Preparation process and application of polyurethane plastic material

Abstract

The invention relates to the technical field of polyurethane, and discloses a preparation process and application of a polyurethane plastic material. 65-80 parts by weight of polyurethane resin, 20-35 parts by weight of fluororubber, 3-12 parts by weight of fluorine-containing hyperbranched polyurethane, 4-10 parts by weight of a reinforcing agent and the like are added into an internal mixer to be mixed; and then adding 0.5-0.9 part by weight of bisphenol AF and 0.1-0.2 part by weight of benzyl triphenyl phosphorus chloride, and carrying out heat treatment to obtain the polyurethane plastic material. The fluorine-containing hyperbranched polyurethane contains a polyurethane main chain and a fluorine-containing group, so that the fluorine-containing hyperbranched polyurethane can play a role of a compatibilizer, the compatibility between polyurethane resin and fluororubber is improved, and the polyurethane plastic material has better mechanical properties. Meanwhile, the wear resistance and the water resistance and water resistance are improved.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane, in particular to a preparation process and application of a polyurethane plastic material. Background Art

[0002] Polyurethane is a high-performance polymer material that has both the strength and processing properties of plastics and the elasticity and oil resistance of rubber. It is widely used in plastic tracks, sports equipment, building materials, thermal insulation materials, etc. Fluorine rubber contains fluorine atoms on the carbon atoms of the main chain or side chain, which makes it have excellent wear resistance, high temperature resistance, anti-aging, waterproof and other properties.

[0003] Combining fluororubber with polyurethane can produce a composite material with better performance. The Chinese invention patent publication with the announcement number CN112080130B discloses a thermoplastic polyurethane elastomer / fluororubber blend material and its preparation method, which uses polyurethane elastomer TPU, fluororubber, fluorinated polyurethane, polydopamine modified layered inorganic matter and the like as raw materials, and the prepared blend material has good processing performance, flame retardancy, heat resistance and other properties. Compared with the polyurethane / fluororubber blend material of the patent, the fluororubber / polyurethane plastic material of the present invention has better wear resistance, water resistance and other properties. Summary of the invention

[0004] The invention resolves the problem that the polyurethane material has poor water resistance, wear resistance, heat resistance and other properties.

[0005] The technical solution of the present invention is: a preparation process of polyurethane plastic material: (1) Hexamethylene diisocyanate, fluorinated naphthyl polymerization monomer and dibutyltin dilaurate are added to N,N-dimethylformamide, and the mixture is stirred at 65-80°C for 3-5 hours in a nitrogen atmosphere. After cooling, the solution is poured into water, filtered, washed with dichloromethane and ethanol in turn, and dried to obtain a fluorinated hyperbranched polyurethane.

[0006] (2) Add 65-80 parts by weight of polyurethane resin, 20-35 parts by weight of fluororubber, 3-12 parts by weight of fluorine-containing hyperbranched polyurethane, 1.2-2.2 parts by weight of calcium hydroxide, 0.6-1.2 parts by weight of magnesium oxide, 0.2-0.4 parts by weight of processing aid, and 4-10 parts by weight of reinforcing agent into an internal mixer, and mix at 150-165° C. for 30-40 minutes. Then, add 0.5-0.9 parts by weight of bisphenol AF and 0.1-0.2 parts by weight of benzyltriphenylphosphonium chloride, and mix for 10-15 minutes. Then, heat press the materials in a flat vulcanizer at 170-175° C. under a pressure of 10-12 MP for 10-20 minutes, and then heat treat them in a blast drying oven at 150-170° C. for 6-12 hours, and cool to obtain a polyurethane plastic material.

[0007] Preferably, the molar ratio of hexamethylene diisocyanate, fluorinated naphthyl polymer monomer and dibutyltin dilaurate in (1) is (200-220):100:(0.04-0.05).

[0008] Preferably, the preparation process of the fluorine-containing naphthyl polymerization monomer is as follows: add 1,5-naphthalene diamine (CAS No. 80-08-0) and 3-(2,2,3,3-tetrafluoropropoxy)-1,2-propylene oxide (CAS No. 19932-26-4) in a molar ratio of 1:2 to tetrahydrofuran, react at 40-50°C for 7-10 hours, distill under reduced pressure, add dichloromethane and water, extract by oscillation, dry the organic phase to remove water, wash with petroleum ether, and dry to obtain the fluorine-containing naphthyl polymerization monomer.

[0009] Preferably, the processing aid in (2) is palm wax, stearic acid or polyethylene wax, and the reinforcing agent is carbon black or white carbon black.

