TWI507469B - Method for making a nano enhanced thermo-durable thermosetting polyester material - Google Patents

Description

Nano-reinforced heat-resistant thermosetting polyester material

The invention relates to a method for preparing a nano-reinforced heat-resistant thermosetting polyester material, in particular to increase the resin use temperature, increase the rigidity and crosslink density of the polyester molecular chain, and greatly improve the heat resistance and heat stability of the material. The effect of sexual and mechanical properties.

According to the general composite material industry, the most widely used resin material is thermosetting unsaturated polyester resin, which has a market output value of up to 66%. The unsaturated polyester resin has easy processing, corrosion resistance, chemical resistance and mechanical properties. They are often used on structural parts that require mechanical strength, corrosion resistance and lightweight, compared to high performance resin materials used in the aerospace industry, including: Bismaleimide, polyammonium Epoxy resin, etc., which are characterized by high price, long hardening reaction time, high temperature resistance and excellent mechanical properties. Unsaturated polyester resin materials have popular price, fast hardening reaction, corrosion resistance, hydrolysis resistance and chemical resistance. Good product characteristics, but high temperature resistance is obviously insufficient.

However, the application of thermosetting unsaturated polyester resin materials is mainly focused on yacht ships, chemical storage tanks, industrial pipelines and tower tank containers. The heat resistance requirements are not as high as that of Aerospace Industries. For example, yachts use water resistance to resins. Sexual and moisture barrier properties are particularly important, and the temperature requirements for use are not more than 100 ° C. However, for harsh industrial applications (160 ° C) with high temperature requirements, such as chemical absorption towers, high temperature chimneys, etc., the requirements cannot be met. On the other hand, the industrial application of a wide range of hot-pressing machine tools, plastic injection machines, heat-sealed packaging machines, wood products, pressure beds and other high-pressure high-temperature forming machinery and electric heaters, ovens, ovens and households Heating equipment such as dryers must use heat-shielding energy-saving materials that are excellent in heat resistance and oxidation resistance, and that are competitive in thermal conduction insulation and low heat loss.

In order to protect the machine-related components, take into account the production process and energy-saving requirements, and meet the safety requirements of field workers, the insulation and heat-insulating materials used in industrial machines must meet high strength, corrosion resistance, chemical resistance, and heat resistance. , durable, and other requirements, but also to mass production and cost competitiveness.

In view of this, the inventors of this case have intensively discussed the above-mentioned problems of conventional inventions, and actively pursued solutions through years of experience in R&D and manufacturing of related industries. After long-term efforts in research and development, they have finally succeeded in developing this book. Invented the "manufacturing method of nano-reinforced heat-resistant thermosetting polyester material" to improve various problems in the conventional use.

The main object of the present invention is to improve the resin use temperature, increase the rigidity and crosslink density of the polyester molecular chain, and greatly improve the heat resistance, thermal stability and mechanical properties of the material.

To achieve the above object, the present invention is a process for preparing a nano-reinforced heat-resistant thermosetting polyester material comprising at least the following steps: Step 1: a polyester resin containing a low molecular weight unsaturated vinyl isononate, a functionalized polyester oligopolymer containing an unsaturated vinyl group, a polyester resin containing a layered decanoate unsaturated vinyl group, and a reactive monomer containing a vinyl group to form a polymer viscous liquid; Step 2: The polymer viscous liquid is subjected to a functional group polymerization hardening reaction by a combination of a catalyst and an auxiliary agent to form a three-dimensional network organic-inorganic hybrid thermosetting polyester resin having a high crosslink density.

In the above embodiment of the present invention, the layered niobate is an organically modified montmorillonite layered niobate.

In the above embodiment of the present invention, the layered tantalate is composed of a layered/peeled layered tantalate layer which is uniformly dispersed by a synchronous intercalation polymerization method.

In the above embodiment of the present invention, the average particle size of the layered citrate is between 0.6 μ and 0.8 μ , and the total amount ranges from 1% to 7.5%.

In the above embodiment of the present invention, the interlayer distance of the layered tantalate is between 3 nm and 100 nm.

In the above embodiment of the present invention, the polyester resin containing a layered citrate unsaturated vinyl group contains a functional group such as bisphenol A and/or phenolic.

