Functionalized polyethers, polydicyclopentadiene composites, and methods of making the same

Abstract

The application discloses a kind of functional polyether, polydicyclopentadiene composite material and its preparation method.Functional polyether with end group being norbornene structure is directly mixed with DCPD, filler and auxiliary agent, then segmented polymerization is carried out, the toughness and low temperature performance of matrix are fundamentally improved, meanwhile, the introduction of functional polyether effectively improves the dispersity and interface effect of filler in matrix, to achieve the purpose of reinforcing and toughening polydicyclopentadiene composite material;Meanwhile, the functional groups on the side chain of polyether make the obtained polydicyclopentadiene composite material have higher heat resistance, aging resistance, flame resistance and antibacterial property.The method has low production cost, short production cycle, simple preparation method, and the modified polydicyclopentadiene composite material meets various engineering material and special material application scenarios.

Description

Technical Field

[0001] This invention belongs to the field of polydicyclopentadiene materials technology, specifically relating to a functionalized polyether, polydicyclopentadiene composite material and its preparation method. Background Technology

[0002] Polydicyclopentadiene (p-DCPD) has a three-dimensional network structure and is a thermosetting polymer material with advantages such as light weight, low and readily available raw materials, high strength, low water absorption, acid and alkali resistance, and low dielectric constant. At the same time, it has a fast curing speed, short production cycle, and low requirements for molding environment conditions. It is especially suitable for reaction injection molding to produce complex or thin parts. Currently, p-DCPD has a wide range of applications in aerospace, shipbuilding, automotive and other fields.

[0003] However, p-DCPD has a high crosslinking density and low molecular weight between crosslinking points, resulting in high rigidity, insufficient toughness, and poor impact resistance in the matrix itself. This makes it difficult to use at low temperatures, limiting its further application in engineering and specialty materials. Current research primarily addresses this issue by directly using solid fillers, reporting composites such as p-DCPD / carbon fiber, p-DCPD / carbon nanotubes, and p-DCPD / glass fiber. However, since p-DCPD itself is entirely hydrocarbon-based and lacks groups that can interact with solid fillers, the wettability of the p-DCPD matrix to the filler is poor, leading to poor compatibility. Under external forces, interfacial dewetting easily occurs at the matrix-interface, creating stress concentration points and ultimately causing overall material failure. Therefore, direct modification with fillers has limited effect on improving the performance of p-DCPD, especially its impact resistance. Secondly, a few studies have reported the use of polar small molecule modifiers to improve the mechanical properties of DCPD composites. However, due to the extremely low viscosity of DCPD monomers, which is close to that of water, the filler is prone to sedimentation during the curing process. This results in poor uniformity of filler dispersion in the matrix, leading to more defects and ultimately material failure. Therefore, the use of small molecule modifiers is not ideal for improving performance.

[0004] Based on the above background, it is necessary to develop a new type of copolymer component that can improve the toughness of the p-DCPD matrix, enhance the compatibility between the matrix and the filler, and solve the problem of filler settling during the curing process. Summary of the Invention

[0005] To address the aforementioned problems in the existing technology, the present invention aims to provide a functionalized polyether and utilize this functionalized polyether to in-situ toughen a polydicyclopentadiene composite material. The present invention introduces a polyether oligomer containing functionalized groups, which copolymerizes with dicyclopentadiene (DCPD) monomers, fundamentally improving the toughness and low-temperature performance of the matrix. Simultaneously, polar functionalized groups such as cyano, ester, and Schiff bases can improve the compatibility between the filler and the matrix, as well as the dispersibility of the filler in the matrix, giving the DCPD composite material excellent flame retardancy and antibacterial properties. The resulting modified polydicyclopentadiene material exhibits high strength, toughness, excellent low-temperature performance, and also possesses excellent flame retardancy and antibacterial properties.

[0006] To achieve the above-mentioned objectives, the present invention adopts the following solution:

[0007] A functionalized polyether in-situ toughened polydicyclopentadiene composite material comprises the following components in parts by mass: 23.5%–61.5% dicyclopentadiene, 5.5%–13.0% functionalized polyether, 25%–60% solid filler, 0.05%–0.3% catalyst, 0.1%–0.5% polymerization inhibitor, and 1.0%–3.3% antioxidant.

[0008] Furthermore, the solid filler is selected from one or more of graphene, carbon fiber, carbon nanotubes, glass fiber, montmorillonite, carbon black or silica, with carbon fiber being preferred.

[0009] Furthermore, the catalyst includes one or more of tungsten-based catalysts or ruthenium-based carbene catalysts, preferably ruthenium-based carbene catalysts, such as second-generation Grubbs catalysts.

