阅读说明：本技术 一种聚双环戊二烯复合材料及其制备方法 (Polydicyclopentadiene composite material and preparation method thereof ) 是由 周飞 翁羽飞 蒋方红 奚军 许艾娜 罗群 于 2019-10-21 设计创作，主要内容包括：本发明高分子材料领域,具体涉及一种聚双环戊二烯复合材料及其制备方法。聚双环戊二烯复合材料,包含质量比的以下组份：双环戊二烯单体与催化剂的物质的量比为5000-50000：1,双环戊二烯单体与抗氧剂的质量为100：0.01-2。其制备步骤包括：溶有双环戊二烯及抗氧剂的有机溶剂与溶有催化剂的有机溶剂经多段管式混合器混合后立即注入模具,于40℃～80℃反应成型后,于120℃～150℃进行后处理。采用多段管式微流道混合聚合工艺,大大提高混合效果,降低催化剂用量,生产工艺简单,所得聚双环戊二烯复合材料性能优良。(The invention belongs to the field of high polymer materials, and particularly relates to a polydicyclopentadiene composite material and a preparation method thereof. The polydicyclopentadiene composite material comprises the following components in percentage by mass: the mass ratio of dicyclopentadiene monomer to catalyst was 5000-50000: 1, the mass of the dicyclopentadiene monomer and the antioxidant is 100: 0.01-2. The preparation method comprises the following steps: mixing the organic solvent with dicyclopentadiene and antioxidant and the organic solvent with catalyst in a multi-section tubular mixer, injecting into a mold, reacting at 40-80 deg.C, molding, and post-treating at 120-150 deg.C. The multi-section tubular micro-channel mixing polymerization process is adopted, the mixing effect is greatly improved, the catalyst consumption is reduced, the production process is simple, and the obtained polydicyclopentadiene composite material has excellent performance.)

1. The polydicyclopentadiene composite material is characterized by comprising the following components: dicyclopentadiene monomer, catalyst, modifier and antioxidant, wherein the mass ratio of the dicyclopentadiene monomer to the catalyst is 5000-50000: 1, the mass ratio of the dicyclopentadiene monomer to the modifier is 100: 5-50, wherein the mass ratio of the dicyclopentadiene monomer to the antioxidant is 100: 0.01-2.

2. The polydicyclopentadiene composite material of claim 1, wherein: the mass ratio of dicyclopentadiene monomer to catalyst is 10000: 1; the mass ratio of the dicyclopentadiene monomer to the modifier is 100: 5; the mass of the dicyclopentadiene monomer and the antioxidant is 100: 0.5-1.

3. A polydicyclopentadiene composite material according to claim 1 or 2 wherein said catalyst is a ruthenium-based catalyst, preferably a Grubbs second generation catalyst.

4. A method of preparing a polydicyclopentadiene composite material of any one of claims 1-3, comprising the steps of: mixing the organic solvent with dicyclopentadiene and antioxidant and the organic solvent with catalyst in a multi-section tubular micro-channel mixer, injecting into a mold, reacting at 40-80 deg.C, and post-treating at 120-150 deg.C.

5. The method according to claim 4, wherein the weight ratio of dicyclopentadiene to the modifier in the organic solvent containing dicyclopentadiene, the modifier and the antioxidant is 100: 5-50, wherein the mass ratio of the dicyclopentadiene monomer to the antioxidant is 100: 0.01-2, wherein the mass ratio of the dicyclopentadiene to the organic solvent is 100: 2-5; the mass volume concentration of the catalyst in the organic solvent for uniformly dissolving the catalyst is 35-50 mg/ml.

6. The method of claim 4 or 5, wherein the organic solvent comprises at least one of dichloromethane, toluene, ethyl acetate, or tetrahydrofuran.

7. The process according to claim 4 or 5, wherein the dicyclopentadiene and the antioxidant are dissolved in an organic solvent, optionally with or without the modifier ethylidene norbornene, and the mass ratio of the dicyclopentadiene monomer to the modifier is 100: 5-50.