[0010] Preferably, polyurethane plastic material is used in the plastic track.

[0011] The technical effect of the present invention is as follows: the fluorine-containing naphthyl polymerization monomer prepared by the present invention contains two hydroxyl groups and two imino polymerization sites, and undergoes polymerization reaction with hexamethylene diisocyanate having less steric hindrance to obtain a fluorine-containing hyperbranched polyurethane. Then, it is mixed with polyurethane resin, fluororubber, reinforcing agent, auxiliary agent, etc. to obtain a polyurethane plastic material. The fluorine-containing hyperbranched polyurethane contains a polyurethane main chain and a fluorine-containing group, and has a similar polarity to that of the polyurethane resin and the fluororubber, and can play the role of a compatibilizer, thereby improving the compatibility between the polyurethane resin and the fluororubber, and making the polyurethane plastic material have better mechanical properties.

[0012] The fluorine-containing hyperbranched polyurethane of the invention contains a unique hyperbranched molecular chain, and the main chain of the molecule contains a rigid naphthalene ring structure, which has a good toughening and reinforcing effect, significantly improves the tensile strength and elongation at break of the polyurethane plastic material, reduces the relative volume abrasion, and improves the wear resistance. At the same time, the hyperbranched polyurethane contains a hydrophobic fluorine-containing group, which is beneficial to improving the hydrophobicity of the polyurethane plastic material, reducing the water absorption rate, and improving the water resistance and waterproof performance. DETAILED DESCRIPTION

[0013] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0014] Polyurethane resin, model BASF 785 A HPM, Dongguan Julong Plastic Raw Materials Co., Ltd. Fluororubber, model DS2603, Shabite Plastic Trading (Suzhou) Co., Ltd. Carbon black N220, Dongguan Canyu Chemical Co., Ltd. White carbon black, average particle size 1900 mesh, Foshan Shunde Jinchun Silicon Materials Co., Ltd.

[0015] Example 1 (1) Add 30 mmol 1,5-naphthalene diamine and 60 mmol 3-(2,2,3,3-tetrafluoropropoxy)-1,2-propylene oxide to 50 mL tetrahydrofuran, react at 40°C for 10 h, distill under reduced pressure, add dichloromethane and water, extract by oscillation, dry the organic phase to remove water, wash with petroleum ether, and dry to obtain a fluorinated naphthyl polymerization monomer. The reaction formula is: .

[0016] (2) Add 40 mmol hexamethylene diisocyanate, 20 mmol fluorinated naphthyl polymerization monomer, and 0.01 mmol dibutyltin dilaurate to 150 mL N,N-dimethylformamide, stir and react at 70°C in a nitrogen atmosphere for 5 h, and after cooling, pour the solution into water, filter, wash with dichloromethane and ethanol in turn, and dry to obtain fluorinated hyperbranched polyurethane. The reaction formula is: .

[0017] (3) Add 800 g of polyurethane resin, 200 g of fluororubber, 30 g of fluorine-containing hyperbranched polyurethane, 12 g of calcium hydroxide, 6 g of magnesium oxide, 2 g of palm wax, and 40 g of reinforcing agent white carbon black into an internal mixer, mix at 155°C for 40 min, then add 5 g of bisphenol AF and 1 g of benzyltriphenylphosphonium chloride, mix for 10 min, and then hot-press the material at 175°C for 10 min under a pressure of 10 MPa in a flat vulcanizer, and then heat-treat at 150°C for 12 h in a forced air drying oven, and cool to obtain a polyurethane plastic material.

[0018] Example 2 (1) Add 30 mmol of 1,5-naphthalenediamine and 60 mmol of 3-(2,2,3,3-tetrafluoropropoxy)-1,2-propylene oxide to 60 mL of tetrahydrofuran, react at 50°C for 7 h, distill under reduced pressure, add dichloromethane and water, extract by oscillation, dry the organic phase to remove water, wash with petroleum ether, and dry to obtain a fluorinated naphthyl polymerization monomer.

[0019] (2) To 200 mL of N,N-dimethylformamide, 44 mmol of hexamethylene diisocyanate, 20 mmol of fluorinated naphthyl polymerization monomer, and 0.008 mmol of dibutyltin dilaurate were added. The mixture was stirred at 65 °C in a nitrogen atmosphere for 5 h. After cooling, the solution was poured into water, filtered, washed with dichloromethane and ethanol, and dried to obtain a fluorinated hyperbranched polyurethane.