[0010] Furthermore, the polymerization inhibitor includes one or more of phosphite or phosphate compounds.

[0011] Furthermore, the antioxidant includes one or more of antioxidant 1010 or antioxidant 4010.

[0012] Furthermore, the functionalized polyether is a functionalized polyether with a norbornene end group, which is prepared from an acid anhydride containing a norbornene group and a polyetheramine.

[0013] Specifically, the functionalized polyether can be prepared using existing technologies, such as the preparation method described in CN116535621A.

[0014] Specifically, in a preferred embodiment, the present invention provides a method for preparing a functionalized polyether, comprising the following steps:

[0015] (1) Prepare an organic solution of an acid anhydride containing norbornene group, add polyetheramine and triethylamine and react overnight at a reaction temperature of 25℃~100℃;

[0016] (2) After the reaction is complete, the resulting solution is distilled under reduced pressure to obtain a yellow viscous liquid, which is a functionalized polyether with a norbornene end group.

[0017] Further, the solvent of the organic solution in step (1) is dichloromethane;

[0018] Furthermore, the anhydride containing norbornene groups mentioned in step (1) is such as norbornene anhydride, etc.

[0019] Further, the molar ratio of the anhydride containing norbornene groups, polyetheramine, and triethylamine in step (1) is (0.03-0.06): 0.03: (0.02-0.05).

[0020] Further, the polyetheramine mentioned in step (1) is selected from one or more of polyetheramines containing Schiff bases, chlorinated polyetheramines, cyano-containing polyetheramines, and ester-containing polyetheramines. Specifically, it can be one or more of the following polymers, but not limited to the following polymers. The molecular weight of the polyetheramine is preferably between 200 g / mol and 2000 g / mol.

[0021]

[0022] Furthermore, the polyetheramines listed above can be prepared using the preparation method described in CN117327212A, or commercially available raw materials can be used.

[0023] Furthermore, the vacuum distillation in step (2) can be carried out under existing technical conditions. In a specific embodiment, vacuum distillation at 70-100°C for 1-5 hours can be used.

[0024] In another aspect, the present invention provides a method for preparing a functionalized polyether in-situ toughened polydicyclopentadiene composite material, the preparation method comprising the following steps:

[0025] (1) Mix the dicyclopentadiene monomer with the functionalized polyether, polymerization inhibitor and antioxidant evenly;

[0026] (2) Add the solid filler to the system obtained in step (1) and mix thoroughly;

[0027] (3) Prepare a catalyst solution, add the catalyst solution to the system obtained in step (2) and mix evenly;

[0028] (4) After degassing the mixture obtained in step (3), pour it into a mold and heat it to cure it to obtain a functionalized polyether in-situ toughened polydicyclopentadiene composite material.

[0029] Furthermore, in step (3), the concentration of the catalyst solution is 50-200 g / L, and the solvent used can be selected from toluene, cyclohexane, etc.

[0030] Furthermore, the heating and curing described in step (4) is not limited in this invention, as long as the curing effect is achieved. In a specific embodiment, for example, pre-curing can be carried out at 35-50℃ for 1-3 hours, and then cured at 80-100℃ for 3-12 hours.

[0031] The beneficial effects of this invention are as follows:

[0032] (1) The polyether structure has excellent flexibility and low temperature performance. This invention is the first to use the method of direct copolymerization of oligomers with DCPD monomers to introduce the polyether structure into the p-DCPD matrix, which fundamentally improves the toughness, impact resistance and low temperature performance of the p-DCPD matrix.

[0033] (2) Functionalized polyether is an oligomer whose viscosity increases with increasing molecular weight. This solves the problem of low viscosity of pure DCPD monomer and easy sedimentation of solid filler during curing, effectively improving the dispersibility of filler in matrix and further improving the mechanical properties of composite material.

[0034] (3) The introduction of functional groups improves the compatibility and interfacial interaction between the matrix and the solid filler, and greatly improves the mechanical properties of p-DCPD composite material; at the same time, the introduction of functional groups gives the composite material good flame retardancy and antibacterial properties. Detailed Implementation

[0035] To better understand the technical solution of the present invention, the content of the present invention will be further described below with reference to the following specific embodiments, but the content of the present invention is not limited to the following embodiments.

[0036] The main raw material sources in the embodiments and comparative examples of this invention are as follows; unless otherwise specified, all other raw materials were obtained through ordinary commercial channels.

[0037] Polyetheramine: Custom-made by Beijing Innocare Technology Co., Ltd.

[0038] Toluene: Beijing Innocare Technology Co., Ltd.

