Plant phenol diglycidyl ether-based polyester polyols, and methods of making and using the same

Abstract

The application discloses a polyester polyol based on plant phenol diglycidyl ether and a preparation method and application thereof. The polyester diol product is obtained by reacting plant phenol diglycidyl ether and a dibasic acid under the action of a catalyst, then diethanolamine is added to perform an epoxy ring-opening reaction, and the polyester polyol target product containing 8 hydroxyl groups is generated. The polyester polyol synthesized by the application has more benzene ring structures, a long chain structure containing 15 carbons and 8 hydroxyl groups with high reactivity, and has the advantages of high mechanical strength, strong hydrophobicity and high crosslinking density, and can effectively improve the water resistance, fire resistance and mechanical strength of polyurethane.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyol synthesis, in particular to a polyester polyol based on plant phenol diglycidyl ether and a preparation method and application thereof. BACKGROUND

[0002] Polyol is an important chemical raw material, which is widely used in textile, papermaking, coating, adhesive, plastic foam and other industries. Among them, the largest use of polyol is to produce polyurethane foam plastic.

[0003] Polyurethane is a high molecular material formed by polycondensation reaction of polyol and polyisocyanate, which has strong plasticity and is widely used in textile, building, aviation, ship, automobile and other fields.

[0004] However, the rigidity and flame retardance of the polyurethane material prepared by the reaction of the existing polyol and polyisocyanate are poor, which limits its development to some extent. SUMMARY

[0005] The present application provides a polyester polyol based on plant phenol diglycidyl ether and a preparation method and application thereof, which can solve the above-mentioned defects of the polyurethane obtained by synthesizing the existing polyol.

[0006] To solve the above technical problems, the present application provides a polyester polyol based on plant phenol diglycidyl ether, which at least comprises a compound with the following structural formula:

[0007]

[0008] In the formula, m is 2, 4, 6 or 8; n is 0, 2, 4 or 6.

[0009] To solve the above technical problems, the present application further provides a preparation method of the polyester polyol based on plant phenol diglycidyl ether, comprising the following steps:

[0010] (1) Synthesis of polyester diol: taking plant phenol diglycidyl ether and diacid as raw materials, heating and refluxing under the action of a catalyst to generate polyester diol;

[0011] The structural formula of the plant phenol diglycidyl ether is:

[0012]

[0013] In the formula, n is 0, 2, 4 or 6;

[0014] (2) Synthesis of polyester polyol: cooling the material after reaction in step (1) to 40-60℃, then adding diethanolamine and heating and refluxing to perform epoxy ring-opening reaction to generate the polyester polyol based on plant phenol diglycidyl ether.

[0015] In a preferred embodiment of the present application, in step (1), the molar ratio of the plant phenol diglycidyl ether and the dibasic acid is 1.9-2.2:1.

[0016] In a preferred embodiment of the present application, the catalyst is added in an amount of 0.1-2% of the total mass of the plant phenol diglycidyl ether and the dibasic acid.

[0017] In a preferred embodiment of the present application, the dibasic acid comprises at least one of succinic acid, adipic acid, suberic acid or sebacic acid.

[0018] In a preferred embodiment of the present application, the catalyst comprises at least one of boron trifluoride benzylamine, quaternary ammonium salt, boron trifluoride diethyl ether, hydrogen fluoride, triphenylphosphine or tertiary amine.

[0019] In a preferred embodiment of the present application, in step (1), the process conditions of the heating reflux reaction are: temperature 100-130℃, time 5-9h.

[0020] In a preferred embodiment of the present application, the molar ratio of the diethanolamine and the plant phenol diglycidyl ether is 0.9-1:1.

[0021] In a preferred embodiment of the present application, in step (2), the conditions of the ring-opening reaction of the epoxy are: temperature 100-110℃, time 2-3h.

[0022] To solve the above technical problems, the present application further provides an application of the polyester polyol based on plant phenol diglycidyl ether, characterized by being used for synthesizing polyurethane.

[0023] The present application has the following advantages: the polyester polyol based on plant phenol diglycidyl ether, the preparation method and the application thereof use plant phenol diglycidyl ether, dibasic acid and diethanolamine as raw materials, and the synthesized polyester polyol has more benzene ring structures, a long chain structure containing 15 carbons and 8 hydroxyl groups with high reactivity, and the advantages of high mechanical strength, strong hydrophobicity and high crosslinking density, which can effectively improve the water resistance, fire resistance and mechanical strength of polyurethane. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is the infrared spectrum of the polyester polyol prepared in a preferred embodiment 1 of the present application. DETAILED DESCRIPTION

[0025] The preferred embodiments of the present application are described in detail below with reference to the drawings, so that the advantages and features of the present application can be more easily understood by those skilled in the art, and the protection scope of the present application can be more clearly defined.

