CN116217510A - Rosin-based polymer with high hydrogen bond acting force, preparation method and application thereof - Google Patents

Rosin-based polymer with high hydrogen bond acting force, preparation method and application thereof Download PDF

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CN116217510A
CN116217510A CN202310392749.4A CN202310392749A CN116217510A CN 116217510 A CN116217510 A CN 116217510A CN 202310392749 A CN202310392749 A CN 202310392749A CN 116217510 A CN116217510 A CN 116217510A
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rosin
based polymer
high hydrogen
hydrogen bond
acting force
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李盛林
谢愉翔
罗晟
彭树海
叶锦亮
纪云云
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Guangdong Weisida New Material Co ltd
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Guangdong Weisida New Material Co ltd
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    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D273/00Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C07D273/08Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and more than one oxygen atom
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    • C09FNATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
    • C09F1/00Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
    • C09F1/04Chemical modification, e.g. esterification

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Abstract

The invention discloses a rosin-based polymer with high hydrogen bond acting force, a preparation method and application thereof, wherein the rosin-based polymer with high hydrogen bond acting force has the following molecular structural formula:
Figure DDA0004176416520000011
wherein R is the reaction residue of epoxidized soybean oil. The rosin-based polymer with high hydrogen bond acting force takes biomass rosin and epoxidized soybean oil as raw materials, belongs to green environment-friendly resource chemicals, has no problems of biotoxicity, environmental pollution and the like, is easy to obtain, low in cost, simple in synthesis process, environment-friendly and accords with the concept of sustainable development; the plasticizer has good plasticizing performance to polyvinyl chloride, can replace the traditional phthalate type traditional plasticizer, is beneficial to improving the performance of polyvinyl chloride products, can be bonded with the polyvinyl chloride to form an integrated structure, and effectively overcomes the migration of the plasticizerIs a problem of (a).

