Phenolic resin material for high-elasticity fishing rod and preparation method of phenolic resin material

Abstract

The invention discloses a phenolic resin material for a high-elasticity fishing rod and a preparation method of the phenolic resin material, and belongs to the technical field of phenolic resin materials, a pyrrolidone-modified polyethylene derivative is used for modifying phenolic resin, the pyrrolidone-modified polyethylene derivative contains a polyvinylpyrrolidone group, and further contains an alkane long chain and a polyethylene chain; polyethylene derivatives modified by pyrrolidone react with phenolic resin to form a net structure, so that the mechanical strength of the material is improved, and through the combined action of the net structure and flexible groups, it is guaranteed that the material has excellent mechanical strength; the prepared high-elasticity phenolic resin material for the fishing rod not only has good flexibility, impact resistance and wear resistance, but also has excellent ageing resistance, and is an ideal material for the outdoor fishing rod.

Description

Technical Field

[0001] The invention belongs to the technical field of phenolic resin materials, and in particular to a phenolic resin material for a high-elasticity fishing rod and a preparation method thereof. Background Art

[0002] As people's living standards continue to improve, fishing has become an important entertainment and leisure activity for people. At present, most of the fishing rods on the market are carbon fiber fishing rods, which are made of shuttleless carbon fiber longitudinal cloth tubes and impregnated with resin for curing. Among them, phenolic resin has excellent mechanical properties, heat resistance and good compatibility with fibers, becoming one of the important materials for fishing rod manufacturing and is widely used in fishing rod manufacturing.

[0003] However, phenolic resin itself is brittle and has low toughness. In addition, phenolic resin is sensitive to environmental factors such as ultraviolet rays and temperature, has poor weather resistance, and is prone to aging and discoloration, which affects the appearance and service life of fishing rods. These defects limit the application of phenolic resin in high-end fishing rods. Therefore, it is of great significance to improve the performance of phenolic resin materials and develop a phenolic resin material with high elasticity for fishing rods. Summary of the invention

[0004] To solve the above problems, the object of the present invention is to provide a phenolic resin material for a high-elastic fishing rod and a preparation method thereof.

[0005] In order to achieve the above object, the present invention is implemented through the following technical solutions: A phenolic resin material for a high-elastic fishing rod, prepared by reacting a phenolic resin with a pyrrolidone-modified polyethylene derivative; The pyrrolidone-modified polyethylene derivative is prepared according to the following method: (1) Add 1,11-undecanediol, propylene bromide and sodium hydride to an organic solvent 1, stir and dissolve, heat to 50-60°C and react for 5-10 hours. After the reaction is completed, add water to the reaction solution to quench the reaction, then add dichloromethane, separate the organic phase, distill the obtained organic phase under reduced pressure to remove the solvent, and dry to obtain a terminal olefin undecane alcohol derivative; (2) Add N-vinyl pyrrolidone, the terminal olefin undecyl alcohol derivative obtained in step (1) and azobisisobutyronitrile to toluene, heat to 60-90°C and react for 12-20 hours. After the reaction is completed, remove the solvent by distillation under reduced pressure, wash the obtained residue with ethanol for 3-5 times, and dry to obtain a pyrrolidone-modified polyethylene derivative.

[0006] The organic solvent 1 in step (1) is acetone, tetrahydrofuran or acetonitrile.

[0007] The mass ratio of 1,11-undecanediol, propylene bromide, sodium hydride, organic solvent, water and dichloromethane in step (1) is 1:0.2-0.3:0.03-0.06:5-10:2-3:10-15.

[0008] The mass ratio of N-vinyl pyrrolidone, terminal olefin undecyl alcohol derivative, azobisisobutyronitrile and toluene in step (2) is 1-5:2-10:0.005-0.1:10-30.

