CN116178634B - A tung oil-based polymer and its preparation method and application - Google Patents

Abstract

A tung oil-based polymer and its preparation method and application, wherein natural tung oil is subjected to a series of reactions to obtain an active monomer containing multiple functional groups; then the obtained tung oil-based active monomer is subjected to a cross-linking and curing reaction with a hydroxyl-containing acrylate active monomer and an isocyanate-terminated polyurethane prepolymer to obtain a compression-resistant tung oil-based polymer pavement material. The polymer network prepared by this technology contains two different cross-linking structures of polyurethane and polyacrylate, and the system has a high cross-linking density, which can give the prepared polymer excellent bonding strength, compressive rigidity and weather resistance, and the material has a certain toughness. The raw material of the compression-resistant tung oil-based polymer pavement material mainly uses renewable tung oil as the main raw material, which is environmentally friendly, cheap and of high quality. The technical invention has a simple preparation process, can be cured at medium and low temperatures, and has broad application prospects.

Description

A tung oil-based polymer and its preparation method and application

Technical Field

The invention belongs to the technical field of functional polymer preparation, and in particular relates to a tung oil-based polymer and a preparation method and application thereof.

Background Art

There are three main types of common steel bridge deck paving materials: (1) cement concrete materials. (2) asphalt concrete materials. (3) polymer concrete materials. In comparison, polymer concrete materials have many advantages. They are lightweight and can significantly reduce the load on bridges. They have high bonding strength, tensile strength, bending strength and elastic recovery rate, and can withstand repeated fatigue under heavy loads. They are also impermeable and can effectively protect steel bridge decks from corrosion. Cement-based materials have high stiffness and deadweight, and the problems of drying and temperature shrinkage cracks in cement materials are difficult to avoid. Asphalt concrete has insufficient high temperature performance and is prone to permanent deformation and damage such as rutting, bulging and shifting.

With the increase in the number of steel bridges under construction, the demand for new polymer paving materials is becoming more and more urgent. On the other hand, with the gradual scarcity of fossil raw materials and the gradual increase in people's environmental awareness, the development of new polymer materials based on bio-based raw materials has received more and more attention. Tung oil is the most common oil crop in my country. It is widely distributed in southwest my country and has abundant sources. Tung oil contains a large number of ester groups and unsaturated double bonds, which can undergo a variety of chemical reactions, such as ester exchange, pyrolysis, epoxidation, addition reaction, etc. It is widely used in coatings, construction, plastics, rubber and other fields.

Conventional pavement materials on the market today are basically developed using fossil resources such as coal and oil as raw materials. The industrial chain is cumbersome, the price is high and it is easy to cause environmental pollution. The pavement polymer materials produced also crack, and the compressive strength is mostly difficult to meet the use requirements while ensuring flexibility. This technology uses natural tung oil to prepare a compressive tung oil-based polymer pavement material, which minimizes the use of petrochemical products. This type of polymer prepared by this technical achievement has the advantages of being raw material friendly, energy-saving and environmentally friendly, and has broad market application prospects. This material can solve the problems faced by the steel bridge deck pavement structure, and at the same time expand the application of bio-based raw materials in steel bridge deck pavement.

Summary of the invention

Technical problem to be solved: In order to address the inherent defects of existing conventional cement pavement materials and asphalt pavement materials on the market and break the foreign technology monopoly, the present invention provides a tung oil-based polymer and its preparation method and application. Using natural tung oil as raw material, a compression-resistant tung oil-based polymer pavement material is provided, and the polymer has excellent compression resistance and weather resistance.