In the above embodiment of the invention, the vinyl-containing reactive single system comprises at least styrene, styrene or triallyl melamine and mixtures thereof.

In the above embodiment of the present invention, the viscosity of the polymer viscous liquid is between 200 cps and 1800 cps, and preferably between 300 cps and 700 cps.

In the above embodiment of the invention, the thermosetting polyester material can be subjected to a polymerization hardening reaction at room temperature or at a high temperature.

In the above embodiment of the present invention, the thermosetting polyester material which is subjected to the hardening reaction has a glass transition temperature of at least 160 ° C or higher.

Please refer to FIG. 1 and FIG. 2, which are schematic diagrams of the first step of the present invention and the second step of the present invention. As shown in the figure: The present invention is a method for preparing a nano-reinforced heat-resistant thermosetting polyester material, which comprises at least the following steps:

Step 1: a polyester resin containing a low molecular weight unsaturated vinyl group, a functionalized polyester oligopolymer 12 containing an unsaturated vinyl group, a polyester resin containing a layered decanoate unsaturated vinyl group, And the vinyl-containing reactive monomer 14 forms a polymer viscous liquid 10; wherein the layered citrate is an organically modified layered citrate, and the layered citrate is produced by a simultaneous intercalation polymerization method A uniformly dispersed intercalated/peeled layered tantalate layer having an average particle size of between 0.6 μ and 0.8 μ and a total amount ranging from 1% to 7.5%. The interlayer distance of the layered niobate is between 3 nm and 100 nm, and the polyester resin 13 containing the layered niobate unsaturated vinyl group contains functional groups such as bisphenol A and/or phenolic, and The vinyl-containing reactive monomer 14 comprises at least styrene, styrene or triallyl melamine and a mixture thereof, and the viscosity of the polymer viscous liquid 10 is between 200 cps and 1800 cps. It is best between 300cps and 700cps.

Step 2: the polymer viscous liquid 10 is subjected to a functional group polymerization hardening reaction by the combination of the catalyst 15 and the auxiliary agent 16, thereby forming a three-dimensional network organic-inorganic hybrid thermosetting polyester resin 1 having a high crosslink density, wherein The thermosetting polyester material 1 can be subjected to a polymerization hardening reaction at room temperature or a high temperature, and the thermosetting polyester material obtained by the hardening reaction has a glass transition temperature of at least 160 ° C or higher.

Thus, a thermosetting polyester material 1 can be produced by the above steps, thereby being fabricated by means of nano-strengthening and chemical modification, to improve the heat resistance and mechanical properties of the thermosetting polyester resin, thereby further enabling the present invention. At least the following advantages are achieved:

1. Introducing nano citrate into a polymer resin to form an organic-inorganic hybrid thermosetting polyester resin 1 by nanometer-scale strengthening, and further utilizing a tortuous path between bismuth silicates to effectively block heat and gas, and strengthen the lifting material. Thermal inferior solution temperature and thermal stability.

2. The main polymer chain and cross-linking monomer are modified, and the groups such as bisphenol A and phenolic are introduced into the polymer chain skeleton, and the main molecular chain composition of the resin is adjusted, and the high heat-resistant styrene-butadiene is combined. The monomer hardening reaction produces a three-dimensional network organic-inorganic hybrid thermosetting polyester resin 1 having a high crosslink density, which increases the resin use temperature and increases the rigidity and crosslink density of the polyester molecular chain to improve the heat resistance of the material. Thermal stability, and mechanical properties.

3. Nano-scale dispersed bismuth silicate is a lightweight, high-rigidity, high-strength inorganic reinforcement with excellent diffusion barrier properties, including unsaturated polyester, epoxy, compared to traditional micron-sized reinforcing materials. Thermosetting materials such as resins and phenolic resins can be prepared by simultaneous intercalation polymerization to prepare nano-reinforced composites by first-organizing montmorillonite (MMT) with appropriate polymerizable monomers. The expansion is expanded, followed by crosslinking polymerization. During the expansion and expansion process, the polymerizable monomer diffuses into the interlayer channel of the layered tantalate, and the end of the monomer penetrates into the interlayer of the tantalate layer, and the formed nano composite material can be divided into intercalations ( Intercalated) and exfoliated or delaminated.

