A rosin-based polymer with high hydrogen bonding force, preparation method thereof and application thereof

Abstract

The invention discloses a rosin-based polymer with high hydrogen bonding force, a preparation method and an application thereof. The rosin-based polymer with high hydrogen bonding force has a molecular structural formula of: wherein R is an epoxy soybean oil reaction residue. The rosin-based polymer with high hydrogen bonding force of the invention uses biomass rosin and epoxy soybean oil as raw materials, belongs to green environment-friendly resource chemicals, has no problems such as biological toxicity and environmental pollution, is easy to obtain raw materials, has low cost, has a simple synthesis process, is environmentally friendly, and conforms to the concept of sustainable development; has good plasticizing performance for polyvinyl chloride, can replace traditional phthalate traditional plasticizers, helps to improve the performance of polyvinyl chloride products, and can be bonded with polyvinyl chloride to form an integrated structure, effectively overcoming the problem of plasticizer migration.

Description

Technical Field

[0001] The invention relates to a rosin-based polymer with high hydrogen bonding force, a preparation method and application thereof, and belongs to the technical field of natural resource modification and utilization. Background Art

[0002] Plasticizers are a type of fine chemical products that are widely used in polyvinyl chloride (PVC) to improve the performance of plastic products. Phthalate plasticizers are the most widely used type of traditional plasticizers. These plasticizers are highly practical and have good performance, but they are easy to migrate during processing and use, causing a certain degree of environmental pollution. In view of the defects of traditional plasticizers, finding new environmentally friendly and non-toxic plasticizers has become a hot topic in the industry.

[0003] Rosin is a renewable forest resource with the characteristics of wide distribution, low price and high quality. At the same time, soybean oil raw materials also have the advantages of wide planting, high output and low cost. The inventor uses rosin and epoxidized soybean oil as raw materials to synthesize rosin-based polymers with high hydrogen bonding force, which can effectively plasticize polyvinyl chloride and can be bonded with polyvinyl chloride to form an integral structure, overcoming the problem of plasticizer migration, broadening the utilization rate of rosin and epoxidized soybean oil, and can replace non-renewable petrochemical products. Summary of the invention

[0004] The invention provides a rosin-based polymer with high hydrogen bonding force, a preparation method and application thereof, which has good plasticizing performance, simple preparation, low cost and high yield.

[0005] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0006] A rosin-based polymer with high hydrogen bonding force, the molecular structure of which is:

[0007] Wherein, R is the reaction residue of epoxidized soybean oil.

[0008] The above rosin-based polymer has many hydrogen bonding groups and high reactivity. It not only has an excellent plasticizing effect, but also can be bonded with polyvinyl chloride to form an integral structure, effectively overcoming the problem of plasticizer migration.

[0009] A rosin-based polymer with high hydrogen bonding strength, prepared by the reaction of epoxy soybean rosin ester and hexamethylene diisocyanate.

[0010] The above method does not require a solvent, and its yield can reach nearly 100%, without the need for purification and other treatments. This application regards a conversion greater than 99.99% as 100% conversion.

[0011] The reaction temperature is 80-95°C and the reaction time is 0.5-1.5h, which has the advantages of low energy consumption and high efficiency.

[0012] In order to better ensure the application effect, the molar ratio of epoxy soybean rosin ester to hexamethylene diisocyanate is 1: (3-3.5).

[0013] As one specific implementation scheme, the preparation of the above-mentioned epoxy soybean oil rosin ester is as follows: rosin and epoxy soybean oil are mixed, a catalyst is added, and the mixture is reacted at 105-130°C for 1-3 hours. After the reaction is completed, the mixture is washed with water and dried to obtain the epoxy soybean oil rosin ester. The catalyst is at least one of triethoxybenzyl ammonium chloride, tetrabutyl ammonium chloride or trioctylmethyl ammonium chloride; the molar ratio of the epoxy group of the epoxy soybean oil to the carboxyl group of the rosin is 1:(6-6.5); the drying temperature is 70-150°C, and the drying time is 3-20 hours.

