Environment-friendly dicyclopentadiene polymer material and preparation method thereof

Abstract

The present application relates to the technical field of dicyclopentadiene polymerization, and particularly relates to an environment-friendly dicyclopentadiene polymer material, which is prepared from the following raw materials in parts by weight: dicyclopentadiene 80-90 parts, catalyst 0.003-0.05 parts, activator 1-3.5 parts, adjusting agent 20-30 parts and modified lignin 8-12 parts. In the preparation process of the DCPD polymer, the modified lignin, which is a raw material prepared on the basis of natural biomass, is added to improve the environmental performance of the DCPD polymer. After the lignin on the modified lignin and aluminum hydroxide are subjected to microwave treatment, the lignin is partially carbonized, the aluminum hydroxide is partially decomposed to generate aluminum oxide, and the surface of the modified lignin generates rich pores. These pores can absorb free DCPD in the DCPD polymer to reduce the release probability of DCPD, thereby reducing the peculiar smell of the product and further improving the environmental performance of the product.

Description

Technical Field

[0001] This invention relates to the field of dicyclopentadiene polymerization technology, and in particular to an environmentally friendly dicyclopentadiene polymer material and its preparation method. Background Technology

[0002] Dicyclopentadiene (DCPD) polymer, prepared through polymerization, is a novel engineering plastic. DCPD is polymerized under the action of ring-opening metathesis catalysts and exhibits excellent heat resistance, creep resistance, dimensional stability, corrosion resistance, and wear resistance. Currently, the catalyst systems used for the polymerization of dicyclopentadiene include tungsten-molybdenum complexes or molybdenum-ruthenium carbene catalysts. The process employed is reaction injection molding (RIM), which offers advantages such as fast molding speed, high efficiency, and low energy consumption, and can be used to manufacture various large, thin-walled, and complex-shaped parts.

[0003] DCPD polymers processed using RIM technology possess excellent mechanical properties, thermal stability, and anti-aging properties, and can be widely used in automotive parts, industrial equipment, medical devices, and other fields.

[0004] Existing DCPD polymers release an unpleasant odor during use. This odor is primarily caused by incomplete DCPD reaction, resulting in the volatilization of residual monomers and the generation of the odor. Furthermore, the flame-retardant properties of existing DCPD polymers are not ideal. Therefore, we propose an environmentally friendly dicyclopentadiene polymer material and its preparation method to address these issues. Summary of the Invention

[0005] The purpose of this invention is to address the shortcomings of existing technologies by proposing an environmentally friendly dicyclopentadiene polymer material and its preparation method.

[0006] An environmentally friendly dicyclopentadiene polymer material is prepared from the following raw materials in parts by weight: 80-90 parts dicyclopentadiene, 0.003-0.05 parts catalyst, 1-3.5 parts activator, 20-30 parts regulator and 8-12 parts modified lignin.

[0007] Preferably, the method for preparing the modified lignin includes the following steps: Step a: Dissolve lignin in sodium hydroxide solution, slowly add aluminum salt solution to the lignin solution while stirring at high speed. After the aluminum salt solution is added, adjust the pH of the solution to 7-9 to hydrolyze aluminum ions to generate aluminum hydroxide. After the reaction is complete, let it stand for aging for 2-4 hours, filter, wash, and dry to obtain lignin loaded with aluminum hydroxide; Step b: Use a mixer to stir the lignin loaded with aluminum hydroxide at high speed, dilute the silane coupling agent with ethanol, atomize and spray it onto the lignin loaded with aluminum hydroxide while stirring at high speed, continue stirring for 30-60 minutes, control the temperature at 50-80℃, let it stand for aging for 2-4 hours after stirring, and then microwave treat it to obtain the modified lignin.

[0008] Preferably, in the preparation process of modified lignin: the mass ratio of lignin to aluminum in aluminum salt is 8-15:1; the mass ratio of lignin to silane coupling agent is 6-12:1; the concentration of sodium hydroxide solution is 0.5-2 mol / L; and the mass ratio of silane coupling agent to ethanol is 1:0.3-1.5.

[0009] Preferably, the aluminum salt is one of aluminum nitrate or aluminum chloride, and the silane coupling agent is one of KH550 or KH570.

[0010] Preferably, in step a, the high-speed stirring speed is 800-1000 r / min, in step b, the high-speed stirring speed is 1200-1500 r / min, in step b, the microwave reaction power is 50-1000 W, and the microwave treatment time is 10-15 seconds.

[0011] Preferably, the activator is a mixture of diethylaluminum monochloro and diethylzinc, wherein the mass ratio of diethylaluminum monochloro to diethylzinc is 1:1.5-3.