Technical solution: A method for preparing a tung oil-based polymer, the preparation steps are as follows: the first step: adding tung oil and acrylic acid into a reactor in a mass ratio of 1:0.2, then adding a polymerization inhibitor accounting for 0.5‰-1.0‰ of the mass of the tung oil, reacting at 160°C for 3h, and obtaining an intermediate product 1 after cooling; adding a double bond hydroxylation catalyst accounting for 0.5%-1.2% of the mass of the intermediate product 1, formic acid accounting for 30%-40% of the mass of the intermediate product 1, and hydrogen peroxide accounting for 50%-80% of the mass of the intermediate product 1, reacting at 55-70°C for 4-6h, and obtaining a hydroxyl-containing intermediate product 2 after liquid separation and washing; adding a polymerization inhibitor accounting for 0.5‰-1.0‰ of the mass of the intermediate product 2 and 0.5%-1.5% of the weight of the epoxy ring-opening esterification catalyst and methacrylic acid glycidyl in an equal molar ratio to the carboxyl contained in the intermediate product 2 are reacted at 115-118°C for 2.0-3.0h to obtain a tung oil-based active monomer; the second step: adding 30%-50% of the weight of the tung oil-based active monomer to hydroxyethyl methacrylate, and then adding polyurethane prepolymer-E95C for cross-linking and curing reaction, the addition amount of polyurethane prepolymer-E95C is 150%-300% of the weight of the tung oil-based active monomer, and then adding an initiator, pre-mixing and stirring at 50°C, and then heating to 60-70°C and reacting for 2-3h to obtain a tung oil-based polymer.

Preferably, the polymerization inhibitor is any one of hydroquinone, 2-tert-butylhydroquinone and 2,5-di-tert-butylhydroquinone.

Preferably, the double bond hydroxylation catalyst is any one of toluene-4-sulfonic acid and m-xylene-4-sulfonic acid.

Preferably, the epoxy ring-opening esterification catalyst is any one of triethylbenzylammonium chloride, benzyltrimethylammonium chloride and hexadecyltrimethylammonium chloride.

Preferably, the initiator is any one of benzoyl peroxide and tert-butyl perbenzoate.

The tung oil-based polymer is prepared by the above preparation method.

Application of the above tung oil-based polymer in the preparation of pavement materials.

Beneficial effects: ① The polymer pavement material provided by the present invention contains two different cross-linked structures, a flexible polyurethane structure of fatty acid carbon chains and a polyacrylate, which can give the prepared polymer excellent bonding strength, compressive rigidity and weather resistance, and ensure that the polymer material has a certain toughness while ensuring high compressive strength.

② The final material can be obtained by curing at medium and low temperatures, which is convenient for construction, energy-saving and environmentally friendly. Compared with the current technical level, its strength performance is more superior and can meet the requirements of the base pavement of large-span bridges and conventional viaducts.

③ The raw materials for preparing compression-resistant tung oil-based polymer pavement materials by this technology mainly use renewable tung oil as the main raw material, which is abundant in source, reduces dependence on fossil resources, and meets the requirements of sustainable development.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is an infrared spectrum of the compression-resistant tung oil-based polymer pavement material in Example 1; in the infrared spectrum of the tung oil-based active monomer, 1730 cm ^-1 is the stretching vibration absorption peak of the C=O bond in the ester group. 1790 cm ^-1 is the stretching vibration absorption peak of the C=O bond in the residual carboxyl group. 1238 cm ^-1 is the asymmetric stretching vibration absorption peak of the COC bond, and 1167 cm ^-1 is the symmetric stretching vibration absorption peak of the COC bond. 2926 cm ^-1 and 2856 cm ^-1 are the asymmetric and symmetric stretching vibration absorption peaks of the CH bonds in -CH ₃ - and -CH ₂ - in the tung oil-based active monomer. The broad peak at 3500 cm ^-1 is the absorption peak generated by the hydrogen bond association between -OH in the carboxyl group, 1635 cm ^-1 is the stretching vibration absorption peak of the C=C double bond, and 985 cm ^-1 is the out-of-plane bending vibration absorption peak of the CH bond on the unsaturated carbon atom. The appearance of these peaks indicates that the tung oil-based active monomer has been successfully synthesized.