[0026] The application discloses a polyester polyol based on plant phenol diglycidyl ether and a preparation method and application thereof, and specifically, plant phenol diglycidyl ether and dibasic acid are used as raw materials, a polyester diol product is obtained through reaction under the action of a catalyst, diethanolamine is added, an epoxy ring-opening reaction is carried out, and a polyester polyol target product containing 8 hydroxyl groups is generated, and the structural formula is as follows:

[0027]

[0028] In the formula, m is 2, 4, 6 or 8; and n is 0, 2, 4 or 6.

[0029] The polyester polyol has a structure formula containing more benzene ring structures, can effectively improve the rigidity, compressive strength, heat resistance and flame retardance of polyurethane, has a long chain structure containing 15 carbons, has strong hydrophobicity and can improve water resistance, has 8 hydroxyl groups with relatively high reactivity, can improve the crosslinking density with polyisocyanate, and thus can effectively improve the mechanical properties of polyurethane.

[0030] The preparation method of the polyester polyol based on plant phenol diglycidyl ether is specifically as follows:

[0031] (1) synthesizing a polyester diol: plant phenol diglycidyl ether and dibasic acid are used as raw materials, heated reflux reaction is carried out under the action of a catalyst, and a polyester diol is generated;

[0032] Specifically, plant phenol diglycidyl ether and dibasic acid are added into a four-necked flask in a proportion of 1.9-2.2:1 in terms of molar ratio, stirring is started, condensation reflux is started, the temperature is increased to 80-90 DEG C, 0.1-2 % of the catalyst based on the total mass of the plant phenol diglycidyl ether and dibasic acid is added, the temperature is increased to 100-130 DEG C after uniform stirring, and the temperature is kept constant for 5-9 hours, and the epoxy equivalent weight (EEW) is tested to reach the theoretical value, and the polyester diol is synthesized.

[0033] The structural formula of the plant phenol diglycidyl ether is as follows:

[0034]

[0035] In the formula, n is 0, 2, 4 or 6.

[0036] The dibasic acid includes at least one of butanedioic acid, hexanedioic acid, octanedioic acid or decanedioic acid.

[0037] The catalyst includes at least one of boron trifluoride benzylamine, quaternary ammonium salt, boron trifluoride diethyl ether, hydrogen fluoride, triphenylphosphine or tertiary amine.

[0038] (2) Synthesis of polyester polyol: the reacted material in step (1) is cooled to 40-60°C, diethanolamine is added, and an epoxy ring-opening reaction is carried out to generate the polyester polyol based on the plant phenol diglycidyl ether.

[0039] Specifically, the reacted material in step (1) is cooled to 40-60°C, diethanolamine is added at a molar ratio of 0.9-1:1 of diethanolamine to plant phenol diglycidyl ether, stirred uniformly, heated to 100-110°C, and kept at the temperature for 2-3 hours, and then cooled to room temperature to obtain the target product.

[0040] The technical content of the present application is described in detail below through specific examples.

[0041] Example 1

[0042] 828g of plant phenol diglycidyl ether and 141.6g of adipic acid are added to a four-necked flask, stirring is started, condensation reflux is started, and the temperature is raised to 90°C under nitrogen protection, 1.5g of boron trifluoride benzylamine is added, the temperature is raised to 100°C, and the temperature is kept for 7 hours, the EEW is detected by sampling to be 480-500, the temperature is lowered to 60°C, 210.2g of diethanolamine is added, stirred uniformly, the temperature is raised to 100°C, and the temperature is kept for 3 hours, and then the temperature is lowered to room temperature after the reaction is completed to obtain the final product.

[0043] Example 2

[0044] 869.4g of plant phenol diglycidyl ether and 141.6g of adipic acid are added to a four-necked flask, stirring is started, condensation reflux is started, and the temperature is raised to 90°C under nitrogen protection, 1.5g of boron trifluoride benzylamine is added, the temperature is raised to 110°C, and the temperature is kept for 7 hours, the EEW is detected by sampling to be 500-520, the temperature is lowered to 60°C, 220.7g of diethanolamine is added, stirred uniformly, the temperature is raised to 100°C, and the temperature is kept for 3 hours, and then the temperature is lowered to room temperature after the reaction is completed to obtain the final product.

[0045] Example 3

[0046] 828g of plant phenol diglycidyl ether and 141.6g of adipic acid are added to a four-necked flask, stirring is started, condensation reflux is started, and the temperature is raised to 90°C under nitrogen protection, 4g of boron trifluoride benzylamine is added, the temperature is raised to 130°C, and the temperature is kept for 9 hours, the EEW is detected by sampling to be 480-500, the temperature is lowered to 60°C, 210.2g of diethanolamine is added, stirred uniformly, the temperature is raised to 100°C, and the temperature is kept for 3 hours, and then the temperature is lowered to room temperature after the reaction is completed to obtain the final product.