4. The polymer chain penetrates the citrate layer to make the interlayer channel become larger, and the ordered polymer/geranate intercalated intercalation mixture is formed. The dense polymer penetration eventually leads to delamination of the citrate layer. A suspension-dispersed stripped citrate layer-mixed polymer is produced.

5. Compared with traditional unsaturated polyester materials, this creation greatly enhances the use temperature of thermosetting polyester materials, and has resistance at high temperatures of at least 160 °C. Heat.

6. The creative materials have the advantages of easy processing, corrosion resistance, chemical resistance, excellent mechanical properties, and low price, and successfully overcome the aerospace high performance resin, such as: Bismaleimide, polyammonium, The price of epoxy resin is high and the hardening reaction time is long.

7. Nano-reinforced heat-resistant thermosetting polyester resin has the characteristics of easy processing and hardening reaction time which can be mass-produced, and can be applied to the market of heat-resistant heat-blocking energy-saving materials which require a high temperature environment of at least 160 ° C for a long time. The gap is expected to open up new areas of high temperature energy-saving applications for thermoset polyester resin materials.

In summary, the method for preparing the nano-reinforced heat-resistant thermosetting polyester material of the invention can effectively improve various disadvantages of the conventional use, and can improve the use temperature of the resin, increase the rigidity of the polyester molecular chain, crosslink density, and greatly improve the material. The effects of heat resistance, thermal stability and mechanical properties; furthermore, the invention can be made more progressive, more practical, and more in line with the needs of consumers, and indeed meet the requirements of the invention patent application, and file a patent application according to law.

However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto; therefore, the simple equivalent changes and modifications made in accordance with the scope of the present invention and the contents of the invention are modified. All should remain within the scope of the invention patent.

1‧‧‧ thermosetting polyester resin

10‧‧‧Polymer viscous liquid

11‧‧‧Polyester resin containing low molecular weight unsaturated vinyl

12‧‧‧Functional polyester oligopolymers containing unsaturated vinyl groups

13‧‧‧ Polyester resin containing layered phthalate unsaturated vinyl

14‧‧‧Reactive monomer containing vinyl

15‧‧‧ Catalyst

16‧‧‧Auxiliary

Figure 1 is a schematic view of the first step of the present invention.

Figure 2 is a schematic diagram of the second step of the present invention.

1‧‧‧ thermosetting polyester resin

10‧‧‧Polymer viscous liquid

15‧‧‧ Catalyst

16‧‧‧Auxiliary

Claims (5)

The invention relates to a method for preparing a nano-reinforced heat-resistant thermosetting polyester material, which comprises at least the following steps: Step 1: a polyester resin containing a low molecular weight unsaturated vinyl group, and a functionalized polyester oligo polymer containing an unsaturated vinyl group a polyester resin containing a layered bismuth silicate unsaturated vinyl group, which is an organically modified layered silicate, which is a uniformly dispersed intercalation/peel layer obtained by simultaneous intercalation polymerization. The silicate layer comprises a layered bismuth silicate unsaturated vinyl resin containing functional groups such as bisphenol A and/or phenolic, and a vinyl-containing reactive monomer to form a polymer viscous layer. a liquid, wherein the vinyl-containing reactive single system comprises at least styrene, styrene or triallyl melamine and mixtures thereof; and step 2: using the polymer viscous liquid as a catalyst and an adjuvant The functional group polymerization hardening reaction is carried out to form a three-dimensional network organic-inorganic hybrid thermosetting polyester resin having a high crosslinking density. According to the method for preparing a nano-reinforced heat-resistant thermosetting polyester material according to the first aspect of the patent application, wherein the average particle size of the layered silicate is between 0.6 μ and 0.8 μ, and the total amount is in the range 1%~7.5%. The method for preparing a nano-reinforced heat-resistant thermosetting polyester material according to the first aspect of the patent application, wherein the interlayer distance of the layered tantalate is between 3 nm and 100 nm. The method for preparing a nano-reinforced heat-resistant thermosetting polyester material according to the first aspect of the patent application, wherein the viscosity of the polymer viscous liquid is between 200 cps and 1800 cps. Nano-reinforced heat-resistant thermosetting polyester material according to item 1 of the patent application scope The method for preparing a material, wherein the thermosetting polyester material obtained by the hardening reaction has a glass transition temperature of at least 160 ° C or higher.