Flame-retardant automotive interior panel composite and method of making

Abstract

The application relates to a preparation method of a flame-retardant automobile interior plate composite material, which comprises the following steps: (1) uniformly mixing nitrogen and boron rich dibasic acid olefin copolymer, polyvinylpyrrolidone and a solvent to obtain a spinning dope; the spinning dope and a core liquid in a center tube of a hollow fiber spinning nozzle are simultaneously extruded into an outer coagulation bath to obtain nitrogen and boron rich hollow fiber filaments; (2) the hollow fiber filaments are immersed in a mixed solution prepared by compounding p-benzenediboronic acid and an aqueous metal salt solution, and after hydrothermal reaction under temperature rising, flame-retardant hollow fiber filaments after surface modification treatment are obtained; (3) the flame-retardant hollow fiber filaments are compounded and spun with natural plant fiber filaments to obtain the flame-retardant automobile interior plate composite material. The flame-retardant automobile interior plate composite material prepared by the application not only has excellent flame-retardant and smoke suppression performances, but also has good high and low temperature resistance, stain resistance and aging resistance, and can meet the manufacturing requirements of light weight automobile parts.

Description

Technical Field

[0001] This invention relates to the technical field of composite fiber materials, and in particular to a flame-retardant automotive interior panel composite material and its preparation method. Background Technology

[0002] With rapid economic development and rising living standards, automobiles have become increasingly popular as a means of transportation. Automotive interior panels, as a crucial component, typically require aesthetic appeal, softness, comfort, and odorlessness. Currently, composite substrates used in automotive interior panel manufacturing are gradually being replaced by natural fiber composite materials. In the prior art, patent document (publication number: CN102145553A) discloses an environmentally friendly and recyclable basalt fiber and hemp fiber composite board for automotive interior parts, which boasts advantages such as light weight, low cost, high strength, good toughness, high adaptability, high safety, and environmental recyclability. However, it struggles to simultaneously meet requirements for flame retardancy, smoke suppression, and other comprehensive performance characteristics such as resistance to high and low temperatures, stain resistance, and aging resistance. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the present invention provides a method for preparing a flame-retardant automotive interior panel composite material to solve the problem that existing automotive interior panel composite materials cannot simultaneously possess excellent flame-retardant and smoke-suppressing properties, as well as other comprehensive performance requirements such as high and low temperature resistance, stain resistance, and aging resistance.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0005] A method for preparing a flame-retardant automotive interior panel composite material, the method comprising the following steps:

[0006] (1) A nitrogen- and boron-rich dibasic acid olefin copolymer, polyvinylpyrrolidone, and solvent are mixed evenly, and air bubbles are removed by vacuuming to obtain a spinning solution. The spinning solution is injected into a hollow fiber spinning spinneret, and the spinning solution and the core liquid in the central tube of the spinneret are simultaneously extruded into an external coagulation bath to obtain nitrogen- and boron-rich hollow fiber filaments. The hollow fiber filaments prepared by this invention not only contribute to the development of lightweight automobiles but also improve the impact toughness and other mechanical properties of automotive interior panel composite materials. This invention uses a nitrogen- and boron-rich dibasic acid olefin copolymer as one of the spinning solutions, thereby improving the flame retardant properties of automotive interior panel composite materials.

[0007] (2) The nitrogen- and boron-rich hollow fiber obtained in step (1) is immersed in a mixed solution of terephthalic acid and metal salt aqueous solution. After hydrothermal reaction, flame-retardant hollow fiber with surface modification is obtained. The surface of the hollow fiber of the present invention is rich in phenylboronic acid. The two phenylboronic acid groups grafted on the triazine derivative chain segment can undergo molecular self-assembly reaction with metal ions in the metal salt together with terephthalic acid, thereby obtaining flame-retardant hollow fiber with metal-organic framework material grafted on the surface. Furthermore, flame-retardant material composed of boron and metal elements is uniformly distributed on the surface of the hollow fiber, thereby further improving the flame-retardant performance and smoke suppression performance of automotive interior panel composite material.