DETAILED DESCRIPTION

The present invention is further described below in conjunction with embodiments:

Example 1

Tung oil and acrylic acid are added into a reactor in a mass ratio of 1:0.2, and then 0.5‰ of the mass of tung oil as a hydroquinone inhibitor is added, and the reaction is carried out at 160°C for 3.0 hours. After cooling, an intermediate product 1 is obtained; 0.5% of the mass of toluene-4-sulfonic acid catalyst, 30% of the mass of formic acid, and 50% of the mass of hydrogen peroxide are added to the intermediate product 1, and the reaction is carried out at 70°C for 4.0 hours. After liquid separation and washing, a hydroxyl-containing intermediate product 2 is obtained; 0.5‰ of the mass of an inhibitor and 0.5% of a triethylbenzylammonium chloride catalyst, and methacrylic acid glycidyl in an equal molar ratio to the carboxyl group contained in the intermediate product 2 are added to the intermediate product 2, and the reaction is carried out at 115°C for 3.0 hours to obtain a tung oil-based active monomer. Add 50% of the mass of hydroxyethyl methacrylate to the tung oil-based active monomer, and then add polyurethane prepolymer-E95C for cross-linking and curing reaction. The addition amount of polyurethane prepolymer-E95C is 150% of the mass of the tung oil-based active monomer. Add benzoyl peroxide initiator, pre-mix and stir evenly at 50°C, then heat to 70°C and react for 2.0h to obtain a compression-resistant tung oil-based polymer pavement material.

Example 2

Tung oil and acrylic acid are added into a reactor in a mass ratio of 1:0.2, and then 2,5-di-tert-butylhydroquinone inhibitor with a mass ratio of 1.0‰ of tung oil is added, and the reaction is carried out at 160°C for 3.0 hours. After cooling, an intermediate product 1 is obtained; 1.2% of the mass of m-xylene-4-sulfonic acid catalyst, 40% of the mass of formic acid, and 80% of the mass of hydrogen peroxide are added to the intermediate product 1, and the reaction is carried out at 55°C for 6.0 hours. After liquid separation and washing, a hydroxyl-containing intermediate product 2 is obtained; 1.0‰ of the mass of inhibitor and 1.5% of hexadecyltrimethylammonium chloride catalyst, and methyl glycidyl methacrylate with a molar ratio equal to the carboxyl group contained in the intermediate product 2 are added to the intermediate product 2, and the reaction is carried out at 118°C for 2 hours to obtain a tung oil-based active monomer. Add 30% of hydroxyethyl methacrylate by weight to the tung oil-based active monomer, and then add polyurethane prepolymer-E95C for cross-linking and curing reaction. The addition amount of polyurethane prepolymer-E95C is 300% of the mass of the tung oil-based active monomer. Add tert-butyl perbenzoate initiator, pre-mix and stir evenly at 50°C, then heat to 60°C and react for 3.0 hours to obtain a compression-resistant tung oil-based polymer pavement material.

Example 3

Tung oil and acrylic acid are added into a reactor in a mass ratio of 1:0.2, and then 2-tert-butylhydroquinone inhibitor with a mass ratio of 0.8‰ of tung oil is added, and the reaction is carried out at 160°C for 3.0 hours. After cooling, an intermediate product 1 is obtained; 0.75% of toluene-4-sulfonic acid catalyst, 35% of formic acid, and 60% of hydrogen peroxide are added to the intermediate product 1, and the reaction is carried out at 60°C for 5.0 hours. After liquid separation and washing, a hydroxyl-containing intermediate product 2 is obtained; 0.75‰ of the mass inhibitor and 1.2% of benzyltrimethylammonium chloride catalyst, and methacrylic acid glycidyl in an equal molar ratio to the carboxyl group contained in the intermediate product 2 are added to the intermediate product 2, and the reaction is carried out at 116°C for 2.5 hours to obtain a tung oil-based active monomer. Add 40% of hydroxyethyl methacrylate by weight to the tung oil-based active monomer, and then add polyurethane prepolymer-E95C for cross-linking and curing reaction. The addition amount of polyurethane prepolymer-E95C is 200% of the mass of the tung oil-based active monomer. Add benzoyl peroxide initiator, pre-mix and stir evenly at 50°C, then heat to 65°C and react for 2.5 hours to obtain a compression-resistant tung oil-based polymer pavement material.