[0014] The above-mentioned rosin-based polymer with high hydrogen bonding force can be used as a polyvinyl chloride plasticizer. The applicant has found through research that the above-mentioned new rosin-based polymer plasticizer with high hydrogen bonding force introduces more ester groups and hydrogen bonding effects, such as NH and Cl-C, C=O and HC, N=H and C=O, which will form strong hydrogen bonding forces and bond with polyvinyl chloride to form a uniform and stable overall structure, thereby avoiding the migration of the plasticizer from the molecular structure of polyvinyl chloride.

[0015] The amount of the rosin-based polymer with high hydrogen bonding force is 10-30% of the mass of the polyvinyl chloride.

[0016] In order to further improve the plasticizing effect, a rosin-based polymer with high hydrogen bonding force is mixed with cardanol glycidyl ether for use as a polyvinyl chloride plasticizer. Preferably, the mass ratio of the new rosin-based polymer plasticizer with high hydrogen bonding force to cardanol glycidyl ether is (2-5):1, preferably (2-3):1. The new rosin-based polymer plasticizer with high hydrogen bonding force and cardanol glycidyl ether are both reactive bio-based materials. The inventors have found that compounding the two in a specific ratio not only has good processing performance, but also promotes the improvement of reaction activity, and can form a network cross-linked structure with polyvinyl chloride to promote the improvement of strength, flexibility, waterproofness and corrosion resistance.

[0017] The technologies not mentioned in the present invention are all referred to the prior art.

[0018] The rosin-based polymer with high hydrogen bonding force of the invention uses biomass rosin and epoxidized soybean oil as raw materials, belongs to green and environmentally friendly resource chemicals, has no problems such as biological toxicity and environmental pollution, is easy to obtain raw materials, has low cost, has a simple synthesis process, is environmentally friendly, and conforms to the concept of sustainable development; has good plasticizing performance on polyvinyl chloride, can replace traditional phthalate traditional plasticizers, helps to improve the performance of polyvinyl chloride products, can be bonded with polyvinyl chloride to form an integrated structure, and effectively overcomes the problem of plasticizer migration. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the infrared spectrum of the rosin-based polymer with high hydrogen bonding force obtained in Example 1;

[0020] Figure 2 This is the H NMR spectrum of the rosin-based polymer with high hydrogen bonding force obtained in Example 1;

[0021] Figure 3 This is the C NMR spectrum of the rosin-based polymer with high hydrogen bonding force obtained in Example 1. DETAILED DESCRIPTION

[0022] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0023] In each case, unless otherwise specified, the reaction was carried out at room temperature (15-25°C).

[0024] Example 1

[0025] A method for preparing a novel rosin-based polymer plasticizer with high hydrogen bonding force comprises the following steps:

[0026] 1) Rosin (22.68 g, first grade, softening point 71°C, Henan Yuheng Chemical Co., Ltd.) and epoxidized soybean oil (20.00 g, Qingzhou Hongwei Auxiliary Co., Ltd., viscosity 325 mPa.S) were placed in a three-necked flask and mixed, and a catalyst triethoxybenzyl ammonium chloride (0.05 g) was added. The mixture was stirred and heated to 115°C under a nitrogen atmosphere, and reacted for 2 h. The mixture was then washed with deionized water and dried at 140°C for 3 h to obtain epoxidized soybean rosin ester.

[0027] 2) All the epoxy soybean oil rosin ester prepared in step 1) was reacted with hexamethylene diisocyanate (10.09 g) at 85° C. for 0.5 h to obtain a rosin-based polymer with high hydrogen bonding force, with a conversion rate of 100%.