[0008] (3) The flame-retardant hollow fiber obtained in step (2) is combined with natural plant fiber to obtain the flame-retardant automotive interior panel composite material.

[0009] Preferably, the mass ratio of the nitrogen-boron-rich dicarboxylic acid olefin copolymer, polyvinylpyrrolidone, and solvent is 15-35:10-20:40-70.

[0010] Preferably, the nitrogen- and boron-rich diacid olefin copolymer is obtained by copolymerization of a nitrogen- and boron-containing diacid olefin intermediate and fluorinated vinylidene. Specifically, the nitrogen- and boron-containing diacid olefin intermediate is uniformly dispersed in a solvent, fluorinated vinylidene and an initiator are added, and the mixture is stirred and reacted for a certain period of time to obtain the nitrogen- and boron-rich olefin copolymer. The fluorinated vinylidene involved in the copolymerization reaction of this invention introduces fluorinated segments, which, in conjunction with triazine derivative segments and the hollow fiber filaments obtained from the copolymerization structure of this application, further improve the high and low temperature resistance, stain resistance, and aging resistance of the automotive interior panel composite material.

[0011] Preferably, the preparation method of the nitrogen- and boron-containing dicarboxylic acid olefin intermediate is as follows: 1,3,5-triacryloylhexahydro-1,3,5-triazine is uniformly dispersed in a solvent, and acrylamide-phenylboronic acid is added at a molar ratio of 2:1 to acrylamide-phenylboronic acid. The reaction is carried out at a temperature under an inert atmosphere for a period of time. After the reaction is completed, the reaction mixture is separated to obtain the nitrogen- and boron-containing dicarboxylic acid olefin intermediate. This invention involves an addition reaction between the two unsaturated double bonds on 1,3,5-triacryloylhexahydro-1,3,5-triazine and the unsaturated double bonds on acrylamide-phenylboronic acid to obtain a triazine derivative grafted with two phenylboronic acid groups and one remaining olefin unsaturated double bond, i.e., a nitrogen- and boron-containing dicarboxylic acid olefin intermediate. The two phenylboronic acid groups and terephthalic acid can undergo intermolecular chelation reactions with metal ions in metal salts, while the remaining olefin unsaturated double bond can undergo copolymerization reactions with fluorinated vinyl. In addition, the introduction of triazine derivative segments in this invention helps to improve the high and low temperature resistance and aging resistance of the composite material.

[0012] Preferably, the acrylamide phenylboronic acid is at least one selected from 3-acrylamidophenylboronic acid, 3-methylacrylamidophenylboronic acid, and 2-acrylamidophenylboronic acid. The acrylamide phenylboronic acid of this invention contains an unsaturated double bond at one end, which can participate in the copolymerization reaction of unsaturated double bonds in olefins. The phenylboronic acid at the other end, after undergoing an addition reaction with 1,3,5-triacryloylhexahydro-1,3,5-triazine, can then combine with metal ions through a chelation reaction.

[0013] Preferably, the fluorinated ethylene is at least one of tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, 1,2-difluorodichloroethylene, trifluorochloroethylene, and 1,1-dichloro-2,2-difluoroethylene.

[0014] Preferably, the core solution is a polyethylene glycol aqueous solution with a mass concentration of 5-10%. The core solution flow rate is 5-15 mL / min, the core solution temperature is 20-80°C, and the spinning speed is 6-12 m / min. The spinning temperature of the spinning solution is 60-90°C.

[0015] Preferably, the cation in the aqueous solution of the metal salt is at least one of calcium ion, magnesium ion, zinc ion or aluminum ion, and the anion is at least one of sulfate ion, chloride ion or nitrate ion.

[0016] Preferably, the reaction temperature of the hydrothermal reaction is 95–105°C.