[0039] Dicyclopentadiene: Beijing Innocare Technology Co., Ltd.;

[0040] Norborneol olefinic anhydride: Beijing Inokai Technology Co., Ltd.;

[0041] Triethylamine: Beijing Innocare Technology Co., Ltd.;

[0042] Dichloromethane: Beijing Innocare Technology Co., Ltd.;

[0043] Short-cut carbon fiber: Sigma-Aldrich (Shanghai) Trading Co., Ltd.;

[0044] Carbon nanotubes: Sigma-Aldrich (Shanghai) Trading Co., Ltd.;

[0045] Fiberglass: Sigma-Aldrich (Shanghai) Trading Co., Ltd.;

[0046] Second-generation Grubbs catalyst: Sigma-Aldrich (Shanghai) Trading Co., Ltd.;

[0047] The performance test parameters and corresponding test methods in the various embodiments and comparative examples of this invention are as follows:

[0048] Tensile strength: conformed to national standard GB / T 1040.2-2006 "Determination of tensile properties of plastics";

[0049] Elongation at break: conformed to national standard GB / T 1040.2-2006 "Determination of tensile properties of plastics";

[0050] Impact strength: conforming to ASTM D6110-2010 standard;

[0051] Limiting oxygen index: Based on national standard GB / T 2406.1-2008 "Test Method for Burning Performance of Plastics";

[0052] Viscosity: conformed to national standard GB / T 1632-1993 "Determination of viscosity and intrinsic viscosity of dilute polymer solutions";

[0053] Aging test: The anti-aging performance was determined according to the national standard GB / T 3512-2014 "Accelerated aging and heat resistance test of vulcanized rubber and thermoplastic rubber in hot air", specifically, accelerated aging at 120℃ for 15 days.

[0054] Example 1

[0055] The structure of a polyetheramine oligomer containing Schiff bases is as follows, with a molecular weight of 600 g / mol.

[0056]

[0057] 0.05 mol of an anhydride containing norbornene groups was added to 150 mL of dichloromethane solution and stirred at room temperature until completely dissolved. Then, 0.025 mol of the above-mentioned Schiff base polyetheramine oligomer and 0.03 mol of triethylamine were added, and the reaction was allowed to proceed overnight at room temperature. The resulting solution was distilled under reduced pressure to obtain functionalized polyether A, the structure of which is shown below:

[0058]

[0059] The formulation of the functionalized polyether in-situ toughened polydicyclopentadiene composite material is shown in the table below, where the values ​​are by mass.

[0060] Components Comparative Example 1 Formula I Formula II Formula III DCPD / % 65 59.5 59 56 Functionalized A polyether / % 0 5.5 6 9 Short-cut carbon fiber / % 32 32 32 32 Second-generation Grubbs catalyst / % 0.2 0.2 0.2 0.2 Polymerization inhibitor TPP / % 0.5 0.5 0.5 0.5 Antioxidant 1010 / % 2.3 2.3 2.3 2.3

[0061] According to the formulation, the functionalized polyether in-situ toughened polydicyclopentadiene composite material was prepared by the following method:

[0062] (1) Heat the dicyclopentadiene monomer to 35°C to melt it, and mix it evenly with the functionalized polyether, polymerization inhibitor and antioxidant.

[0063] (2) Add the solid filler carbon fiber to the system obtained in step (1) and ultrasonically disperse for 1 hour;

[0064] (3) Dissolve the catalyst in toluene at a concentration of 100 g / L, add the dissolved catalyst solution to the system obtained in step (2) and mix well;

[0065] (4) After degassing the mixture obtained in step (3), pour it into the mold, heat it to 35°C, and pre-cur it for 2 hours; then heat it to 80°C for post-curing for 6 hours.

[0066] The performance test results are shown in the table below:

[0067]

[0068]

[0069] Example 2

[0070] The structure of a Cl-containing polyetheramine oligomer is as follows, with a molecular weight of 900 g / mol.

[0071]

[0072] The method for preparing the functionalized polyether is the same as in Example 1, yielding functionalized polyether B, the structure of which is shown below:

[0073]

[0074] The formulations of Cl-functionalized polyether-modified polydicyclopentadiene composites are shown in the table below, where the values ​​are by mass:

[0075]

[0076] The functionalized polyether in-situ toughened polydicyclopentadiene composite material was prepared using the same method as in Example 1, and the performance test results are shown in the table below.

[0077]

[0078]

[0079] Example 3

[0080] A cyano-containing functionalized polyetheramine has the following structure and a molecular weight of 400 g / mol.