Description

Rosin-based polymer with high hydrogen bond acting force, preparation method and application thereof
Technical Field
The invention relates to a rosin-based polymer with high hydrogen bond acting force, a preparation method and application thereof, belonging to the technical field of natural resource modification and utilization.
Background
Plasticizers are a type of fine chemical products widely used in polyvinyl chloride (PVC) to improve the properties of plastic products. Phthalate plasticizers are traditional plasticizers with the largest usage amount, and have strong practicability and good performance, but are easy to migrate in the processing and using processes, and can cause a certain degree of pollution to the environment. In view of the shortcomings of the traditional plasticizers, the search for novel plasticizers that are environmentally friendly and nontoxic has become a great hotspot in the industry.
Rosin is a renewable forest resource and has the characteristics of wide distribution, low price, excellent quality and the like. Meanwhile, the soybean oil raw material also has the advantages of wide planting, high yield, low cost and the like. The inventor adopts rosin and epoxidized soybean oil as raw materials, synthesizes rosin-based polymers with high hydrogen bond acting force, can play an effective plasticizing role on polyvinyl chloride, can be bonded with the polyvinyl chloride to form an integral structure, overcomes the problem of plasticizer migration, widens the utilization rate of the rosin and the epoxidized soybean oil, and can replace non-renewable petrochemical products.
Disclosure of Invention
The invention provides a rosin-based polymer with high hydrogen bond acting force, a preparation method and application thereof, and the rosin-based polymer has the advantages of good plasticizing performance, simple preparation, low cost and high yield.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a rosin-based polymer with high hydrogen bond acting force has a molecular structural formula as follows:
Figure BDA0004176416500000021
wherein R is the reaction residue of epoxidized soybean oil.
The rosin-based macromolecule hydrogen bond has a plurality of groups and high reactivity, not only has excellent plasticizing effect, but also can be bonded with polyvinyl chloride to form an integrated structure, and effectively solves the problem of plasticizer migration.
A rosin-based polymer with high hydrogen bond acting force is prepared by reacting epoxy soybean oil rosin ester with hexamethylene diisocyanate.
The method does not need solvent, the yield can reach approximately 100 percent, and the treatment such as purification and purification is not needed. Greater than 99.99% conversion is considered 100% conversion herein.
The reaction temperature is 80-95 ℃ and the reaction time is 0.5-1.5 h. Has the advantages of low energy consumption and high efficiency.
In order to better ensure the application effect, the molar ratio of the epoxidized soybean oil rosin ester to the hexamethylene diisocyanate is 1: (3-3.5).
As a specific implementation scheme, the preparation method of the epoxidized soybean oil rosin ester comprises the following steps: mixing rosin and epoxidized soybean oil, adding a catalyst, reacting for 1-3 hours at 105-130 ℃, washing with water and drying after the reaction is finished to obtain the epoxidized soybean oil rosin ester. Wherein the catalyst is at least one of triethoxybenzyl ammonium chloride, tetrabutylammonium chloride or trioctylmethyl ammonium chloride; the molar ratio of the epoxy groups of the epoxidized soybean oil to the functional groups of the carboxyl groups of the rosin is 1: (6-6.5); the drying temperature is 70-150 ℃ and the drying time is 3-20 h.
The Gao Qingjian acting force rosin-based polymer can be used as a polyvinyl chloride plasticizer, and the applicant finds that the novel high hydrogen bond acting force rosin-based polymer plasticizer introduces more ester groups and hydrogen bonds, such as N-H and Cl-C, C=O and H-C, and N=H and C=O can form strong hydrogen bond acting force, and can be bonded with polyvinyl chloride to form a uniform and stable integral structure, so that the plasticizer is prevented from migrating from the polyvinyl chloride molecular structure.
The dosage of the rosin-based polymer with the acting force of Gao Qingjian is 10-30% of the mass of polyvinyl chloride.
In order to further improve the plasticizing effect, the rosin-based polymer with high hydrogen bond acting force is mixed with cardanol glycidyl ether for the polyvinyl chloride plasticizer. Preferably, the mass ratio of the novel rosin-based high molecular plasticizer with high hydrogen bond acting force to the cardanol glycidyl ether is (2-5): 1, preferably (2 to 3): 1. the inventor finds that the novel rosin-based high molecular plasticizer with high hydrogen bond acting force and cardanol glycidyl ether are both reactive biological base materials, and the inventor combines the rosin-based high molecular plasticizer with cardanol glycidyl ether in a specific proportion, so that the novel rosin-based high molecular plasticizer not only has good processability, but also promotes the improvement of reactivity, can form a network crosslinking structure with an integrated structure with polyvinyl chloride, and promotes the improvement of strength, flexibility, water resistance and corrosion resistance.
The technology not mentioned in the present invention refers to the prior art.
The rosin-based polymer with high hydrogen bond acting force takes biomass rosin and epoxidized soybean oil as raw materials, belongs to green environment-friendly resource chemicals, has no problems of biotoxicity, environmental pollution and the like, is easy to obtain, low in cost, simple in synthesis process, environment-friendly and accords with the concept of sustainable development; the plasticizer has good plasticizing performance on polyvinyl chloride, can replace the traditional phthalate type traditional plasticizer, is beneficial to improving the performance of polyvinyl chloride products, can be bonded with the polyvinyl chloride to form an integrated structure, and effectively solves the problem of plasticizer migration.
Drawings
FIG. 1 is an infrared spectrum of a rosin-based polymer with high hydrogen bonding force obtained in example 1;
FIG. 2 is a nuclear magnetic H-spectrum of a rosin-based polymer with high hydrogen bonding force obtained in example 1;
FIG. 3 is a nuclear magnetic resonance C spectrum of the rosin-based polymer with high hydrogen bonding force obtained in example 1.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
In each case, the temperatures were not specified and were all carried out at room temperature (15-25 ℃).
Example 1
A preparation method of a novel rosin-based polymer plasticizer with high hydrogen bond acting force comprises the following steps:
1) Rosin (22.68 g, first-order, softening point 71 ℃ C., henan Hendel chemical Co., ltd.) and epoxidized soybean oil (20.00 g, qingzhou Cheng Hongwei auxiliary agent Co., ltd., viscosity 325 mpa.S) were put into a three-necked flask and mixed, and catalyst triethoxybenzyl ammonium chloride (0.05 g) was added, and after stirring and heating to 115 ℃ under nitrogen atmosphere, the mixture was reacted for 2 hours, and then washed with deionized water and dried at 140 ℃ for 3 hours to obtain epoxidized soybean oil rosin ester.
2) All the epoxidized soybean oil rosin ester obtained in the step 1) and hexamethylene diisocyanate (10.09 g) were reacted at a temperature of 85℃for 0.5 hours to obtain a rosin-based polymer having a high hydrogen bonding force, and the conversion was 100%.