[0017] Another aspect of the present invention is to provide a flame-retardant automotive interior panel composite material, wherein the composite material is prepared by the preparation method of the flame-retardant automotive interior panel composite material described above.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0019] The flame-retardant automotive interior panel composite material of the present invention is obtained by composite blending flame-retardant hollow fiber filaments and natural plant fiber filaments. It not only has excellent flame-retardant and smoke-suppressing properties, but also good resistance to high and low temperatures, stains and aging, which can meet the requirements of lightweight automotive parts manufacturing. Detailed Implementation

[0020] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art. Example 1

[0021] The preparation method of the flame-retardant automotive interior panel composite material in this embodiment includes the following steps:

[0022] (1) A nitrogen-boron-rich dicarboxylic acid olefin copolymer, polyvinylpyrrolidone, and solvent N,N-dimethylformamide are mixed evenly, and the air bubbles are removed by vacuum to obtain a spinning solution. The spinning solution is injected into a hollow fiber spinning spinneret, and the spinning solution and the core liquid in the central tube of the spinneret are simultaneously extruded into an external coagulation bath to obtain nitrogen-boron-rich hollow fiber filaments. The mass ratio of the nitrogen-boron-rich dicarboxylic acid olefin copolymer, polyvinylpyrrolidone, and N,N-dimethylformamide is 15:10:70. The core liquid is a 5% (w / w) polyethylene glycol aqueous solution. The core liquid flow rate is 5 mL / min, the core liquid temperature is 80℃, and the spinning speed is 8 m / min. The spinning temperature of the spinning solution is 90℃.

[0023] (2) 35 parts by weight of the nitrogen- and boron-rich hollow fiber obtained in step (1) are impregnated in a mixed solution composed of 10 parts by weight of terephthalic acid and 100 parts by weight of a metal salt aqueous solution (mass concentration of 12%). After hydrothermal reaction, flame-retardant hollow fiber with surface modification is obtained. The reaction temperature of the hydrothermal reaction is 95°C. The cation in the metal salt aqueous solution is calcium ion and the anion is chloride ion.

[0024] (3) The flame-retardant hollow fiber filaments obtained in step (2) are combined and spun with natural plant fiber filaments to obtain the flame-retardant automotive interior panel composite material. The mass ratio of the flame-retardant hollow fiber filaments to the natural plant fiber filaments is 1:1.

[0025] The nitrogen- and boron-rich dicarboxylic acid olefin copolymer is obtained by copolymerization of a nitrogen- and boron-containing dicarboxylic acid olefin intermediate and a fluorinated vinyl group. Specifically, 12.5 parts by weight of 1,3,5-triacryloylhexahydro-1,3,5-triazine were first uniformly dispersed in 100 parts by weight of the solvent N,N-dimethylformamide. 3-Acrylamidophenylboronic acid was added at a molar ratio of 2:1 to 1, and the reaction was carried out under a nitrogen inert atmosphere at 70°C for 1 hour. After the reaction, the reaction mixture was separated to obtain a nitrogen- and boron-containing diacid olefin intermediate. Then, 20 parts by weight of the nitrogen- and boron-containing diacid olefin intermediate were uniformly dispersed in 100 parts by weight of the solvent N,N-dimethylformamide. 50 parts by weight of tetrafluoroethylene and 1.2 parts by weight of the initiator ammonium persulfate were added, and the mixture was stirred for a certain time at 120°C for 2 hours to obtain a nitrogen- and boron-rich olefin copolymer. Example 2

[0026] The preparation method of the flame-retardant automotive interior panel composite material in this embodiment includes the following steps:

[0027] (1) A nitrogen-boron-rich dicarboxylic acid olefin copolymer, polyvinylpyrrolidone, and solvent N,N-dimethylformamide are mixed evenly, and the air bubbles are removed by vacuum to obtain a spinning solution. The spinning solution is injected into a hollow fiber spinning spinneret, and the spinning solution and the core liquid in the central tube of the spinneret are simultaneously extruded into an external coagulation bath to obtain nitrogen-boron-rich hollow fiber filaments. The mass ratio of the nitrogen-boron-rich dicarboxylic acid olefin copolymer, polyvinylpyrrolidone, and N,N-dimethylformamide is 30:20:70. The core liquid is a 10% (w / w) polyethylene glycol aqueous solution. The core liquid flow rate is 5 mL / min, the core liquid temperature is 50°C, and the spinning speed is 7 m / min. The spinning temperature of the spinning solution is 60°C.