[0028] Figure 1This is the infrared spectrum of Example 1, where a is rosin, b is epoxidized soybean oil rosin ester, and c is the target product (rosin-based polymer with high hydrogen bonding force). -1 The carboxyl peak is near the center. In b, the carboxyl peak disappears at 1744 cm -1 The ester peak appears at 3565cm -1 The hydroxyl peak appears at 1246 cm -1 and 2944cm -1 Ether bond peaks and amide bond peaks appeared at the positions, respectively, indicating that hexamethylene diisocyanate and product 1 had reacted.

[0029] Figure 2 This is the H NMR spectrum of Example 1, 5.77ppm is the H atom peak of the double bond carbon atom of rosin, 2.31ppm is the H atom peak on the methylene group next to the epoxidized soybean oil ester group, and 7.26ppm is the H atom peak on the amide bond generated after the reaction of hexamethylene diisocyanate and product 1. After analysis, it can be seen that the target product has been successfully synthesized.

[0030] Figure 3 The C NMR spectrum of Example 1 shows that 122.36ppm, 135.58ppm and 145.32ppm are characteristic peaks of double bonds in the rosin structure, 173.24ppm is a characteristic peak of the epoxy soybean oil ester group, and 150.32ppm is a characteristic peak of the amide bond. The target product has been successfully synthesized. The structure of the target product is: Wherein, R is the reaction residue of epoxidized soybean oil.

[0031] Example 2

[0032] A method for preparing a novel rosin-based polymer plasticizer with high hydrogen bonding force comprises the following steps:

[0033] 1) Rosin (18.50 g) and epoxidized soybean oil (21.50 g) were placed in a three-necked flask and mixed, and a catalyst triethoxybenzyl ammonium chloride (0.07 g) was added. The mixture was stirred and heated to 108° C. under a nitrogen atmosphere, and reacted for 2.5 h. The mixture was washed with deionized water and dried at 120° C. for 6 h to obtain epoxidized soybean oil rosin ester.

[0034] 2) All the epoxy soybean rosin ester prepared in step 1) was reacted with hexamethylene diisocyanate (8.80 g) at 95° C. for 1 h to obtain a rosin-based polymer with high hydrogen bonding force, with a conversion rate of 100%.

[0035] After analysis, the spectrum of the product obtained in Example 2 has no substantial difference from that in Example 1, and is not provided again.

[0036] Example 3

[0037] A method for preparing a novel rosin-based polymer plasticizer with high hydrogen bonding force comprises the following steps:

[0038] 1) Rosin (19.30 g) and epoxidized soybean oil (17.80 g) were placed in a three-necked flask and mixed, and a catalyst, triethoxybenzyl ammonium chloride (0.058 g), was added. The mixture was stirred and heated to 128° C. under a nitrogen atmosphere, and reacted for 1.5 h. The mixture was washed with deionized water and dried at 135° C. for 2 h to obtain epoxidized soybean oil rosin ester.

[0039] 2) All the epoxy soybean rosin ester prepared in step 1) was reacted with hexamethylene diisocyanate (7.77 g) at 88° C. for 0.5 h to obtain a rosin-based polymer with high hydrogen bonding force, with a conversion rate of 100%.

[0040] After analysis, the spectrum of the product obtained in Example 3 has no substantial difference from that in Example 1, and is not provided again.

[0041] Example 4

[0042] A method for preparing a novel rosin-based polymer plasticizer with high hydrogen bonding force comprises the following steps:

[0043] 1) Rosin (19.80 g) and epoxidized soybean oil (21.20 g) were placed in a three-necked flask and mixed, and a catalyst, triethoxybenzyl ammonium chloride (0.06 g), was added, and the mixture was heated to 130° C. under a nitrogen atmosphere with stirring, and reacted for 1 h. The mixture was washed with deionized water and dried at 110° C. for 12 h to obtain epoxidized soybean oil rosin ester.

[0044] 2) All the epoxy soybean oil rosin ester prepared in step 1) was reacted with hexamethylene diisocyanate (8.50 g) at 80° C. for 1 h to obtain a rosin-based polymer with high hydrogen bonding force, with a conversion rate of 100%.