[0012] Preferably, the regulator is a mixture of diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, wherein the mass ratio of diethylene glycol dimethyl ether to diethylene glycol dibutyl ether is 1:0.3-1.

[0013] Preferably, the catalyst comprises a main catalyst and a co-catalyst, wherein the main catalyst is a ruthenium-based catalyst, the co-catalyst is triethylamine, and the mass ratio of the main catalyst to the co-catalyst is 1:20-30.

[0014] Preferably, a method for preparing an environmentally friendly dicyclopentadiene polymer material includes the following steps:

[0015] Step 1: Accurately weigh each raw material, and mix dicyclopentadiene, regulator and modified lignin evenly to obtain a mixture;

[0016] Step 2: Divide the mixture into two portions. Add the catalyst to the first portion and mix well. This portion is labeled as component A. Add the activator to the first portion and mix well. This portion is labeled as component B.

[0017] Step 3: Mix components A and B by impact at the RIM die head, control the material temperature at 20-40℃ and the pressure at 3.0MPa, and inject it into a mold preheated to 40-60℃ to complete the polymerization and curing.

[0018] The beneficial effects of this invention are:

[0019] 1. The DCPD polymer proposed in this invention incorporates modified lignin, a raw material prepared based on natural biomass, during its preparation process. This improves the environmental performance of the DCPD polymer. Furthermore, after microwave treatment, the lignin and aluminum hydroxide on the modified lignin undergo partial carbonization, and the aluminum hydroxide partially decomposes to generate porous alumina. This results in abundant pores on the surface of the modified lignin. These pores can absorb free DCPD in the DCPD polymer, reducing the probability of DCPD release and thus reducing the odor of the product, further improving its environmental performance.

[0020] 2. The DCPD polymer proposed in this invention incorporates modified lignin during its preparation process. The dispersion performance of the modified lignin can be improved by using a silane coupling agent. The uniform dispersion of the modified lignin can improve the strength and wear resistance of the product to a certain extent. Furthermore, the flame retardant properties of the lignin modified with aluminum hydroxide are significantly enhanced, thus expanding the application range of the DCPD polymer.

[0021] 3. The DCPD polymer proposed in this invention, with its porous modified lignin, can also serve as a catalyst support, improving the catalyst's dispersibility in the reactants, thereby increasing the reaction conversion rate and reducing the content of free DCPD in the finished product, thus improving the product's environmental performance to a certain extent. Detailed Implementation

[0022] The present invention will be further explained below with reference to specific embodiments.

[0023] Example 1: An environmentally friendly dicyclopentadiene polymer material is prepared from the following raw materials in parts by weight: 80 parts dicyclopentadiene, 0.003 parts catalyst, 1 part activator, 20 parts regulator and 8 parts modified lignin.

[0024] The preparation method of modified lignin includes the following steps: Step a: Dissolve lignin in sodium hydroxide solution, slowly add aluminum salt solution to the lignin solution while stirring at high speed. After the aluminum salt solution is added, adjust the pH of the solution to 7 to hydrolyze aluminum ions to generate aluminum hydroxide. After the reaction is complete, let it stand for 2 hours, filter, wash, and dry to obtain lignin loaded with aluminum hydroxide; Step b: Use a mixer to stir the lignin loaded with aluminum hydroxide at high speed, dilute the silane coupling agent with ethanol, atomize and spray it onto the lignin loaded with aluminum hydroxide while stirring at high speed, continue stirring for 30 minutes, control the temperature at 50℃, let it stand for 2 hours after stirring, and then microwave treat it to obtain modified lignin.

[0025] In the preparation of modified lignin: the mass ratio of lignin to aluminum in aluminum salt is 8:1; the mass ratio of lignin to silane coupling agent is 6:1; the concentration of sodium hydroxide solution is 0.5 mol / L; and the mass ratio of silane coupling agent to ethanol is 1:0.3.

[0026] The aluminum salt is aluminum nitrate, and the silane coupling agent is KH550.

[0027] In step a, the high-speed stirring speed is 800 r / min; in step b, the high-speed stirring speed is 1200 r / min; in step b, the microwave reaction power is 50 W; and the microwave treatment time is 10 seconds.

[0028] The activator is a mixture of diethylaluminum monochloro and diethylzinc monochloro, with a mass ratio of 1:1.5.

[0029] The regulator is a mixture of diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, with a mass ratio of 1:0.3.

[0030] The catalyst consists of a main catalyst and a co-catalyst. The main catalyst is a ruthenium-based catalyst, and the co-catalyst is triethylamine. The mass ratio of the main catalyst to the co-catalyst is 1:20.