[0028] (2) 35 parts by weight of the nitrogen- and boron-rich hollow fiber obtained in step (1) are immersed in a mixed solution composed of 9 parts by weight of terephthalic acid and 100 parts by weight of a metal salt aqueous solution (mass concentration of 11%). After a hydrothermal reaction, flame-retardant hollow fiber with surface modification is obtained. The reaction temperature of the hydrothermal reaction is 95°C. The cation in the metal salt aqueous solution is magnesium ion and the anion is chloride ion.

[0029] (3) The flame-retardant hollow fiber filaments obtained in step (2) are combined and spun with natural plant fiber filaments to obtain the flame-retardant automotive interior panel composite material. The mass ratio of the flame-retardant hollow fiber filaments to the natural plant fiber filaments is 2:3.

[0030] The nitrogen- and boron-rich dicarboxylic acid olefin copolymer is obtained by copolymerization of a nitrogen- and boron-containing dicarboxylic acid olefin intermediate and a fluorinated vinyl group. Specifically, 12.5 parts by weight of 1,3,5-triacryloylhexahydro-1,3,5-triazine were first uniformly dispersed in 100 parts by weight of the solvent N,N-dimethylformamide. 2-Acrylamidophenylboronic acid was added at a molar ratio of 2:1 to 1, and the reaction was carried out under a nitrogen inert atmosphere at 70°C for 1 hour. After the reaction, the reaction mixture was separated to obtain a nitrogen- and boron-containing diacid olefin intermediate. Then, 20 parts by weight of the nitrogen- and boron-containing diacid olefin intermediate were uniformly dispersed in 100 parts by weight of the solvent N,N-dimethylformamide. 45 parts by weight of vinylidene fluoride and 1.0 part by weight of the initiator ammonium persulfate were added. After stirring and reacting for a certain period, the reaction temperature was 115°C and the reaction time was 2.5 hours to obtain a nitrogen- and boron-rich olefin copolymer. Example 3

[0031] The preparation method of the flame-retardant automotive interior panel composite material in this embodiment includes the following steps:

[0032] (1) A nitrogen-boron-rich dicarboxylic acid olefin copolymer, polyvinylpyrrolidone, and solvent N,N-dimethylformamide are mixed evenly, and the air bubbles are removed by vacuum to obtain a spinning solution. The spinning solution is injected into a hollow fiber spinning spinneret, and the spinning solution and the core liquid in the central tube of the spinneret are simultaneously extruded into an external coagulation bath to obtain nitrogen-boron-rich hollow fiber filaments. The mass ratio of the nitrogen-boron-rich dicarboxylic acid olefin copolymer, polyvinylpyrrolidone, and N,N-dimethylformamide is 25:15:60. The core liquid is a 5% (w / w) polyethylene glycol aqueous solution. The core liquid flow rate is 15 mL / min, the core liquid temperature is 60°C, and the spinning speed is 8 m / min. The spinning temperature of the spinning solution is 70°C.

[0033] (2) 35 parts by weight of the nitrogen- and boron-rich hollow fiber obtained in step (1) are impregnated in a mixed solution composed of 8 parts by weight of terephthalic acid and 100 parts by weight of a metal salt aqueous solution (mass concentration of 10%). After hydrothermal reaction, flame-retardant hollow fiber with surface modification is obtained. The reaction temperature of the hydrothermal reaction is 105°C. The cation in the metal salt aqueous solution is zinc ion and the anion is chloride ion.