[0020] (3) Add 730 g of polyurethane resin, 270 g of fluororubber, 70 g of fluorine-containing hyperbranched polyurethane, 17 g of calcium hydroxide, 8 g of magnesium oxide, 3 g of stearic acid, and 70 g of reinforcing agent white carbon black into an internal mixer, mix at 150 ° C for 40 min, then add 7 g of bisphenol AF and 1.5 g of benzyltriphenylphosphonium chloride, mix for 15 min, and then hot-press the materials at 170 ° C for 20 min at a pressure of 10 MP in a flat vulcanizer, and then heat-treat at 170 ° C for 6 h in a forced air drying oven, and cool to obtain a polyurethane plastic material.

[0021] Example 3 (1) To 200 mL of N,N-dimethylformamide, 42 mmol of hexamethylene diisocyanate, 20 mmol of fluorinated naphthyl polymerization monomer (the same preparation process as in Example 1), and 0.008 mmol of dibutyltin dilaurate were added, and the mixture was stirred at 80° C. in a nitrogen atmosphere for 3 h. After cooling, the solution was poured into water, filtered, washed with dichloromethane and ethanol in turn, and dried to obtain a fluorinated hyperbranched polyurethane.

[0022] (2) Add 650 g of polyurethane resin, 350 g of fluororubber, 30 g of fluorine-containing hyperbranched polyurethane, 22 g of calcium hydroxide, 12 g of magnesium oxide, 4 g of polyethylene wax, and 100 g of reinforcing agent carbon black into an internal mixer, mix at 165°C for 30 min, then add 9 g of bisphenol AF and 2 g of benzyltriphenylphosphonium chloride, mix for 10 min, and then hot-press the material at 175°C for 10 min at a pressure of 12 MP in a flat vulcanizer, and then heat-treat at 160°C for 12 h in a forced air drying oven, and cool to obtain a polyurethane plastic material.

[0023] Comparative Example 1 The difference between this comparative example and Example 1 is that no fluorine-containing hyperbranched polyurethane is added.

[0024] (1) Add 800 g of polyurethane resin, 200 g of fluororubber, 12 g of calcium hydroxide, 6 g of magnesium oxide, 2 g of palm wax, and 40 g of reinforcing agent white carbon black into an internal mixer, mix at 155°C for 40 min, then add 5 g of bisphenol AF and 1 g of benzyltriphenylphosphonium chloride, mix for 10 min, and then hot-press the material at 175°C for 10 min under a pressure of 10 MP in a flat vulcanizer, and then heat-treat at 150°C for 12 h in a forced air drying oven, and cool to obtain a polyurethane plastic material.

[0025] Comparative Example 2 The difference between this comparative example and Example 1 is that, when preparing the polyurethane, 40 mmol of 1,5-naphthalene diol (2 polymerization sites) is used to replace 20 mmol of the fluorine-containing naphthyl polymerization monomer (4 polymerization sites).

[0026] (1) Add 40 mmol hexamethylene diisocyanate, 40 mmol 1,5-naphthalene diol, and 0.01 mmol dibutyltin dilaurate to 150 mL N,N-dimethylformamide, and stir the mixture at 70 °C in a nitrogen atmosphere for 5 h. After cooling, pour the solution into water, filter it, wash it with dichloromethane and ethanol, and dry it to obtain a polyurethane-based polymer.

[0027] (2) Add 800 g of polyurethane resin, 200 g of fluororubber, 30 g of polyurethane-based polymer, 12 g of calcium hydroxide, 6 g of magnesium oxide, 2 g of palm wax, and 40 g of reinforcing agent white carbon black into an internal mixer, mix at 155°C for 40 min, then add 5 g of bisphenol AF and 1 g of benzyltriphenylphosphonium chloride, mix for 10 min, and then hot-press the material at 175°C for 10 min under a pressure of 10 MP in a flat vulcanizer, and then heat-treat at 150°C for 12 h in a forced air drying oven, and cool to obtain a polyurethane plastic material.

[0028] Comparative Example 3 The difference between this comparative example and Example 1 is that ethylenediamine is used instead of 1,5-naphthalenediamine when preparing the fluorine-containing naphthyl polymer monomer.

[0029] (1) Add 30 mmol of ethylenediamine and 60 mmol of 3-(2,2,3,3-tetrafluoropropoxy)-1,2-propylene oxide to 50 mL of tetrahydrofuran, react at 40°C for 10 h, distill under reduced pressure, add dichloromethane and water, extract by oscillation, dry the organic phase to remove water, wash with petroleum ether, and dry to obtain a fluorine-containing polymer monomer.