[0031] A method for preparing an environmentally friendly dicyclopentadiene polymer material includes the following steps:

[0032] Step 1: Accurately weigh each raw material, and mix dicyclopentadiene, regulator and modified lignin evenly to obtain a mixture;

[0033] Step 2: Divide the mixture into two equal parts. Add the catalyst to the first part and mix well. This part is labeled as component A. Add the activator to the first part and mix well. This part is labeled as component B.

[0034] Step 3: Mix components A and B in a 1:1 ratio at the RIM head, control the material temperature at 20℃ and the pressure at 3.0MPa, and inject it into a mold preheated to 40℃ to complete the polymerization and curing.

[0035] Example 2: An environmentally friendly dicyclopentadiene polymer material is prepared from the following raw materials in parts by weight: 90 parts dicyclopentadiene, 0.05 parts catalyst, 3.5 parts activator, 30 parts regulator and 12 parts modified lignin.

[0036] The preparation method of modified lignin includes the following steps: Step a: Dissolve lignin in sodium hydroxide solution, slowly add aluminum salt solution to the lignin solution while stirring at high speed. After the aluminum salt solution is added, adjust the pH of the solution to 9 to hydrolyze aluminum ions to generate aluminum hydroxide. After the reaction is complete, let it stand for 4 hours, filter, wash, and dry to obtain lignin loaded with aluminum hydroxide; Step b: Use a mixer to stir the lignin loaded with aluminum hydroxide at high speed, dilute the silane coupling agent with ethanol, atomize and spray it into the lignin loaded with aluminum hydroxide while stirring at high speed, continue stirring for 60 minutes, control the temperature at 80℃, let it stand for 4 hours after stirring, and after aging, perform microwave treatment to obtain modified lignin.

[0037] In the preparation of modified lignin: the mass ratio of lignin to aluminum in aluminum salt is 15:1; the mass ratio of lignin to silane coupling agent is 12:1; the concentration of sodium hydroxide solution is 2 mol / L; and the mass ratio of silane coupling agent to ethanol is 1:1.5.

[0038] The aluminum salt is either aluminum nitrate or aluminum chloride, and the silane coupling agent is KH570.

[0039] In step a, the high-speed stirring speed is 1000 r / min; in step b, the high-speed stirring speed is 1500 r / min; in step b, the microwave reaction power is 1000 W; and the microwave treatment time is 15 seconds.

[0040] The activator is a mixture of diethylaluminum monochloro and diethylzinc monochloro, with a mass ratio of 1:3.

[0041] The regulator is a mixture of diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, with a mass ratio of 1:1.

[0042] The catalyst consists of a main catalyst and a co-catalyst. The main catalyst is a ruthenium-based catalyst, and the co-catalyst is triethylamine. The mass ratio of the main catalyst to the co-catalyst is 1:30.

[0043] A method for preparing an environmentally friendly dicyclopentadiene polymer material includes the following steps:

[0044] Step 1: Accurately weigh each raw material, and mix dicyclopentadiene, regulator and modified lignin evenly to obtain a mixture;

[0045] Step 2: Divide the mixture into two portions. Add the catalyst to the first portion and mix well. This portion is labeled as component A. Add the activator to the first portion and mix well. This portion is labeled as component B.

[0046] Step 3: Mix components A and B in a 1:2 ratio at the RIM head, control the material temperature at 40℃ and the pressure at 3.0MPa, and inject the mixture into a mold preheated to 60℃ to complete the polymerization and curing.

[0047] Example 3: An environmentally friendly dicyclopentadiene polymer material, prepared from the following raw materials in parts by weight: 85 parts dicyclopentadiene, 0.03 parts catalyst, 1-2 parts activator, 25 parts regulator and 10 parts modified lignin.

[0048] The method for preparing the modified lignin includes the following steps: Step a: Dissolve lignin in sodium hydroxide solution, slowly add aluminum salt solution to the lignin solution while stirring at high speed. After the aluminum salt solution is added, adjust the pH of the solution to 8 to hydrolyze aluminum ions to generate aluminum hydroxide. After the reaction is complete, let it stand for 3 hours, filter, wash, and dry to obtain lignin loaded with aluminum hydroxide; Step b: Use a mixer to stir the lignin loaded with aluminum hydroxide at high speed, dilute the silane coupling agent with ethanol, atomize and spray it onto the lignin loaded with aluminum hydroxide while stirring at high speed, continue stirring for 40 minutes, control the temperature at 60°C, let it stand for 3 hours after stirring, and then microwave treat it to obtain the modified lignin.