FIG. 1 is an infrared spectrum of example 1, wherein a is rosin, b is epoxidized soybean oil rosin ester, and c is the target product (rosin-based polymer with high hydrogen bonding force). In a, 1696cm -1 The carboxyl peak was near, in b, the carboxyl peak disappeared, at 1744cm -1 The peak of ester group appears at 3565cm -1 A hydroxyl peak appears at this point, indicating that rosin and epoxidized soybean oil have reacted. In c, at 1246cm -1 And 2944cm -1 The ether bond peak and the amide bond peak appear respectively, indicating that hexamethylene diisocyanate and product 1 have reacted.
FIG. 2 is a nuclear magnetic H spectrum of example 1, wherein 5.77ppm is H atom peak of double bond carbon atom of rosin, 2.31ppm is H atom peak of epoxy soybean oil ester group side methylene, and 7.26ppm is H atom peak of amide bond generated after reaction of hexamethylene diisocyanate and product 1, and the analysis shows that the target product is successfully synthesized.
FIG. 3 is a graph of nuclear magnetic resonance C of example 1, wherein 122.36ppm, 135.58ppm and 145.32ppm are characteristic peaks of double bonds in rosin structure, 173.24ppm is characteristic peak of epoxidized soybean oil ester group, 150.32ppm is characteristic peak of amide bond, and analysis shows that the target product has been successfully synthesized. The structure of the target product is as follows:
Figure BDA0004176416500000041
wherein R is the reaction residue of epoxidized soybean oil.
Example 2
A preparation method of a novel rosin-based polymer plasticizer with high hydrogen bond acting force comprises the following steps:
1) Rosin (18.50 g) and epoxidized soybean oil (21.50 g) were put into a three-necked flask and mixed, and a catalyst triethoxybenzyl ammonium chloride (0.07 g) was added thereto, followed by stirring and heating to 108℃under nitrogen atmosphere, followed by reaction for 2.5 hours, washing with deionized water, and drying at 120℃for 6 hours to obtain epoxidized soybean oil rosin ester.
2) All the epoxy soybean oil rosin ester prepared in the step 1) and hexamethylene diisocyanate (8.80 g) are reacted for 1h at the temperature of 95 ℃ to obtain rosin-based polymer with high hydrogen bond acting force, and the conversion rate is 100%.
The spectrum of the product obtained in example 2, analyzed, was not substantially different from that of example 1 and was not provided repeatedly.
Example 3
A preparation method of a novel rosin-based polymer plasticizer with high hydrogen bond acting force comprises the following steps:
1) Rosin (19.30 g) and epoxidized soybean oil (17.80 g) were put into a three-necked flask and mixed, and a catalyst triethoxybenzyl ammonium chloride (0.058 g) was added thereto, followed by stirring and heating to 128℃under nitrogen atmosphere, then reaction was carried out for 1.5 hours, washing with deionized water, and drying at 135℃for 2 hours, to obtain epoxidized soybean oil rosin ester.
2) All the epoxidized soybean oil rosin ester obtained in the step 1) and hexamethylene diisocyanate (7.77 g) were reacted at 88 ℃ for 0.5h to obtain a rosin-based polymer with high hydrogen bonding force, and the conversion was 100%.
The spectrum of the product obtained in example 3, analyzed, was not substantially different from that of example 1 and was not provided repeatedly.
Example 4
A preparation method of a novel rosin-based polymer plasticizer with high hydrogen bond acting force comprises the following steps:
1) Rosin (19.80 g) and epoxidized soybean oil (21.20 g) were put into a three-necked flask and mixed, and a catalyst triethoxybenzyl ammonium chloride (0.06 g) was added thereto, followed by stirring and heating to 130 ℃ under nitrogen atmosphere, then reacting for 1h, washing with deionized water, and then drying at 110 ℃ for 12h to obtain epoxidized soybean oil rosin ester.
2) All the epoxidized soybean oil rosin ester obtained in the step 1) and hexamethylene diisocyanate (8.50 g) were reacted at 80 ℃ for 1 hour to obtain a rosin-based polymer with high hydrogen bonding force, and the conversion was 100%.
The spectrum of the product obtained in example 4, analyzed, was not substantially different from that of example 1 and was not provided repeatedly.
Application example 1
3.0g of polyvinyl chloride powder (Aba Ding Shiji Co., ltd., specification: K-value 72-71), 0.6g of the rosin-based polymer with high hydrogen bonding force obtained in example 1 and 0.3g of cardanol glycidyl ether (XY 767, anhui New technology Co., ltd.) were weighed, stirred in 50ml of tetrahydrofuran at 40℃for 0.5 hours, and the solution was poured into a petri dish and dried at 40℃for 24 hours to obtain a modified polyvinyl chloride film.
Application example 2
3.0g of polyvinyl chloride powder (Aba Ding Shiji Co., ltd., specification: K-value 72-71) and 0.9g of the rosin-based polymer with high hydrogen bonding force obtained in example 1 were weighed, stirred in 50ml of tetrahydrofuran at 40℃for 0.5 hours, and the solution was poured into a petri dish and dried at 40℃for 24 hours to obtain a modified polyvinyl chloride film.
Application example 3
3.0g of polyvinyl chloride powder (Aba Ding Shiji Co., ltd., specification: K-value 72-71), 0.3g of the novel high hydrogen bond force rosin-based polymer plasticizer obtained in example 1 and 0.6g of cardanol glycidyl ether (XY 767, anhui Xinyu technology Co., ltd.) were weighed, stirred in 50ml of tetrahydrofuran at 50℃for 0.5 hours, and the solution was poured into a petri dish and dried at 45℃for 24 hours to obtain a modified polyvinyl chloride film.
Comparative example 1
3.0g of polyvinyl chloride powder was weighed, stirred at 45℃for 0.5h and dissolved in 50ml of tetrahydrofuran, and the solution was poured into a petri dish and dried at 45℃for 24h to prepare a modified polyvinyl chloride film.
Comparative example 2
3.0g of polyvinyl chloride powder and 1.8g of dioctyl phthalate were weighed, stirred in 50ml of tetrahydrofuran at 45℃for 0.5h, and the solution was poured into a petri dish and dried at 45℃for 24h to prepare a modified polyvinyl chloride film.
Comparative example 3
3.0g of polyvinyl chloride powder, 0.6g of dioctyl phthalate and 0.3g of cardanol glycidyl ether (XY 767, anhui New technology Co., ltd.) were weighed, stirred in 50ml of tetrahydrofuran at 45℃for 0.5h, and the solution was poured into a petri dish and dried at 45℃for 24h to prepare a modified polyvinyl chloride film.
The samples were tested for mechanical properties according to the GB-T1040-92 plastic tensile test method and the GB/T1039-1992 plastic mechanical test method, and the properties of the polyvinyl chloride films obtained in each example are shown in Table 1.
TABLE 1 mechanical Property results
Sample of 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 ofExample 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
The plasticizer migration test uses 10% ethyl acetate aqueous solution as a solvent, and a sample is placed in the solvent and soaked for 144 hours at room temperature, and the loss rate of the test weight is the plasticizer migration rate.
As can be seen from table 1, the rosin-based polymer with high hydrogen bond acting force prepared by the method has excellent plasticizing performance on polyvinyl chloride, and can be bonded with polyvinyl chloride to form an integrated structure, so that the tensile strength and the elongation at break are improved simultaneously, the stability is improved simultaneously, and migration is avoided; the modified polyvinyl chloride film prepared in application example 1 is respectively soaked in 10wt% of H at normal temperature 2 S0 4 The weight change rate of the solution and the 10wt% NaOH solution after soaking for 48 hours is 0 (the change rate is less than 0.0001 percent and is regarded as zero), and the solution has excellent acid and alkali corrosion resistance.