[0034] (3) The flame-retardant hollow fiber filaments obtained in step (2) are combined and spun with natural plant fiber filaments to obtain the flame-retardant automotive interior panel composite material. The mass ratio of the flame-retardant hollow fiber filaments to the natural plant fiber filaments is 3:2.

[0035] The nitrogen- and boron-rich dicarboxylic acid olefin copolymer is obtained by copolymerization of a nitrogen- and boron-containing dicarboxylic acid olefin intermediate and a fluorinated vinyl group. Specifically, 12.5 parts by weight of 1,3,5-triacryloylhexahydro-1,3,5-triazine were uniformly dispersed in 100 parts by weight of the solvent N,N-dimethylformamide. 3-Acrylamidophenylboronic acid was added at a molar ratio of 2:1 to 1,3,5-triacryloylhexahydro-1,3,5-triazine. The reaction was carried out under a nitrogen inert atmosphere at 80°C for 1.5 hours. After the reaction, the reaction mixture was separated to obtain a nitrogen- and boron-containing diacid olefin intermediate. Then, 20 parts by weight of the nitrogen- and boron-containing diacid olefin intermediate were uniformly dispersed in 100 parts by weight of the solvent N,N-dimethylformamide. 40 parts by weight of trifluoroethylene and 1.1 parts by weight of the initiator ammonium persulfate were added. The mixture was stirred and reacted for a certain period at 110°C for 3 hours to obtain a nitrogen- and boron-rich olefin copolymer. Example 4

[0036] The preparation method of the flame-retardant automotive interior panel composite material in this embodiment is basically the same as that in Example 1. The difference is that, in the preparation method of the flame-retardant automotive interior panel composite material in this embodiment, magnesium ions are used instead of calcium ions as cations in the metal salt aqueous solution, and nitrate ions are used instead of chloride ions as anions. 3-Methylacrylamidophenylboronic acid is used instead of 3-acrylamidophenylboronic acid. 1,2-Difluorodichloroethylene is used instead of tetrafluoroethylene. Example 5

[0037] The preparation method of the flame-retardant automotive interior panel composite material in this embodiment is basically the same as that in Example 1. The difference is that, in the preparation method of the flame-retardant automotive interior panel composite material in this embodiment, aluminum ions are used instead of calcium ions in the metal salt aqueous solution. 2-Acrylamidophenylboronic acid is used instead of 3-acrylamidophenylboronic acid. Trifluorochloroethylene is used instead of tetrafluoroethylene. Example 6

[0038] The preparation method of the flame-retardant automotive interior panel composite material in this embodiment is basically the same as that in Example 1. The difference is that, in the preparation method of the flame-retardant automotive interior panel composite material in this embodiment, magnesium ions are used instead of calcium ions in the metal salt aqueous solution. 2-Acrylamidophenylboronic acid is used instead of 3-acrylamidophenylboronic acid. 1,1-Dichloro-2,2-difluoroethylene is used instead of tetrafluoroethylene.

[0039] The flame-retardant automotive interior panel composite materials prepared in Examples 1-6 were subjected to performance tests, and the performance results are shown in Table 1.

[0040] Table 1

[0041]

[0042] Mechanical property testing: Tensile properties were tested according to GB / T 1040.2-2006 standard. The flame-retardant automotive interior panel composite materials of Examples 1-6 were warp-knitted and cut into strips with dimensions of 200mm×10mm×4mm. The tensile speed was 50mm / min, and the test was conducted using a CMT4101 electronic tensile testing machine. Notched impact strength was tested according to GB / T1843-2008 standard, using a XIJ-5 simply supported beam impact testing machine.

[0043] The flame retardant performance was tested according to the GB / T 5454 test standard, which determined the average limiting oxygen index of the samples.

[0044] High and low temperature resistance test: The sample was placed in a low temperature oven at -40℃ and a high temperature oven at 85℃ for 168 hours; the high and low temperature resistance of the sample was evaluated as qualified if the tensile strength was not less than 95% of the initial tensile strength of the sample.