[0049] In the preparation of modified lignin: the mass ratio of lignin to aluminum in aluminum salt is 12:1; the mass ratio of lignin to silane coupling agent is 10:1; the concentration of sodium hydroxide solution is 1.2 mol / L; and the mass ratio of silane coupling agent to ethanol is 1:1.2.

[0050] The aluminum salt is either aluminum nitrate or aluminum chloride, and the silane coupling agent is KH550.

[0051] In step a, the high-speed stirring speed is 900 r / min; in step b, the high-speed stirring speed is 1300 r / min; in step b, the microwave reaction power is 800 W; and the microwave treatment time is 12 seconds.

[0052] The activator is a mixture of diethylaluminum monochloro and diethylzinc monochloro, with a mass ratio of 1:2.

[0053] The regulator is a mixture of diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, with a mass ratio of 1:0.8.

[0054] The catalyst includes a main catalyst and a co-catalyst. The main catalyst is a ruthenium-based catalyst, and the co-catalyst is triethylamine. The mass ratio of the main catalyst to the co-catalyst is 1:25.

[0055] A method for preparing an environmentally friendly dicyclopentadiene polymer material includes the following steps:

[0056] Step 1: Accurately weigh each raw material, and mix dicyclopentadiene, regulator and modified lignin evenly to obtain a mixture;

[0057] Step 2: Divide the mixture into two equal parts. Add the catalyst to the first part and mix well. This part is labeled as component A. Add the activator to the first part and mix well. This part is labeled as component B.

[0058] Step 3: Mix components A and B in a 1:1 ratio using the RIM head, with the material temperature controlled at 30℃ and the pressure at 3.0MPa. Pour the mixture into a mold preheated to 50℃ to complete the polymerization and curing process.

[0059] Comparative Example 1, compared with Example 3, did not add modified lignin, and the rest was the same as Example 3.

[0060] Comparative Example 2, compared with Example 3, added an equal amount of lignin to replace the modified lignin, and the rest was the same as Example 3.

[0061] Comparative Example 3, compared with Example 3, the steps in the preparation process of modified lignin are as follows: Step a, dissolve lignin in sodium hydroxide solution, stir at high speed, let stand for 3 hours, filter, wash and dry to obtain sodium hydroxide-treated lignin; Step b, use a mixer to stir the sodium hydroxide-treated lignin at high speed, dilute the silane coupling agent with ethanol, atomize and spray it into the sodium hydroxide-treated lignin being stirred at high speed, continue stirring for 40 minutes, control the temperature at 60°C, let stand for 3 hours after stirring, after aging, microwave treatment to obtain modified lignin, the rest is the same as in Example 3.

[0062] Comparative Example 4, compared with Example 3, the steps in the preparation process of modified lignin are as follows: Step a, dissolve lignin in sodium hydroxide solution, slowly add aluminum salt solution to the lignin solution while stirring at high speed. After the aluminum salt solution is added, adjust the pH of the solution to 8 so that aluminum ions are hydrolyzed to generate aluminum hydroxide. After the reaction is completed, let it stand for 3 hours, filter, wash and dry to obtain lignin loaded with aluminum hydroxide; Step b, use a mixer to stir the lignin loaded with aluminum hydroxide at high speed, dilute the silane coupling agent with ethanol, atomize and spray it into the lignin loaded with aluminum hydroxide that is being stirred at high speed, continue stirring for 40 minutes, control the temperature at 60°C, after stirring is completed, let it stand for 3 hours to mature, after maturation is completed, the modified lignin is obtained, and the rest is the same as in Example 3.

[0063] The environmentally friendly dicyclopentadiene polymer materials obtained in Examples 1-3 and Comparative Examples 1-4 were subjected to the following performance tests:

[0064] Flame retardancy: Tested according to UL-94 testing standards;

[0065] Thermogravimetric analysis at 200℃: Tested according to GB / T27761-2011 standard;

[0066] Abrasion resistance: Tested according to ISO 9352 standard;

[0067] Bending strength and bending modulus: tested according to ISO 178 standard.

[0068] The test results are shown in Table 1.

[0069] Table 1

[0070]

[0071] As can be seen from Table 1, the environmentally friendly dicyclopentadiene polymer materials of Examples 1-3 have certain flame retardancy, low thermal weight loss at 200℃, and are not prone to releasing free DCPD. The addition of modified lignin can improve the wear resistance, flexural strength and flexural modulus of the environmentally friendly dicyclopentadiene polymer materials to a certain extent.