[0009] The method for preparing the phenolic resin material for a high-elastic fishing rod comprises the following steps: 1) In parts by weight, 1 part of phenol, 0.65-0.8 parts of formaldehyde aqueous solution and 0.01-0.02 parts of acidic catalyst are added into a reactor, heated to 90-100° C., reacted for 4-8 hours, then heated to 145-150° C., evacuated to 0.03-0.06 MPa, stirred and reacted for 0.5-1 hour to obtain phenolic resin; 2) In parts by weight, add 1 part of the phenolic resin prepared in step 1) and 0.5-0.8 parts of a pyrrolidone-modified polyethylene derivative to 10-20 parts of an organic solvent 2, stir to dissolve, then add 2.5-3 parts of triphenylphosphine and 2-2.5 parts of diisopropyl azodicarboxylate, and react at 25-45°C for 3-5 hours. After the reaction is completed, filter and distill the filtrate under reduced pressure to remove the solvent. Wash the residue with ether 2-3 times to obtain a phenolic resin material for a highly elastic fishing rod.

[0010] The mass fraction of the formaldehyde aqueous solution in step 1) is 35-37%.

[0011] The acidic catalyst in step 1) is hydrochloric acid, oxalic acid, sulfuric acid or phosphoric acid.

[0012] The organic solvent 2 in step 2) is tetrahydrofuran, dichloromethane, acetone or acetonitrile.

[0013] Compared with the prior art, the present invention has the following advantages: The high-elasticity phenolic resin material for fishing rods of the present invention uses a phenolic resin modified by a pyrrolidone-modified polyethylene derivative. The pyrrolidone-modified polyethylene derivative contains a polyvinyl pyrrolidone group. Polyvinyl pyrrolidone has good flexibility and ductility, and has certain impact resistance and wear resistance, and excellent processing performance, thereby improving the mechanical properties of the material. In addition, polyvinyl pyrrolidone can effectively absorb ultraviolet radiation, has excellent weather resistance, can resist ultraviolet rays, high temperature, humidity and chemical corrosion, and is not prone to aging during long-term use.

[0014] The pyrrolidone-modified polyethylene derivative of the present invention also contains long alkane chains and polyethylene chains, which further increase the flexibility of the material; and by using the pyrrolidone-modified polyethylene derivative to react with phenolic resin to form a network structure, the mechanical strength of the material is improved. The network structure and the flexible group work together to ensure that the material has excellent mechanical strength.

[0015] The high-elastic phenolic resin material for fishing rods prepared by the present invention not only has good flexibility, impact resistance and wear resistance, but also has excellent anti-aging performance, and is an ideal material for outdoor fishing rods. DETAILED DESCRIPTION

[0016] In order to better understand the technical solution of the present invention, the above content of the present invention is further described in detail below through specific implementation methods in the form of embodiments, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples. All technologies realized based on the above content of the present invention belong to the scope of the present invention.

[0017] Example 1 Preparation of pyrrolidone-modified polyethylene derivatives: 0.1 kg of 1,11-undecanediol, 0.02 kg of propylene bromide and 0.003 kg of sodium hydride were added to 0.5 kg of acetone, stirred and dissolved, and heated to 50°C for reaction for 10 hours. After the reaction was completed, 0.2 kg of water was added to the reaction solution to quench the reaction, and 1 kg of dichloromethane was added to separate the organic phase. The obtained organic phase was distilled under reduced pressure to remove the solvent and dried to obtain a terminal olefin undecane alcohol derivative; 1 H NMR (300 MHz, 298 K, DMSO-d6): δ 5.95-6.17 (m, 1H), 5.48 (d, 1H), 5.29(d, 1H), 4.80 (s, 1H), 4.02 (d, 2H), 3.61-3.75(m, 2H), 3.31(t, 2H), 1.38-1.65(m, 8H), 1.17-1.39(m, 10H).