[0081]

[0082] The method for preparing the functionalized polyether is the same as in Example 1, yielding functionalized polyether C, the structure of which is shown below:

[0083]

[0084] The formulation of the cyano-functionalized polyether-modified polydicyclopentadiene composite material is shown in the table below, where the values ​​are by mass:

[0085]

[0086] The functionalized polyether in-situ toughened polydicyclopentadiene composite material was prepared using the same method as in Example 1, and the performance test results are shown in the table below:

[0087]

[0088]

[0089] Example 4

[0090] An ester-containing functionalized polyetheramine has the following structure and a molecular weight of 1100 g / mol.

[0091]

[0092] The method for preparing the functionalized polyether is the same as in Example 1, yielding functionalized polyether D with the following structure:

[0093]

[0094] The formulation of the functionalized polyether in-situ toughened polydicyclopentadiene composite material is shown in the table below, where the values ​​are by mass:

[0095]

[0096] The functionalized polyether in-situ toughened polydicyclopentadiene composite material was prepared using the same method as in Example 1, and the performance test results are shown in the table below:

[0097]

[0098]

Claims

1. A functionalized polyether in-situ toughened polydicyclopentadiene composite, characterized in that, The application relates to a functionalized polyether in-situ toughened polydicyclopentadiene composite material, which comprises the following components in mass fraction: 23.5-61.5% of dicyclopentadiene, 5.5-13.0% of functionalized polyether, 25-60% of solid filler, 0.05-0.3% of catalyst, 0.1-0.5% of polymerization inhibitor and 1.0-3.3% of antioxidant. The preparation method of the functionalized polyether comprises the following steps: (1) preparing an organic solution of acid anhydride containing a norbornene group, adding polyether amine and triethylamine and reacting overnight; (2) after the reaction is completed, the obtained solution is distilled under reduced pressure to obtain yellow viscous liquid as the functionalized polyether.

2. The functionalized polyether in-situ toughened polydicyclopentadiene composite material according to claim 1, wherein, The acid anhydride containing a norbornene group is norbornene diacid anhydride; the polyether amine is selected from one or more of Schiff base group-containing polyether amine, chlorine-containing polyether amine, cyano-containing polyether amine and ester group-containing polyether amine, and the molecular weight is 200-2000 g / mol; the molar ratio of the acid anhydride containing a norbornene group, the polyether amine and triethylamine is (0.03-0.06):0.03:(0.02-0.05).

3. The functionalized polyether in-situ toughened polydicyclopentadiene composite of claim 1, wherein, The solid filler comprises one or more of graphene, carbon fiber, carbon nanotube, glass fiber, montmorillonite, carbon black or white carbon black.

4. The functionalized polyether in-situ toughened polydicyclopentadiene composite of claim 3, wherein, The catalyst comprises one or more of tungsten-based catalyst or ruthenium-based carbene catalyst.

5. The functionalized polyether in-situ toughened polydicyclopentadiene composite of claim 1, wherein, The catalyst is a second-generation Grubbs catalyst.

6. The functionalized polyether in-situ toughened polydicyclopentadiene composite of claim 1, wherein, The polymerization inhibitor comprises one or more of phosphite or phosphate compound.

7. The functionalized polyether in-situ toughened polydicyclopentadiene composite of claim 1, wherein, The antioxidant comprises one or more of antioxidant 1010 or antioxidant 4010.

8. The functionalized polyether in-situ toughened polydicyclopentadiene composite of claim 1, wherein, The solvent of the organic solution in the preparation method of the functionalized polyether is dichloromethane.

9. A method for the preparation of a functionalized polyether in-situ toughened polydicyclopentadiene composite according to claim 1, characterized in that, The polyether amine is one or more of the following polymers, The application further discloses a preparation method of the functionalized polyether in-situ toughened polydicyclopentadiene composite material, which comprises the following steps: (1) uniformly mixing dicyclopentadiene monomer with the functionalized polyether, the polymerization inhibitor and the antioxidant; (2) adding the solid filler into the mixed system obtained in the step (1); (3) preparing a catalyst solution, adding the catalyst solution into the system obtained in the step (2) and uniformly mixing; 10. The method of claim 9, wherein, (4) degassing the mixed system obtained in the step (3) and pouring into a mold to be heated and solidified, so that the functionalized polyether in-situ toughened polydicyclopentadiene composite material is obtained.

11. The preparation method according to claim 9, characterized in that, The concentration of the catalyst solution in the step (3) is 50-200 g / L, and the solvent used is selected from toluene and cyclohexane. The heating and solidification in the step (4) is pre-solidified at 35-50 DEG C for 1-3 h, and then solidified at 80-100 DEG C for 3-12 h.

Images