[0030] (2) Add 40 mmol hexamethylene diisocyanate, 20 mmol fluorinated polymer monomer and 0.01 mmol dibutyltin dilaurate to 150 mL N,N-dimethylformamide, and stir the mixture at 70 °C in a nitrogen atmosphere for 5 h. After cooling, pour the solution into water, filter it, wash it with dichloromethane and ethanol, and dry it to obtain a fluorinated hyperbranched polyurethane.

[0031] (3) Add 800 g of polyurethane resin, 200 g of fluororubber, 30 g of fluorine-containing hyperbranched polyurethane, 12 g of calcium hydroxide, 6 g of magnesium oxide, 2 g of palm wax, and 40 g of reinforcing agent white carbon black into an internal mixer, mix at 155°C for 40 min, then add 5 g of bisphenol AF and 1 g of benzyltriphenylphosphonium chloride, mix for 10 min, and then hot-press the material at 175°C for 10 min under a pressure of 10 MPa in a flat vulcanizer, and then heat-treat at 150°C for 12 h in a forced air drying oven, and cool to obtain a polyurethane plastic material.

[0032] Comparative Example 4 The difference between this comparative example and Example 1 is that when preparing the hyperbranched polyurethane, 26.67 mmol of diethanolamine (3 polymerization sites) is used to replace 20 mmol of the fluorinated naphthyl polymerization monomer (4 polymerization sites).

[0033] (1) To 150 mL of N,N-dimethylformamide, 40 mmol of hexamethylene diisocyanate, 26.67 mmol of diethanolamine, and 0.01 mmol of dibutyltin dilaurate were added. The mixture was stirred at 70 °C in a nitrogen atmosphere for 5 h. After cooling, the solution was poured into water, filtered, washed with dichloromethane and ethanol, and dried to obtain a hyperbranched polyurethane.

[0034] (2) Add 800 g of polyurethane resin, 200 g of fluororubber, 30 g of hyperbranched polyurethane, 12 g of calcium hydroxide, 6 g of magnesium oxide, 2 g of palm wax, and 40 g of reinforcing agent white carbon black into an internal mixer, mix at 155°C for 40 min, then add 5 g of bisphenol AF and 1 g of benzyltriphenylphosphonium chloride, mix for 10 min, and then hot-press the material at 175°C for 10 min under a pressure of 10 MP in a flat vulcanizer, and then heat-treat at 150°C for 12 h in a forced air drying oven, and cool to obtain a polyurethane plastic material.

[0035] The tensile properties of polyurethane plastic materials are tested according to the national standard GB / T 528-2009. The wear resistance is tested according to the national standard GB / T 9867-2008.

[0036] A 10 cm × 10 cm × 1 cm sample of polyurethane plastic material was made and immersed in water for 48 hours. The sample was taken out, the surface moisture was wiped off, and the sample was weighed to calculate the water absorption rate. Water absorption rate = (m-m0) / m0×100%. m is the mass of the sample after water absorption. m0 is the mass before water absorption.

[0037] Table 1 Properties of polyurethane plastic materials Tensile strength (MPa) Elongation at break (%) Relative volume wear (mm3) Water absorption (%) Example 1 32.3 762.1 213.5 3.24 Example 2 46.6 713.5 143.9 1.46 Example 3 36.0 627.8 169.2 0.77 Comparative Example 1 23.5 605.3 248.4 4.58 Comparative Example 2 24.1 602.5 242.7 4.50 Comparative Example 3 30.8 769.6 230.5 3.79 Comparative Example 4 23.9 672.7 246.1 4.63

[0038] Compared with Comparative Example 1, Examples 1-3 add fluorine-containing hyperbranched polyurethane, which contains a polyurethane main chain and a fluorine-containing group, has a similar polarity to the polyurethane resin and the fluorine rubber, can play the role of a compatibilizer, improve the compatibility between the polyurethane resin and the fluorine rubber, and make the polyurethane plastic material have better mechanical properties. At the same time, the fluorine-containing hyperbranched polyurethane contains a unique hyperbranched molecular chain, and the main chain of the molecule contains a rigid naphthalene ring structure, which has a good toughening and reinforcing effect, significantly improves the tensile strength and elongation at break of the polyurethane plastic material, and improves the wear resistance, and the relative volume wear is significantly reduced. At the same time, the hyperbranched polyurethane contains a hydrophobic fluorine-containing group, which is beneficial to improving the hydrophobicity of the polyurethane plastic material, reducing the water absorption rate, and improving the water resistance and waterproof performance.