[0072] In Comparative Example 1, without the addition of modified lignin, the resulting material did not exhibit significant flame retardant properties. Its thermal weight loss and volumetric abrasion at 200℃ increased significantly, while its flexural strength and flexural modulus decreased significantly. In Comparative Example 2, with the addition of an equal amount of lignin to replace the modified lignin, the resulting material did not exhibit significant flame retardant properties. Its thermal weight loss and volumetric abrasion at 200℃ were superior to those of Comparative Example 1, and its flexural strength and flexural modulus were also superior. In Comparative Example 3, the resulting material did not exhibit significant flame retardant properties. Its thermal weight loss at 200℃ was superior to that of Comparative Example 2, and its flexural strength and flexural modulus were also superior to those of Comparative Example 2, while its volumetric abrasion was close to that of Comparative Example 2. In Comparative Example 4, the resulting material exhibited certain flame retardant properties. Its thermal weight loss and volumetric abrasion at 200℃ were superior to those of Comparative Example 3, and its flexural strength and flexural modulus were also superior to those of Comparative Example 3.

[0073] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. An environmentally friendly dicyclopentadiene polymer material, characterized in that, It is prepared from the following raw materials in parts by weight: 80-90 parts of dicyclopentadiene, 0.003-0.05 parts of catalyst, 1-3.5 parts of activator, 20-30 parts of regulator and 8-12 parts of modified lignin; The method for preparing the modified lignin includes the following steps: Step a: Dissolve lignin in sodium hydroxide solution, slowly add aluminum salt solution to the lignin solution while stirring at high speed. After the aluminum salt solution is added, adjust the pH of the solution to 7-9 to hydrolyze aluminum ions to generate aluminum hydroxide. After the reaction is complete, let it stand for aging for 2-4 hours, filter, wash, and dry to obtain lignin loaded with aluminum hydroxide; Step b: Use a mixer to stir the lignin loaded with aluminum hydroxide at high speed, dilute the silane coupling agent with ethanol, atomize and spray it onto the lignin loaded with aluminum hydroxide while stirring at high speed, continue stirring for 30-60 minutes, control the temperature at 50-80℃, let it stand for aging for 2-4 hours after stirring, and then microwave treat it to obtain the modified lignin.

2. The environmentally friendly dicyclopentadiene polymer material according to claim 1, characterized in that, In the preparation of modified lignin: the mass ratio of lignin to aluminum in aluminum salt is 8-15:1; the mass ratio of lignin to silane coupling agent is 6-12:1; the concentration of sodium hydroxide solution is 0.5-2 mol / L; and the mass ratio of silane coupling agent to ethanol is 1:0.3-1.

5.

3. The environmentally friendly dicyclopentadiene polymer material according to claim 2, characterized in that, The aluminum salt is either aluminum nitrate or aluminum chloride, and the silane coupling agent is either KH550 or KH570.

4. The environmentally friendly dicyclopentadiene polymer material according to claim 2, characterized in that, In step a, the high-speed stirring speed is 800-1000 r / min; in step b, the high-speed stirring speed is 1200-1500 r / min; in step b, the microwave reaction power is 50-1000 W; and the microwave treatment time is 10-15 seconds.

5. The environmentally friendly dicyclopentadiene polymer material according to claim 1, characterized in that, The activator is a mixture of diethylaluminum monochloro and diethylzinc monochloro, with a mass ratio of 1:1.5-3.

6. The environmentally friendly dicyclopentadiene polymer material according to claim 1, characterized in that, The regulator is a mixture of diethylene glycol dimethyl ether and diethylene glycol dibutyl ether, with a mass ratio of 1:0.3-1.

7. The environmentally friendly dicyclopentadiene polymer material according to claim 1, characterized in that, The catalyst includes a main catalyst and a co-catalyst. The main catalyst is a ruthenium-based catalyst, and the co-catalyst is triethylamine. The mass ratio of the main catalyst to the co-catalyst is 1:20-30.

8. A method for preparing an environmentally friendly dicyclopentadiene polymeric material according to any one of claims 1-7, characterized in that, Includes the following steps: Step 1: Accurately weigh each raw material, and mix dicyclopentadiene, regulator and modified lignin evenly to obtain a mixture; Step 2: Divide the mixture into two portions. Add the catalyst to the first portion and mix well. This portion is labeled as component A. Add the activator to the first portion and mix well. This portion is labeled as component B. Step 3: Mix components A and B by impact at the RIM die head, control the material temperature at 20-40℃ and the pressure at 3.0MPa, and inject it into a mold preheated to 40-60℃ to complete the polymerization and curing.

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