[0045] Aging resistance test: The sample was placed in a high-pressure accelerated aging test chamber at 105±2℃ for 168h; the aging resistance of the sample was evaluated to determine whether it was qualified, provided that the tensile strength was not less than 90% of the initial tensile strength of the sample.

[0046] Therefore, it is evident that this invention patent has significant advantages over currently used technologies. The basic principles, main features, and advantages of this invention have been shown and described above. Those skilled in the art should understand that this invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to this invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A method for preparing a flame-retardant automotive interior panel composite material, characterized in that, The preparation method includes the following steps: (1) Mix nitrogen- and boron-rich dicarboxylic acid olefin copolymer, polyvinylpyrrolidone, and solvent evenly, and remove air bubbles by vacuuming to obtain spinning solution; inject the spinning solution into the hollow fiber spinning spinneret, and simultaneously extrude the spinning solution and the core liquid in the central tube of the spinneret into the external coagulation bath to obtain nitrogen- and boron-rich hollow fiber filaments. (2) The nitrogen- and boron-rich hollow fiber obtained in step (1) is immersed in a mixed solution composed of terephthalic acid and metal salt aqueous solution, and then heated to carry out a hydrothermal reaction to obtain a flame-retardant hollow fiber after surface modification. (3) The flame-retardant hollow fiber obtained in step (2) is combined with natural plant fiber to obtain the flame-retardant automotive interior panel composite material.

2. The preparation method of the flame-retardant automotive interior panel composite material as described in claim 1, characterized in that, The mass ratio of the nitrogen-boron-rich dicarboxylic acid olefin copolymer, polyvinylpyrrolidone, and solvent is 15–35:10–20:40–70.

3. The preparation method of the flame-retardant automotive interior panel composite material as described in claim 1, characterized in that, The nitrogen- and boron-rich dicarboxylic acid olefin copolymer is obtained by copolymerization of a nitrogen- and boron-containing dicarboxylic acid olefin intermediate and a fluorinated vinyl group.

4. The preparation method of the flame-retardant automotive interior panel composite material as described in claim 3, characterized in that, The preparation method of the nitrogen- and boron-containing dicarboxylic acid olefin intermediate is as follows: 1,3,5-triacryloylhexahydro-1,3,5-triazine is uniformly dispersed in a solvent, and acrylamide-phenylboronic acid is added at a molar ratio of 2:1 to acrylamide-phenylboronic acid. The reaction is heated in an inert atmosphere for a period of time. After the reaction is completed, the reaction mixture is separated to obtain the nitrogen- and boron-containing dicarboxylic acid olefin intermediate.

5. The preparation method of the flame-retardant automotive interior panel composite material as described in claim 4, characterized in that, The acrylamide phenylboronic acid is at least one of 3-acrylamidophenylboronic acid, 3-methylacrylamidophenylboronic acid, and 2-acrylamidophenylboronic acid.

6. The preparation method of the flame-retardant automotive interior panel composite material as described in claim 3, characterized in that, The fluorinated ethylene is at least one of tetrafluoroethylene, trifluoroethylene, vinylidene fluoride, 1,2-difluorodichloroethylene, trifluorochloroethylene, and 1,1-dichloro-2,2-difluoroethylene.

7. The preparation method of the flame-retardant automotive interior panel composite material as described in claim 1, characterized in that, The core fluid is a polyethylene glycol aqueous solution with a mass concentration of 5-10%.

8. The method for preparing the flame-retardant automotive interior panel composite material as described in claim 1, characterized in that, The cation in the aqueous solution of the metal salt is at least one of calcium ion, magnesium ion, zinc ion or aluminum ion, and the anion is at least one of sulfate ion, chloride ion or nitrate ion.

9. The method for preparing the flame-retardant automotive interior panel composite material as described in claim 1, characterized in that, The hydrothermal reaction temperature is 95–105°C.

10. A flame-retardant automotive interior panel composite material, characterized in that, The composite material is prepared using the preparation method of the flame-retardant automotive interior panel composite material as described in any one of claims 1 to 9.

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