was removed and extracted with excess water-carrying agent. A white precipitate was precipitated. The precipitate was then washed with deionized water 5-8 times and finally dried in a vacuum oven at 60°C for 12 hours to obtain the halogen-free flame retardant TCPA. The structural formula of piperazine monomers is In this case, R1 = CH2CN, and R2, R3 and R4 are all hydrogen atoms.
[0024] Example 3 A method for preparing a flame-retardant and anti-dripping polymer composite material includes the following steps: each raw material is in parts by weight; Six parts of the flame retardant TCPA prepared in Example 1, 0.05 parts of dicumyl peroxide, 0.05 parts of triallyl isonitrile urate, and 93.9 parts of polylactide were melt-blended at 180°C using a torque rheometer, and then the flame retardant polymer composite material was obtained by compression molding.
[0025] Example 4 A method for preparing a flame-retardant and anti-dripping polymer composite material includes the following steps: each raw material is in parts by weight; Eight parts of the flame retardant TCPA prepared in Example 1, 0.05 parts of dicumyl peroxide, 0.05 parts of triallyl isonitrile urate, and 91.9 parts of polylactide were melt-blended at 180°C using a torque rheometer, and then the flame retardant polymer composite material was obtained by compression molding.
[0026] Example 5 A method for preparing a flame-retardant and anti-dripping polymer composite material includes the following steps: each raw material is in parts by weight; Six parts of the flame retardant TCPA prepared in Example 2, 0.05 parts of dicumyl peroxide, 0.05 parts of triallyl isonitrile urate, and 93.9 parts of polylactide were melt-blended at 180°C using a torque rheometer, and then the flame retardant polymer composite material was obtained by compression molding.
[0027] Example 6 A method for preparing a flame-retardant and anti-dripping polymer composite material includes the following steps: each raw material is in parts by weight; Eight parts of the flame retardant TCPA prepared in Example 2, 0.05 parts of dicumyl peroxide, 0.05 parts of triallyl isonitrile urate, and 91.9 parts of polylactide were melt-blended at 180°C using a torque rheometer, and then the flame retardant polymer composite material was obtained by compression molding.
[0028] Example 7 A method for preparing a flame-retardant and anti-dripping polymer composite material includes the following steps: each raw material is in parts by weight; Eight parts of the flame retardant TCPA prepared in Example 1, 0.1 parts of dicumyl peroxide, 0.1 parts of triallyl isonitrile urate, and 91.8 parts of polylactide were melt-blended at 180°C using a torque rheometer, and then the flame retardant polymer composite material was obtained by compression molding.
[0029] Example 8 A method for preparing a flame-retardant and anti-dripping polymer composite material includes the following steps: each raw material is in parts by weight; Eight parts of the flame retardant TCPA prepared in Example 2, 0.1 parts of dicumyl peroxide, 0.1 parts of triallyl isonitrile urate, and 91.8 parts of polylactide were melt-blended at 180°C using a torque rheometer, and then the flame retardant polymer composite material was obtained by compression molding.
[0030] Example 9 A method for preparing a flame-retardant and anti-dripping polymer composite material includes the following steps: each raw material is in parts by weight; Eight parts of the flame retardant TCPA prepared in Example 1, 0.05 parts of dicumyl peroxide, 0.05 parts of triallyl isonitrile urate, and 91.9 parts of polyhydroxyalkanoate were melt-blended at 160°C using a torque rheometer, and then the flame retardant polymer composite material was obtained by compression molding.
[0031] Example 10 A method for preparing a flame-retardant and anti-dripping polymer composite material includes the following steps: each raw material is in parts by weight; Eight parts of the flame retardant TCPA prepared in Example 2, 0.05 parts of dicumyl peroxide, 0.05 parts of triallyl isonitrile urate, and 91.9 parts of polyhydroxyalkanoate were melt-blended at 160°C using a torque rheometer, and then the flame retardant polymer composite material was obtained by compression molding.
[0032] Test example: The flame retardant prepared in Example 1 was subjected to... 1 H NMR characterization, results as follows Figure 1 As shown in the figure, the chemical shift (δ) shows an absorption peak for -CH3 at 0.94–0.98, absorption peaks for -CH2- at 3.44–3.46 and 2.41–2.43, and an absorption peak for -CH- at 2.49–2.53. 1 The results of 1H NMR confirmed the successful synthesis of the halogen-free flame retardant TCPA. The molecular weight and thermal stability data of the flame retardant TCPA are shown in Table 1 below.