[0018] 0.1 kg of N-vinyl pyrrolidone, 0.2 kg of terminal olefin undecyl alcohol derivative and 0.0005 kg of azobisisobutyronitrile were added to 1 kg of toluene, heated to 60°C for reaction for 20 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed three times with ethanol and dried to obtain a pyrrolidone-modified polyethylene derivative.

[0019] Preparation of phenolic resin materials for high elastic fishing rods: 1 kg of phenol, 0.65 kg of a 37% formaldehyde aqueous solution and 0.01 kg of oxalic acid were added to a reactor, heated to 90°C, reacted for 8 hours, then heated to 145°C, evacuated to 0.03 MPa, stirred and reacted for 1 hour to obtain a phenolic resin; Add 1kg of phenolic resin and 0.5kg of pyrrolidone-modified polyethylene derivative to 10kg of dichloromethane, stir to dissolve, then add 2.5kg of triphenylphosphine and 2kg of diisopropyl azodicarboxylate, and react at 25°C for 5h. After the reaction is completed, filter and distill the filtrate under reduced pressure to remove the solvent. Wash the residue twice with ether to obtain a high-elastic phenolic resin material for fishing rods.

[0020] Example 2 Preparation of pyrrolidone-modified polyethylene derivatives: 0.1 kg of 1,11-undecanediol, 0.022 kg of propylene bromide and 0.0038 kg of sodium hydride were added to 0.6 kg of acetonitrile, stirred and dissolved, and heated to 52°C for reaction for 9 hours. After the reaction was completed, 0.24 kg of water was added to the reaction solution to quench the reaction, and 1.1 kg of dichloromethane was added to separate the organic phase. The obtained organic phase was distilled under reduced pressure to remove the solvent and dried to obtain a terminal olefin undecane alcohol derivative; 0.2 kg of N-vinyl pyrrolidone, 0.4 kg of terminal olefin undecyl alcohol derivative and 0.001 kg of azobisisobutyronitrile were added to 1.5 kg of toluene, heated to 70°C for reaction for 18 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed 4 times with ethanol and dried to obtain a pyrrolidone-modified polyethylene derivative.

[0021] Preparation of phenolic resin materials for high elastic fishing rods: 1 kg of phenol, 0.7 kg of a 36% formaldehyde aqueous solution and 0.012 kg of hydrochloric acid were added into a reactor, heated to 94°C, reacted for 7 hours, then heated to 148°C, evacuated to 0.04 MPa, stirred and reacted for 0.9 hours to obtain a phenolic resin; Add 1kg of phenolic resin and 0.6kg of pyrrolidone-modified polyethylene derivative to 12kg of acetone, stir to dissolve, then add 2.6kg of triphenylphosphine and 2.1kg of diisopropyl azodicarboxylate, and react at 30°C for 4.5h. After the reaction is completed, filter and distill the filtrate under reduced pressure to remove the solvent. Wash the residue three times with ether to obtain a highly elastic phenolic resin material for fishing rods.

[0022] Example 3 Preparation of pyrrolidone-modified polyethylene derivatives: 0.1 kg of 1,11-undecanediol, 0.025 kg of propylene bromide and 0.0042 kg of sodium hydride were added to 0.75 kg of tetrahydrofuran, stirred and dissolved, and heated to 55°C for reaction for 7 hours. After the reaction was completed, 0.26 kg of water was added to the reaction solution to quench the reaction, and 1.3 kg of dichloromethane was added to separate the organic phase. The obtained organic phase was distilled under reduced pressure to remove the solvent and dried to obtain a terminal olefin undecane alcohol derivative; 0.3 kg of N-vinyl pyrrolidone, 0.5 kg of terminal olefin undecyl alcohol derivative and 0.004 kg of azobisisobutyronitrile were added to 2 kg of toluene, heated to 75°C for reaction for 15 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed with ethanol 5 times and dried to obtain a pyrrolidone-modified polyethylene derivative.