8. The preparation method according to claim 4, characterized in that the reaction is carried out at 40-80 ℃ for 1-2 h for molding, and the post-treatment is carried out at 120-150 ℃ for 1-2 h.

Technical Field

The invention belongs to the field of high polymer materials, and particularly relates to a polydicyclopentadiene composite material and a preparation method thereof.

Background

Polydicyclopentadiene (PDCPD) is a novel engineering plastic, is polymerized by dicyclopentadiene (DCPD) under the action of a ring-opening metathesis catalyst, and has the characteristics of good heat resistance, creep resistance, dimensional stability, corrosion resistance, abrasion resistance and the like. At present, a catalyst system used for preparing polydicyclopentadiene comprises a tungsten-molybdenum complex or a carbene catalyst of molybdenum and ruthenium, and the adopted process is a Reaction Injection Molding (RIM) process, so that the polydicyclopentadiene catalyst has the advantages of high molding speed, high efficiency, low energy consumption and the like, and can be used for manufacturing various large-scale thin-walled workpieces with complex shapes.

The PDCPD material processed and formed by the RIM technology has excellent mechanical property, thermal stability, ageing resistance and the like, and can be widely applied to the aspects of automobile parts, industrial equipment, medical appliances and the like. At present, only a few enterprises at home produce and sell PDCPD materials by using foreign core technology, but the foreign technology is mature, and the PDCPD has been developed for many years especially in famous companies such as Katephler, Terex, Labhilaer, Sweden Volvo, Shantevick, Japan Jian, Xiaosong and the like. In the United states, PDCPD materials are used primarily for containers for hazardous waste, side rails for large trucks, bumpers, fenders, and the like. PDCPD is mainly used in japan for producing automobile bumpers and large water treatment containers. Typical brands of polydicyclopentadiene engineering plastics include METTON developed by Hercules and Imperial corporation, TELENE and PENTAM series developed by Goodrich and Reynolds corporation. The PDCPD product is firstly produced and popularized in China at the rate of new Senhui material of a Gallery of the daily enterprises in 2006, and has certain production capacity.

The main research and development mechanisms in China include Tianjin university, Shanghai chemical research institute Co., Ltd, Henan university of science and technology, Keqin New Material science and technology Co., Ltd and the like, but are still in the immature stage of technology.

A, B two materials are mixed and injected in a ratio of 1:1 in the RIM process, but when a ruthenium carbene catalyst is adopted, the ratio of A, B materials is 1000-10000: 1, the mixing effect is difficult to achieve by adopting the traditional process, and the product performance is influenced. The polydicyclopentadiene composite material (CN105199290B) is prepared with dicyclopentadiene, styrene, silica, triphenylphosphine, p-tert-butylphenol, toluene and curing agent and through mixing the materials, mixing with curing agent solution to form slurry and molding.

The invention aims to provide a polydicyclopentadiene composite material and a process thereof, which adopt a multi-section tubular micro-channel mixed polymerization process, are suitable for a ruthenium carbene catalyst system, can greatly improve the mixing effect, reduce the using amount of the catalyst, and have simple production process and excellent product performance.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a polydicyclopentadiene composite material, which greatly reduces the dosage of a catalyst, simplifies the types and the contents of formula components, gradually increases the mechanical properties of the composite material, such as tensile modulus, tensile strength, bending strength and the like along with the gradual reduction of the dosage of the catalyst, gradually reduces the notch impact and elongation at break, gradually increases the thermal deformation temperature, and has excellent overall performance.

The invention provides a preparation method of polydicyclopentadiene composite material, which adopts a multi-section tubular micro-channel mixed polymerization process, is suitable for a ruthenium carbene catalyst system, greatly improves the mixing effect, reduces the catalyst consumption, and has simple production process and excellent product performance.

The technical scheme of the invention is that the polydicyclopentadiene composite material comprises the following components in percentage by mass: the mass ratio of dicyclopentadiene monomer to catalyst was 5000-50000: 1, preferably 10000: 1; if modifier ethylidene norbornene is added, the mass ratio of dicyclopentadiene monomer to ethylidene norbornene is 100: 5-50, preferably 100: 5; the mass of the dicyclopentadiene monomer and the antioxidant is 100: 0.01-2, preferably 100: 0.5-1.