[0045] After analysis, the spectrum of the product obtained in Example 4 has no substantial difference from that in Example 1, and is not provided again.

[0046] Application Example 1

[0047] 3.0 g of polyvinyl chloride powder (Aladdin Reagent Co., Ltd., specification: K-value 72-71), 0.6 g of the rosin-based polymer with high hydrogen bonding force obtained in Example 1 and 0.3 g of cardanol glycidyl ether (XY767, Anhui Xinyuan Technology Co., Ltd.) were weighed in 50 ml of tetrahydrofuran, stirred at 40° C. for 0.5 h, and the solution was poured into a watch glass and dried at 40° C. for 24 h to obtain a modified polyvinyl chloride film.

[0048] Application Example 2

[0049] 3.0 g of polyvinyl chloride powder (Aladdin Reagent Co., Ltd., specification: K-value 72-71) and 0.9 g of the rosin-based polymer with high hydrogen bonding force obtained in Example 1 were weighed, added to 50 ml of tetrahydrofuran, stirred at 40° C. for 0.5 h, poured the solution into a watch glass and dried at 40° C. for 24 h to obtain a modified polyvinyl chloride film.

[0050] Application Example 3

[0051] 3.0 g of polyvinyl chloride powder (Aladdin Reagent Co., Ltd., specification: K-value 72-71), 0.3 g of the new rosin-based polymer plasticizer with high hydrogen bonding force obtained in Example 1 and 0.6 g of cardanol glycidyl ether (XY767, Anhui Xinyuan Technology Co., Ltd.) were weighed in 50 ml of tetrahydrofuran, stirred at 50° C. for 0.5 h, poured the solution into a watch glass and dried at 45° C. for 24 h to obtain a modified polyvinyl chloride film.

[0052] Comparative Example 1

[0053] Weigh 3.0 g of polyvinyl chloride powder and dissolve it in 50 ml of tetrahydrofuran at 45°C with stirring for 0.5 h. Pour the solution into a watch glass and dry it at 45°C for 24 h to obtain a modified polyvinyl chloride film.

[0054] Comparative Example 2

[0055] Weigh 3.0 g of polyvinyl chloride powder and 1.8 g of dioctyl phthalate in 50 ml of tetrahydrofuran, stir at 45°C for 0.5 h, pour the solution into a watch glass and dry at 45°C for 24 h to obtain a modified polyvinyl chloride film.

[0056] Comparative Example 3

[0057] 3.0 g of polyvinyl chloride powder, 0.6 g of dioctyl phthalate and 0.3 g of cardanol glycidyl ether (XY767, Anhui Xinyuan Technology Co., Ltd.) were weighed into 50 ml of tetrahydrofuran, stirred at 45 °C for 0.5 h, poured the solution into a watch glass and dried at 45 °C for 24 h to obtain a modified polyvinyl chloride film.

[0058] The mechanical properties of the samples were tested according to GB-T 1040-92 Plastic Tensile Properties Test Method and GB / T 1039-1992 Plastic Mechanical Properties Test Method. The properties of the polyvinyl chloride films obtained in each case are shown in Table 1.

[0059] Table 1 Mechanical properties results

[0060] sample Tensile strength(Mpa) Elongation at break (%) Plasticizer migration rate (%) Application Example 1 33.61 376.78 0.08 Application Example 2 31.13 359.12 0.20 Application Example 3 32.90 362.32 0.11 Comparative Example 1 28.32 2.61 0 Comparative Example 2 16.53 205.64 8.62 Comparative Example 3 18.16 141.31 7.39

[0061] The above plasticizer migration test uses 10% ethyl acetate aqueous solution as solvent, and the sample is immersed in the solvent at room temperature for 144 hours. The loss rate of the test weight is the plasticizer migration rate.