[0023] Preparation of phenolic resin materials for high elastic fishing rods: 1 kg of phenol, 0.75 kg of a 36% formaldehyde aqueous solution and 0.015 kg of phosphoric acid were added to a reactor, heated to 95°C, reacted for 6 hours, then heated to 148°C, evacuated to 0.05 MPa, stirred and reacted for 0.75 hours to obtain a phenolic resin; Add 1kg of phenolic resin and 0.7kg of pyrrolidone-modified polyethylene derivative to 15kg of acetonitrile, stir to dissolve, then add 2.8kg of triphenylphosphine and 2.3kg of diisopropyl azodicarboxylate, and react at 35°C for 4h. After the reaction is completed, filter and distill the filtrate under reduced pressure to remove the solvent. Wash the residue three times with ether to obtain a highly elastic phenolic resin material for fishing rods.

[0024] Example 4 Preparation of pyrrolidone-modified polyethylene derivatives: 0.1 kg of 1,11-undecanediol, 0.027 kg of propylene bromide and 0.005 kg of sodium hydride were added to 0.9 kg of tetrahydrofuran, stirred and dissolved, and heated to 57°C for reaction for 7 hours. After the reaction was completed, 0.28 kg of water was added to the reaction solution to quench the reaction, and 1.4 kg of dichloromethane was added to separate the organic phase. The obtained organic phase was distilled under reduced pressure to remove the solvent and dried to obtain a terminal olefin undecane alcohol derivative; 0.4 kg of N-vinyl pyrrolidone, 0.8 kg of terminal olefin undecyl alcohol derivative and 0.007 kg of azobisisobutyronitrile were added to 2.5 kg of toluene, heated to 80°C for reaction for 14 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed with ethanol 5 times and dried to obtain a pyrrolidone-modified polyethylene derivative.

[0025] Preparation of phenolic resin materials for high elastic fishing rods: 1 kg of phenol, 0.78 kg of a 36% formaldehyde aqueous solution and 0.018 kg of oxalic acid were added to a reactor, heated to 97°C, reacted for 5 hours, then heated to 146°C, evacuated to 0.05 MPa, stirred and reacted for 0.6 hours to obtain a phenolic resin; Add 1kg of phenolic resin and 0.75kg of pyrrolidone-modified polyethylene derivative to 17kg of tetrahydrofuran, stir to dissolve, then add 2.9kg of triphenylphosphine and 2.4kg of diisopropyl azodicarboxylate, and react at 40°C for 3.5h. After the reaction is completed, filter and distill the filtrate under reduced pressure to remove the solvent. Wash the residue three times with ether to obtain a highly elastic phenolic resin material for fishing rods.

[0026] Example 5 Preparation of pyrrolidone-modified polyethylene derivatives: 0.1 kg of 1,11-undecanediol, 0.03 kg of propylene bromide and 0.006 kg of sodium hydride were added to 1 kg of acetone, stirred and dissolved, and then heated to 60°C for reaction for 5 hours. After the reaction was completed, 0.3 kg of water was added to the reaction solution to quench the reaction, and then 1.5 kg of dichloromethane was added to separate the organic phase. The obtained organic phase was distilled under reduced pressure to remove the solvent and dried to obtain a terminal olefin undecane alcohol derivative; 0.5 kg of N-vinyl pyrrolidone, 1 kg of terminal olefin undecyl alcohol derivative and 0.01 kg of azobisisobutyronitrile were added to 3 kg of toluene, heated to 90°C for reaction for 12 hours. After the reaction was completed, the solvent was removed by reduced pressure distillation, and the residue was washed with ethanol 5 times and dried to obtain a pyrrolidone-modified polyethylene derivative.