The catalyst is ruthenium catalyst, preferably Grubbs second generation catalyst.

The dicyclopentadiene monomer is a polymerization-grade dicyclopentadiene monomer, and the purity is more than 95%.

The antioxidant is a high-molecular antioxidant which can be dissolved in dichloromethane or toluene, and preferably o-di-tert-butyl-p-methylphenol.

The raw materials are mixed by adopting a mixing mode, namely mixing in a multi-section tubular micro-channel mode.

A preparation method of polydicyclopentadiene composite material comprises the following steps: mixing the organic solvent with dicyclopentadiene and antioxidant and the organic solvent with catalyst in a multi-section tubular mixer, injecting into a mould, curing at 40-80 deg.C, and post-treating at 120-150 deg.C.

Dissolving dicyclopentadiene and an antioxidant in an organic solvent, wherein the mass ratio of dicyclopentadiene to the organic solvent is 100: 2-5, preferably 100: 3-5; the mass ratio of dicyclopentadiene to the antioxidant is 100: 0.01-2, preferably 100: 1-2.

Dissolving dicyclopentadiene and an antioxidant in an organic solvent, wherein the mass ratio of a modifier ethylidene norbornene is 100: 5-50, preferably 100: 5.

the mass volume concentration of the catalyst in the organic solvent in which the catalyst is dissolved is 35-50mg/ml, preferably 40 mg/ml.

The organic solvent comprises at least one of dichloromethane, toluene, ethyl acetate or tetrahydrofuran, preferably dichloromethane.

The catalyst is ruthenium catalyst, preferably Grubbs second generation catalyst.

Reacting at 40-80 ℃ for 1-2 h for forming, preferably at 60 ℃ for 1h for forming.

Post-treating at 120-150 deg.c for 1-2 hr, preferably at 140 deg.c for 1 hr.

Compared with the prior art, the invention has the advantages that:

compared with a bimetallic catalyst, the Grubbs second-generation catalyst has more convenient operation because certain activity is kept in air and a small amount of moisture before reaction, and meanwhile, compared with the first-generation catalyst, the Grubbs second-generation catalyst has higher activity and can improve the ratio of a monomer to the catalyst by several orders of magnitude, so that the raw material cost can be effectively saved.

The RIM technology of the invention has the advantages of simple process operation, uniform material mixing, small catalyst dosage, uniform and compact product prepared by copolymerization and better mechanical property.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.

Example 1

This example illustrates the process of the present invention for producing dicyclopentadiene homopolymer at a ratio of dicyclopentadiene to catalyst material of 5000:1 (about 800:1 by mass)

(1) Preparing a catalyst solution A

Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.

(2) Preparing dicyclopentadiene solution B

Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%), stirring for 12h at 80 ℃ under the protection of nitrogen, carrying out reduced pressure distillation for refining, and then adding a dichloromethane solvent with the mass of 2-5% of that of the dicyclopentadiene to fully dissolve in advance. Adding antioxidant o-di-tert-butyl-p-methylphenol accounting for 0.01-2% of the mass of dicyclopentadiene into dicyclopentadiene solution under the protection of nitrogen, fully and uniformly stirring on a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃.

(3) Mixed solidification forming

Measuring 3.85ml of A solution and 120g of B solution, uniformly mixing the A solution and the B solution through a multi-section tubular mixer under the protection of nitrogen, injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.

And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.

The tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer at a 5000:1 ratio of dicyclopentadiene to catalyst material are shown in Table 1.

Example 2

This example illustrates the preparation of a dicyclopentadiene homopolymer according to the invention at a ratio of dicyclopentadiene to catalyst material of 10000:1 (mass ratio of about 1500:1)

(1) Preparing a catalyst solution A

Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.