[0062] As can be seen from Table 1, the rosin-based polymer with high hydrogen bonding force prepared in the present application has excellent plasticizing properties for polyvinyl chloride, and can be bonded with polyvinyl chloride to form an integrated structure, so that the tensile strength and elongation at break are simultaneously improved, while the stability is improved and migration is avoided; the modified polyvinyl chloride film prepared in Application Example 1 is immersed in 10wt% H2S04 solution and 10wt% NaOH solution at room temperature, respectively, and the weight change rate after immersion for 48h is 0 (the change rate <0.0001% is regarded as zero), and it has excellent acid and alkali corrosion resistance.

Claims

1. A rosin-based polymer with high hydrogen bonding force, characterized in that: It is prepared by the following method: Mix 22.68 g of rosin and 20.00 g of epoxidized soybean oil, add 0.05 g of triethoxybenzyl ammonium chloride as a catalyst, stir and heat to 115° C. under nitrogen atmosphere, react for 2 h, then wash with deionized water and dry at 140° C. for 3 h to obtain epoxidized soybean oil rosin ester; The whole epoxy soybean oil rosin ester prepared in step 1) was reacted with 10.09 g of hexamethylene diisocyanate at 85° C. for 0.5 h to obtain a rosin-based polymer with high hydrogen bonding force.

2. A rosin-based polymer with high hydrogen bonding force, characterized in that: It is prepared by the following method: Mix 18.50 g of rosin and 21.50 g of epoxidized soybean oil, add 0.07 g of triethoxybenzyl ammonium chloride as a catalyst, stir and heat to 108°C under nitrogen atmosphere, react for 2.5 hours, wash with deionized water and dry at 120°C for 6 hours to obtain epoxidized soybean oil rosin ester; The whole epoxy soybean oil rosin ester prepared in step 1) was reacted with 8.80 g of hexamethylene diisocyanate at 95° C. for 1 h to obtain a rosin-based polymer with high hydrogen bonding force.

3. A rosin-based polymer with high hydrogen bonding force, characterized in that: It is prepared by the following method: Mix 19.30 g of rosin and 17.80 g of epoxidized soybean oil, add 0.058 g of triethoxybenzyl ammonium chloride as a catalyst, stir and heat to 128°C under nitrogen atmosphere, react for 1.5 h, wash with deionized water and dry at 135°C for 2 h to obtain epoxidized soybean rosin ester; The whole epoxy soybean oil rosin ester prepared in step 1) was reacted with 7.77 g of hexamethylene diisocyanate at 88° C. for 0.5 h to obtain a rosin-based polymer with high hydrogen bonding force.

4. A rosin-based polymer with high hydrogen bonding force, characterized in that: It is prepared by the following method: Mix 19.80 g of rosin and 21.20 g of epoxidized soybean oil, add 0.06 g of triethoxybenzyl ammonium chloride as a catalyst, stir and heat to 130° C. under nitrogen atmosphere, react for 1 h, wash with deionized water and dry at 110° C. for 12 h to obtain epoxidized soybean oil rosin ester; The whole epoxy soybean oil rosin ester prepared in step 1) was reacted with 8.50 g of hexamethylene diisocyanate at 80° C. for 1 h to obtain a rosin-based polymer with high hydrogen bonding force.

5. An application of a rosin-based polymer with high hydrogen bonding force as claimed in any one of claims 1 to 4, characterized in that: Used as a plasticizer for polyvinyl chloride.

6. The use according to claim 5, characterized in that: The mass dosage of rosin-based polymer with high hydrogen bonding force is 10~30% of the mass of polyvinyl chloride.

7. The use according to claim 5 or 6, characterized in that: Rosin-based polymers with high hydrogen bonding forces are mixed with cardanol glycidyl ether for use as polyvinyl chloride plasticizers.

8. The use according to claim 7, characterized in that: The mass ratio of the rosin-based polymer with high hydrogen bonding force to the cardanol glycidyl ether is (2~5):1.

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