[0027] Preparation of phenolic resin materials for high elastic fishing rods: 1 kg of phenol, 0.8 kg of 35% formaldehyde aqueous solution and 0.02 kg of sulfuric acid were added into the reactor, heated to 100°C, reacted for 4 hours, then heated to 150°C, evacuated to 0.06 MPa, stirred and reacted for 0.5 hours to obtain phenolic resin; Add 1kg of phenolic resin and 0.8kg of pyrrolidone-modified polyethylene derivative to 20kg of acetone, stir to dissolve, then add 3kg of triphenylphosphine and 2.5kg of diisopropyl azodicarboxylate, and react at 45°C for 3h. After the reaction is completed, filter and distill the filtrate under reduced pressure to remove the solvent. Wash the residue three times with ether to obtain a highly elastic phenolic resin material for fishing rods.

[0028] Example 6 Preparation of pyrrolidone-modified polyethylene derivatives: 0.1 kg of 1,11-undecanediol, 0.025 kg of propylene bromide and 0.003 kg of sodium hydride were added to 1 kg of acetonitrile, stirred and dissolved, and heated to 60°C for reaction for 10 hours. After the reaction was completed, 0.3 kg of water was added to the reaction solution to quench the reaction, and 1.5 kg of dichloromethane was added to separate the organic phase. The obtained organic phase was distilled under reduced pressure to remove the solvent and dried to obtain a terminal olefin undecane alcohol derivative; 0.5 kg of N-vinyl pyrrolidone, 0.2 kg of terminal olefin undecyl alcohol derivative and 0.005 kg of azobisisobutyronitrile were added to 2.5 kg of toluene, heated to 60°C for reaction for 12 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the residue was washed with ethanol 5 times and dried to obtain a pyrrolidone-modified polyethylene derivative.

[0029] Preparation of phenolic resin materials for high elastic fishing rods: 1 kg of phenol, 0.8 kg of 37% formaldehyde aqueous solution and 0.01 kg of oxalic acid were added into a reactor, heated to 100°C, reacted for 8 hours, then heated to 150°C, evacuated to 0.05 MPa, stirred and reacted for 0.75 hours to obtain phenolic resin; Add 1kg of phenolic resin and 0.6kg of pyrrolidone-modified polyethylene derivative to 10kg of acetone, stir to dissolve, then add 2.8kg of triphenylphosphine and 2.3kg of diisopropyl azodicarboxylate, and react at 45°C for 5h. After the reaction is completed, filter and distill the filtrate under reduced pressure to remove the solvent. Wash the residue twice with ether to obtain a highly elastic phenolic resin material for fishing rods.

[0030] Experimental example In parts by weight, 60 parts of the high-elasticity phenolic resin material for fishing rods prepared in Examples 1 to 6, 2 parts of magnesium oxide and 1 part of calcium stearate were added to a high-speed mixer and mixed evenly, and then 70 parts of acetone, 20 parts of glass fiber and 5 parts of nano-carbon fiber were added thereto. After stirring and mixing for 2 hours, 6 parts of hexamethylenetetramine were added and continued to stir for 10 minutes. After stopping stirring, the solvent was evaporated to obtain a preform. The obtained preform was cured at 120°C for 2 hours, then cured at 150°C for 2 hours, and finally cured at 180°C for 2 hours to obtain a phenolic resin-based composite material for fishing rods. Comparative Example: An unmodified phenolic resin of model PF-YSJ-1904-1 (the applicant's own product) was used to prepare a phenolic resin-based composite material for fishing rods according to the above method. The obtained phenolic resin-based composite material for fishing rods was subjected to performance testing. The elasticity test method is as follows: the obtained phenolic resin-based composite material for fishing rods is cut into a cuboid, and the initial height is measured as h. 1 , apply pressure to the object to be tested to compress it, and measure the height h 2 After the external force is removed, the object to be tested rebounds naturally, and the measured height is h 3, the elasticity calculation formula is: elasticity = (h 3 -h 2 ) / (h 1 -h 2 )×100%. The test results are shown in Table 1.