[0033] Table 1
[0034] To investigate the flame retardancy, non-dripping properties, heat resistance, and mechanical properties of the flame-retardant polymer prepared by the method of the present invention, the samples obtained in Examples 1-8 were tested.
[0035] 1. The flame retardant properties of the obtained flame-retardant polymers were tested using the limiting oxygen index (LOI) experiment, and the results are shown in Table 2. The specific testing method is as follows: According to GB / T 2406.2-2009, the material was cut into 90×10×4mm strips for testing. If the strip extinguishes within 3 minutes at a certain oxygen content (oxygen volume percentage) and does not burn to within 5cm below the ignition point, then the oxygen content should be increased until either of the above two conditions cannot be met. This critical value is the limiting oxygen index (LOI) of the strip. When the oxygen index (LOI) is less than 22%, the material is considered flammable; when the oxygen index (LOI) is between 22% and 27%, the material is considered combustible; when the oxygen index (LOI) is greater than 27%, the material is considered flame-retardant. 2. The material was subjected to a vertical burning test (UL-94) according to ASTM D3801 standard. The sample size was 100×12×3 mm. 3 .
[0036] Table 2
[0037] 3. The mechanical properties of the obtained flame-retardant polymers were tested using a universal tensile testing machine in accordance with standard GB / T 1040-2006. The tensile rate was 30 mm / min, and each group of samples was tested 5 times to calculate the average value. The results are shown in Table 3.
[0038] Table 3
[0039] 4. The thermal decomposition behavior of the obtained flame-retardant polymer was tested using a thermogravimetric analyzer (TGA / DSC / 1100SF). Approximately 10 mg of sample was weighed and placed in a crucible. Under a nitrogen atmosphere, the temperature was increased from 40 °C to 800 °C at a heating rate of 20 °C / min, with a nitrogen flow rate of 50 mL / min. The test results are shown in Table 4 below.
[0040] Table 4
[0041] As shown in Tables 2-4, the prepared flame-retardant polymer has the following advantages: 1) Excellent flame-retardant and drip-suppressing properties, with limiting oxygen indices all above 28%, meeting the standards for flame-retardant materials; almost no dripping occurred during testing, achieving high fire safety; 2) Good mechanical properties, with tensile strength maintaining its original good performance; 3) High thermal stability and high char residue. Therefore, the flame-retardant polymer obtained by this invention can be used in daily necessities, office supplies, transportation equipment, the construction industry, and light industry.
[0042] Comparative Example 1 100 parts of polylactide were melt-blended at 180°C using a torque rheometer, and then the polymer composite material was obtained by compression molding.
[0043] Comparative Example 2 100 parts of polyhydroxyalkanoate were melt-blended at 160°C using a torque rheometer, and then the flame-retardant polymer composite material was obtained by compression molding.
[0044] Comparative Example 3 Eight parts of the flame retardant TCPA-2 prepared in Example 2, 0.5 parts of dicumyl peroxide, 0.5 parts of triallyl isonitrile urate, and 91 parts of polylactide were melt-blended at 180°C using a torque rheometer, and then the flame retardant polymer composite material was obtained by compression molding.
[0045] Comparative Example 4 Eight parts of the flame retardant TCPA prepared in Example 1, 0.2 parts of the anti-dripping agent, and 91.8 parts of polylactide were melt-blended at 180°C using a torque rheometer, and then the flame retardant polymer was obtained by compression molding.
[0046] in, The structure of the anti-dripping agent is as follows: Model: PTFE-105; Source: Shenzhen Jingcai Chemical Co., Ltd.
[0047] Comparative Example 5 Eight parts of flame retardant TCPA prepared in Example 2, 0.2 parts of anti-dripping agent (PTFE-105), and 91.8 parts of polylactide were melt-blended at 180°C using a torque rheometer, and then the flame retardant polymer was obtained by compression molding.
[0048] The flame-retardant polymers in the comparative examples were measured using the same methods mentioned in the examples. The results are shown in Table 5.
[0049] Table 5
[0050] Note: Comparative Example 3 contains a large number of cross-linked structures, making it difficult to mold and process.