Example 4

Tung oil and acrylic acid are added into a reactor in a mass ratio of 1:0.2, and then a hydroquinone inhibitor of 0.5-1.0‰ of the mass of the tung oil is added, and the reaction is carried out at 160°C for 3.0 hours. After cooling, an intermediate product 1 is obtained; 1.0% of the mass of m-xylene-4-sulfonic acid catalyst, 35% of the mass of formic acid, and 70% of the mass of hydrogen peroxide are added to the intermediate product 1, and the reaction is carried out at 65°C for 5.0 hours. After liquid separation and washing, a hydroxyl-containing intermediate product 2 is obtained; 0.75‰ of the mass of the inhibitor and 0.8% of the triethylbenzylammonium chloride catalyst, as well as methacrylic acid glycidyl in an equal molar ratio to the carboxyl group contained in the intermediate product 2 are added to the intermediate product 2, and the reaction is carried out at 117°C for 2.5 hours to obtain a tung oil-based active monomer. Add 40% of hydroxyethyl methacrylate by weight to the tung oil-based active monomer, and then add polyurethane prepolymer-E95C for cross-linking and curing reaction. The addition amount of polyurethane prepolymer-E95C is 250% of the mass of the tung oil-based active monomer. Add tert-butyl perbenzoate initiator, pre-mix and stir evenly at 50°C, then heat to 65°C and react for 2.5 hours to obtain a compression-resistant tung oil-based polymer pavement material.

Comparative Example:

The polymers prepared in Examples 1 to 4 were tested for mechanical properties, and the test results are shown in Table 1.

Table 1 Performance comparison of randomly selected experimental groups

Note: The tensile strength of polymers shall refer to GB/T 1040.3-2006 test; the compressive strength shall refer to GB/T 2567-2008 test; the bonding strength shall refer to GB/T 6329-1996 (23°C) test; the water resistance shall refer to GB/T 22374-2008 test; the accelerated freeze-thaw test (10 times) shall refer to JG/T 25-1999 test.

Claims (7)

1. A preparation method of a tung oil-based polymer is characterized by comprising the following preparation steps: the first step: adding tung oil and acrylic acid into a reactor according to a mass ratio of 1:0.2, then adding a polymerization inhibitor accounting for 0.5-1.0 per mill of the mass of the tung oil, reacting at 160 ℃ for 3h, and cooling to obtain an intermediate product 1; adding a double bond hydroxylation catalyst accounting for 0.5-1.2% of the mass of the intermediate product 1, formic acid accounting for 30-40% of the mass of the intermediate product and hydrogen peroxide accounting for 50-80% of the mass of the intermediate product, reacting for 4-6h at 55-70 ℃, and separating and washing to obtain a hydroxyl-containing intermediate product 2; adding a polymerization inhibitor accounting for 0.5 to 1.0 per mill of the mass of the intermediate product 2, an epoxy ring-opening esterification catalyst accounting for 0.5 to 1.5 percent of the mass of the intermediate product 2, and glycidyl methacrylate with the same molar ratio as carboxyl contained in the intermediate product 2 respectively, and reacting for 2.0 to 3.0 hours at the temperature of 115 to 118 ℃ to obtain a tung oil-based active monomer; and a second step of: adding hydroxyethyl methacrylate accounting for 30-50% of the mass of the tung oil-based active monomer into the tung oil-based active monomer, adding polyurethane prepolymer-E95C for crosslinking and curing reaction, wherein the addition amount of the polyurethane prepolymer-E95C is 150-300% of the mass of the tung oil-based active monomer, adding an initiator, premixing and uniformly stirring at 50 ℃, and then heating to 60-70 ℃ for reacting for 2-3 hours to obtain the tung oil-based polymer.

2. The method for preparing a tung oil-based polymer according to claim 1, wherein the polymerization inhibitor is any one of hydroquinone, 2-tert-butylhydroquinone and 2, 5-di-tert-butylhydroquinone.

3. The method for producing a tung oil-based polymer according to claim 1, wherein the double bond hydroxylation catalyst is any one of toluene-4-sulfonic acid and m-xylene-4-sulfonic acid.

4. The method for preparing a tung oil-based polymer according to claim 1, wherein the epoxy ring-opening esterification catalyst is any one of triethylbenzyl ammonium chloride, benzyltrimethyl ammonium chloride and cetyltrimethylammonium chloride.

5. The method for preparing a tung oil-based polymer according to claim 1, wherein the initiator is any one of benzoyl peroxide and tert-butyl peroxybenzoate.

6. A tung oil based polymer produced by the process of any one of claims 1 to 5.

7. The use of the tung oil-based polymer of claim 6 in the preparation of pavement materials.