[0031] Table 1 Performance parameters of materials prepared in Examples 1 to 6 and Comparative Examples

[0032] It can be seen from the results in Table 1 that the phenolic resin-based composite material for fishing rods prepared by using the high-elastic phenolic resin material for fishing rods of the present invention has high elasticity and good flexibility, and at the same time has excellent anti-aging performance, and has good application prospects as a material for outdoor fishing rods.

[0033] Although the above describes the specific implementation methods of the present invention, it does not limit the scope of protection of the present invention. Based on the technical solution of the present invention, various modifications or variations that can be made by those skilled in the art without creative work are still within the scope of protection of the present invention.

Claims

1. A phenolic resin material for a high elastic fishing rod, Features: It is prepared by reacting phenolic resin with pyrrolidone-modified polyethylene derivatives; The pyrrolidone-modified polyethylene derivative is prepared according to the following method: (1) Add 1,11-undecanediol, propylene bromide and sodium hydride to an organic solvent 1, stir and dissolve, heat to 50-60°C and react for 5-10 hours. After the reaction is completed, add water to the reaction solution to quench the reaction, then add dichloromethane, separate the organic phase, distill the obtained organic phase under reduced pressure to remove the solvent, and dry to obtain a terminal olefin undecane alcohol derivative; (2) Add N-vinyl pyrrolidone, the terminal olefin undecyl alcohol derivative obtained in step (1) and azobisisobutyronitrile to toluene, heat to 60-90°C and react for 12-20 hours. After the reaction is completed, remove the solvent by distillation under reduced pressure, wash the obtained residue with ethanol for 3-5 times, and dry to obtain a pyrrolidone-modified polyethylene derivative.

2. The phenolic resin material for a highly elastic fishing rod according to claim 1, Features: The organic solvent 1 in step (1) is acetone, tetrahydrofuran or acetonitrile.

3. The phenolic resin material for a highly elastic fishing rod according to claim 1, Features: The mass ratio of 1,11-undecanediol, propylene bromide, sodium hydride, organic solvent, water and dichloromethane in step (1) is 1:0.2-0.3:0.03-0.06:5-10:2-3:10-15.

4. The phenolic resin material for a highly elastic fishing rod according to claim 1, Features: The mass ratio of N-vinyl pyrrolidone, terminal olefin undecyl alcohol derivative, azobisisobutyronitrile and toluene in step (2) is 1-5:2-10:0.005-0.1:10-30.

5. A method for preparing the phenolic resin material for a highly elastic fishing rod according to claim 1, Features: The following steps are involved: 1) In parts by weight, 1 part of phenol, 0.65-0.8 parts of formaldehyde aqueous solution and 0.01-0.02 parts of acidic catalyst are added into a reactor, heated to 90-100° C., reacted for 4-8 hours, then heated to 145-150° C., evacuated to 0.03-0.06 MPa, stirred and reacted for 0.5-1 hour to obtain phenolic resin; 2) In parts by weight, add 1 part of the phenolic resin prepared in step 1) and 0.5-0.8 parts of a pyrrolidone-modified polyethylene derivative to 10-20 parts of an organic solvent 2, stir to dissolve, then add 2.5-3 parts of triphenylphosphine and 2-2.5 parts of diisopropyl azodicarboxylate, and react at 25-45°C for 3-5 hours. After the reaction is completed, filter and distill the filtrate under reduced pressure to remove the solvent. Wash the residue with ether 2-3 times to obtain a phenolic resin material for a highly elastic fishing rod.

6. The method for preparing the phenolic resin material for a high elastic fishing rod according to claim 5, Features: The mass fraction of the formaldehyde aqueous solution in step 1) is 35-37%.

7. The method for preparing the phenolic resin material for a high elastic fishing rod according to claim 5, Features: The acidic catalyst in step 1) is hydrochloric acid, oxalic acid, sulfuric acid or phosphoric acid.

8. The method for preparing the phenolic resin material for a high elastic fishing rod according to claim 5, Features: The organic solvent 2 in step 2) is tetrahydrofuran, dichloromethane, acetone or acetonitrile.

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