[0051] The embodiments provided above are not intended to limit the scope of the invention, nor are the described steps intended to limit the order of execution. Any obvious modifications made to the invention by those skilled in the art based on existing common knowledge also fall within the scope of protection defined by the claims.
Claims
1. A flame-retardant and anti-dripping polymer composite material, characterized in that, The raw material composition of the flame-retardant and anti-dripping polymer is as follows: by weight, each raw material is: 88-90 parts of polymer material, 10-12 parts of halogen-free flame retardant, 0.02-0.1 parts of crosslinking agent, and 0.02-0.1 parts of co-crosslinking agent. Halogen-free flame retardants have the structure shown in the following general formula (1): General formula (1) R1-R4 are independently represented by one or more of H, carboxyl, carbonyl, methylene alcohol, cyclohexyl, methyl, cyanomethyl, and aminomethyl. The molecular weight of halogen-free flame retardants is 1000–5000 g / mol.
2. The flame-retardant and anti-dripping polymer composite material according to claim 1, characterized in that, The polymeric material is one or more of polylactide, polyethylene terephthalate, polybutylene terephthalate, and polyglycolic acid.
3. The flame-retardant and anti-dripping polymer composite material according to claim 1, characterized in that, The preparation method of halogen-free flame retardants includes the following steps: (1) Dissolve tris(2-chloropropyl) phosphate in an organic solvent to obtain a tris(2-chloropropyl) phosphate solution; (2) Dissolve piperazine monomers in an organic solvent to prepare an organic solution containing piperazine monomers; (3) Add an organic solution containing piperazine monomers dropwise to a tris(2-chloropropyl) phosphate solution at 0-5℃, react for a period of time, raise the temperature to react, and then lower the temperature to 0-5℃ after the reaction is completed; (4) Add an organic solution containing phosphoric acid dropwise, and add triethylamine dropwise at the same time. Keep the pH of the reaction system at 7.5-8.
5. After reacting for a period of time, extract, wash and dry to obtain the halogen-free flame retardant.
4. The flame-retardant and anti-dripping polymer composite material according to claim 3, characterized in that, In step (2), the structure of the piperazine monomer is shown in any of the following structures: 、 、 、 、 、 、 、 。 5. The flame-retardant and anti-dripping polymer composite material according to claim 3, characterized in that, In steps (1) and (2), the organic solvent is one or more of dichloromethane, trichloromethane, tetrahydrofuran, and aqueous ethanol solution.
6. The flame-retardant and anti-dripping polymer composite material according to claim 3, characterized in that, In step (3), the molar ratio of tris(2-chloropropyl) phosphate to piperazine monomer is 1:3-5; the reaction conditions are: stirring at 0-5℃ for 3-5 h, then raising the temperature to 25-30℃, and stirring for another 5-8 h.
7. The flame-retardant and anti-dripping polymer composite material according to claim 3, characterized in that, In step (4), the organic solution containing phosphoric acid is an organic solution of orthophosphoric acid or polyphosphoric acid, with a concentration of 10-20wt%; the reaction conditions are: maintaining the pH of the system at 6.5-7.5 with triethylamine, the temperature at 20-25℃, and the time at 5-8 h.
8. The flame-retardant and anti-dripping polymer composite material according to claim 1, characterized in that, The crosslinking agent is one or more of dicumyl peroxide, di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, and di(2,4-dichlorobenzoyl) peroxide; the co-crosslinking agent is one or more of triallyl isonitrile urate and epoxyallyl phosphate.
9. A method for preparing the flame-retardant and anti-dripping polymer composite material according to any one of claims 1-8, characterized in that, Includes the following steps: First, dry the halogen-free flame retardant and polymer masterbatch in a vacuum oven at 80℃. Then, weigh 10-12 parts of halogen-free flame retardant, 0.02-0.1 parts of crosslinking agent, 0.02-0.1 parts of co-crosslinking agent, and 88-90 parts of polymer material according to the ratio. After premixing, add the mixture to a torque rheometer or screw extruder and melt-blend at 180-190℃. Then, obtain the flame-retardant and anti-dripping polymer composite material through a molding process.
10. The application of the flame-retardant and anti-dripping polymer composite material of claim 1 in the fields of medical device manufacturing, textiles, construction, or transportation.