[0039] In comparative example 2, when preparing polyurethane, 1,5-naphthalenediol is used to replace 2-fluorine-containing naphthyl polymerization monomers. The obtained polyurethane-based polymer does not have a fluorine-containing group, has a very different polarity from fluororubber, has poor compatibility, cannot play the role of a compatibilizer, and cannot improve the compatibility between polyurethane resin and fluororubber, resulting in low tensile strength and elongation at break of the plastic material, large relative volume wear, poor mechanical properties and wear resistance, high water absorption, and poor water and waterproof properties.

[0040] Comparative Example 3 adds fluorine-containing hyperbranched polyurethane, which can improve the compatibility between polyurethane resin and fluororubber, increase the tensile strength and elongation at break of the plastic material, and improve the mechanical properties. However, the relative volume abrasion and water absorption are significantly higher than those of Example 1. This may be because the fluorine-containing hyperbranched polyurethane in Comparative Example 3 does not contain a rigid and hydrophobic naphthalene ring structure, which is not conducive to improving the wear resistance and water resistance of the plastic material.

[0041] Comparative Example 4 uses diethanolamine as a raw material. The prepared hyperbranched polyurethane does not have a fluorine-containing group, has a very different polarity from fluororubber, has poor compatibility, cannot act as a compatibilizer, and cannot improve the compatibility between the polyurethane resin and the fluororubber, resulting in low tensile strength and elongation at break of the plastic material, large relative volume abrasion, poor mechanical properties and wear resistance, high water absorption, and poor water resistance and waterproofing properties.

[0042] The above embodiments are only used to help understand the method and core idea of ​​the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A process for preparing a polyurethane plastic material, characterized in that: The preparation process comprises the following steps: (1) adding hexamethylene diisocyanate, fluorinated naphthyl polymerization monomer and dibutyltin dilaurate to N,N-dimethylformamide, stirring and reacting in a nitrogen atmosphere, and after cooling, pouring the solution into water, filtering, washing and drying to obtain a fluorinated hyperbranched polyurethane; (2) 65-80 parts by weight of polyurethane resin, 20-35 parts by weight of fluororubber, 3-12 parts by weight of fluorine-containing hyperbranched polyurethane, 1.2-2.2 parts by weight of calcium hydroxide, 0.6-1.2 parts by weight of magnesium oxide, 0.2-0.4 parts by weight of processing aid, and 4-10 parts by weight of reinforcing agent are added to an internal mixer for mixing, and then 0.5-0.9 parts by weight of bisphenol AF and 0.1-0.2 parts by weight of benzyl triphenylphosphonium chloride are added. After mixing, the materials are heat treated to obtain a polyurethane plastic material.

2. The process for preparing the polyurethane plastic material according to claim 1, characterized in that: The reaction temperature in (1) is 65-80°C and the reaction time is 3-5h.

3. The process for preparing the polyurethane plastic material according to claim 1, characterized in that: The molar ratio of hexamethylene diisocyanate, fluorinated naphthyl polymer monomer and dibutyltin dilaurate in (1) is (200-220):100:(0.04-0.05).

4. The process for preparing the polyurethane plastic material according to claim 3, characterized in that: The preparation process of the fluorine-containing naphthyl polymerization monomer is as follows: 1,5-naphthalene diamine and 3-(2,2,3,3-tetrafluoropropoxy)-1,2-propylene oxide are added to tetrahydrofuran, reacted at 40-50° C. for 7-10 hours, distilled under reduced pressure, added dichloromethane and water, extracted by oscillation, dried the organic phase to remove water, washed, and dried to obtain the fluorine-containing naphthyl polymerization monomer.

5. The process for preparing the polyurethane plastic material according to claim 4, characterized in that: The molar ratio of the 1,5-naphthalenediamine to 3-(2,2,3,3-tetrafluoropropoxy)-1,2-propylene oxide is 1:

2.

6. The process for preparing the polyurethane plastic material according to claim 1, characterized in that: The processing aid in (2) is palm wax, stearic acid or polyethylene wax.

7. The process for preparing the polyurethane plastic material according to claim 1, characterized in that: The reinforcing agent in (2) is carbon black or white carbon black.

8. The process for preparing the polyurethane plastic material according to claim 1, characterized in that: The mixing temperature in (2) is 150-165°C; the heat treatment is first performed in a flat vulcanizer at a pressure of 10-12MP at 170-175°C for 10-20 minutes, and then in a blast drying oven at 150-170°C for 6-12 hours.

9. Use of the polyurethane plastic material obtained by the preparation process according to any one of claims 1 to 8 in a plastic track.