Claims (8)

1. A rosin-based polymer with high hydrogen bond acting force is characterized in that: which is a kind ofThe structural formula is as follows:
Figure FDA0004176416490000011
wherein R is the reaction residue of epoxidized soybean oil.
2. A preparation method of a rosin-based polymer with high hydrogen bond acting force is characterized by comprising the following steps: is prepared by reacting epoxy soybean oil rosin ester with hexamethylene diisocyanate.
3. The method of manufacturing as claimed in claim 2, wherein: the reaction temperature is 80-95 ℃ and the reaction time is 0.5-1.5 h.
4. A method of preparation as claimed in claim 2 or 3, wherein: the molar ratio of the epoxidized soybean oil rosin ester to the hexamethylene diisocyanate is 1: (3-3.5).
5. Use of a high hydrogen bond effort rosin-based polymer according to claim 1 or 2, characterized in that: used as a polyvinyl chloride plasticizer.
6. The use according to claim 5, wherein: the mass dosage of the rosin-based polymer with high hydrogen bond acting force is 10-30% of the mass of the polyvinyl chloride.
7. The use according to claim 5 or 6, wherein: the rosin-based polymer with high hydrogen bond acting force is mixed with cardanol glycidyl ether to be used for the polyvinyl chloride plasticizer.
8. The use according to claim 5 or 6, wherein: the mass ratio of the rosin-based polymer with high hydrogen bond acting force to the cardanol glycidyl ether is (2-5): 1.
CN202310392749.4A 2023-04-13 2023-04-13 Rosin-based polymer with high hydrogen bond acting force, preparation method and application thereof Pending CN116217510A (en)

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