(2) Preparing dicyclopentadiene solution B

Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%), stirring for 12h at 80 ℃ under the protection of nitrogen, carrying out reduced pressure distillation for refining, and then adding a dichloromethane solvent with the mass of 2-5% of that of the dicyclopentadiene to fully dissolve in advance. Adding antioxidant o-di-tert-butyl-p-methylphenol accounting for 0.01-2% of the mass of dicyclopentadiene into dicyclopentadiene solution under the protection of nitrogen, fully and uniformly stirring on a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃.

(3) Mixed solidification forming

Measuring 1.93ml of A solution and 120g of B solution, and quickly mixing the A solution and the B solution in a multi-section tubular mixer under the protection of nitrogen until the A solution and the B solution are uniformly mixed. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.

And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.

The tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1 at a ratio of 10000:1 dicyclopentadiene to catalyst material.

Example 3

This example illustrates the preparation of a dicyclopentadiene homopolymer according to the invention at a ratio of amount of dicyclopentadiene to catalyst material of 20000:1 (mass ratio of about 3000:1)

(1) Preparing a catalyst solution A

Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.

(2) Preparing dicyclopentadiene solution B

Adding excessive calcium hydride into dicyclopentadiene (purity is more than 95%), stirring for 12h at 80 ℃ under the protection of nitrogen, carrying out reduced pressure distillation for refining, and then adding a dichloromethane solvent with the mass of 2-5% of that of the dicyclopentadiene to fully dissolve in advance. Adding antioxidant o-di-tert-butyl-p-methylphenol accounting for 0.01-2% of the mass of dicyclopentadiene into dicyclopentadiene solution under the protection of nitrogen, fully and uniformly stirring on a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃.

(3) Mixed solidification forming

Measuring 0.96ml of A solution and 120g of B solution, and quickly mixing the A solution and the B solution in a multi-section tubular mixer under the protection of nitrogen until the A solution and the B solution are uniformly mixed. And (3) quickly injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.

And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.

The tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer at a ratio of 20000:1 to the catalyst material are shown in Table 1.

Example 4

This example is intended to illustrate the preparation of a dicyclopentadiene-ethylidene norbornene copolymer according to the invention when the ratio of the amount of the dicyclopentadiene-ethylidene norbornene mixed solution to the amount of the catalyst substance is 10000:1 (mass ratio is about 1500:1)

(1) Preparing a catalyst solution A

Grubbs second generation catalyst (424.5mg, 0.5mmol) was weighed into a glove box and dissolved in 10.6ml of dichloromethane to make a 40mg/ml catalyst solution.

(2) Preparing a dicyclopentadiene-ethylidene norbornene mixed solution B

Adding excessive calcium hydride into dicyclopentadiene and ethylidene norbornene (purity is higher than 95%), stirring at 80 deg.C under nitrogen protection for 12 hr, and distilling under reduced pressure for refining. Weighing 95% of dicyclopentadiene and 5% of ethylidene norbornene, adding 0.01% -2% of antioxidant o-di-tert-butyl-p-methylphenol (calculated by the mass of dicyclopentadiene) under the protection of nitrogen, fully and uniformly stirring on a low-temperature reaction bath, and controlling the temperature to be 10-30 ℃.

(3) Mixed solidification forming

Measuring 1.93ml of A solution and 120g of B solution, quickly mixing the A solution and the B solution through a multi-section tubular mixer under the protection of nitrogen, injecting the mixture into a reaction mold, starting temperature programming of the mold, keeping the reaction temperature at 60 ℃, keeping the temperature for 1h, keeping the post-treatment temperature at 140 ℃, and keeping the temperature for 1 h.

And (3) after the mold is cooled, demolding the product to obtain two mold cavities, namely 60g of product.

When the quantitative ratio of dicyclopentadiene to the catalyst substance is 10000:1, the mass ratio of dicyclopentadiene to ethylidene norbornene is 95%: at 5%, the tensile, flexural, impact strength, elongation at break and heat distortion temperature of the dicyclopentadiene homopolymer are shown in Table 1.

TABLE 1 Polymer mechanics at different proportions of monomer and catalyst and at different ENB contents