[0047] Example 4

[0048] Put 828 g plant phenol diglycidyl ether and 118.1 g succinic acid into a four-necked flask, open the stirring, condense reflux, nitrogen protection, heat to 90°C, add 4 g of boron trifluoride benzylamine, heat to 130°C, keep reflux for 9 hours, take sample to test EEW to 465-485, cool to 60°C, add 210.2 g diethanolamine, stir evenly, heat to 100°C, keep reflux for 3 hours, after the reaction is completed, cool to room temperature, get the final product.

[0049] Example 5

[0050] Put 828 g plant phenol diglycidyl ether and 118.1 g succinic acid into a four-necked flask, open the stirring, condense reflux, nitrogen protection, heat to 90°C, add 4 g of boron trifluoride benzylamine, heat to 130°C, keep reflux for 9 hours, take sample to test EEW to 465-485, cool to 60°C, add 210.2 g diethanolamine, stir evenly, heat to 100°C, keep reflux for 3 hours, after the reaction is completed, cool to room temperature, get the final product.

[0051] The products obtained in Examples 1-5 are tested for performance, and the results are shown in Table 1 below. The product prepared in Example 1 is tested by infrared, and the test chart is shown in Figure 1. Figure 1

[0052] Table 1

[0053]

[0054] Figure 1 Figure 1 The results show that: 1737 cm -1 has a strong absorption peak, confirming the generation of ester group; 3522 cm -1 has an absorption peak, confirming the generation of hydroxyl group; 910 cm -1 has no absorption peak, proving that the epoxy group has reacted completely, and the reaction has been completed.

[0055] The polyester polyols prepared in Examples 2 and 4 are used as raw materials to prepare rigid polyurethane foam. Example 2 is a polyester polyol containing adipic acid theoretical structure, and Example 4 is a polyester polyol with succinic acid. The specific formula is shown in Table 2 below.

[0056] The specific preparation process is as follows:

[0057] ​According to the formula in Table 2, the corresponding three polyols were mixed according to the formula amount, and the corresponding catalyst, flame retardant, silicone oil, water and cyclopentane were added according to the formula amount, and mixed at a stirring rate of 2500 r / min, to obtain the A component. The A component and the B component (PM200) were poured into a foaming cup according to a mass ratio of 1:1.2, stirred at a speed of 2500 r / min for 8 s, then allowed to foam freely, the stringing and non-stick times were recorded, and after 24 h of complete curing, the relevant performance tests were carried out.

[0058] Table 2

[0059]

[0060] The properties of the specific products in the formula of Table 2 are shown in Table 3.

[0061] Table 3

[0062]

[0063] From the test results in Table 3, it can be seen that in the case of similar hydroxyl values of polyols, the polyurethane rigid foam prepared using the polyester polyol product of the application has improved compressive strength, shortened vertical flame time and improved fire resistance.

[0064] The above description is only an embodiment of the application, and does not limit the patent scope of the application, and any equivalent structure or equivalent process transformation using the content of the specification and drawings, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the application.

Claims

1. A polyester polyol based on plant phenol diglycidyl ether, characterized in that, At least a compound comprising the following structural formula: In the formula, m is 2, 4, 6 or 8; n is 0, 2, 4 or 6.

2. A process for the preparation of a plant phenolic diglycidyl ether based polyester polyol as claimed in claim 1, characterized in that, The method comprises the following steps: (1) Synthesizing polyester diol: using plant phenol diglycidyl ether and diacid as raw materials, under the action of a catalyst, heating and refluxing to react, to generate polyester diol; The structural formula of the plant phenol diglycidyl ether is: In the formula, n is 0, 2, 4 or 6; (2) Synthesizing polyester polyol: cooling the reacted material in step (1) to 40-60℃, then adding diethanolamine thereto, heating and refluxing to perform epoxy ring-opening reaction, to generate the polyester polyol based on plant phenol diglycidyl ether.

3. A process for the preparation of a polyester polyol based on plant phenol diglycidyl ether according to claim 2, characterized in that, In step (1), the molar ratio of the plant phenol diglycidyl ether and diacid is 1.9-2.2:

1.

4. A process for the preparation of a polyester polyol based on plant phenol diglycidyl ether according to claim 3, characterized in that, The catalyst is added in an amount of 0.1-2% of the total mass of the plant phenol diglycidyl ether and diacid.

5. The method for preparing polyester polyol based on plant phenol diglycidyl ether according to claim 4, wherein the diacid comprises at least one of succinic acid, adipic acid, suberic acid or sebacic acid.

6. The method for preparing polyester polyol based on plant phenol diglycidyl ether according to claim 4, wherein the catalyst comprises at least one of boron trifluoride benzylamine, quaternary ammonium salt, boron trifluoride diethyl ether, hydrogen fluoride, triphenylphosphine or tertiary amine.

7. A process for the preparation of a polyester polyol based on plant phenol diglycidyl ether according to claim 2, characterized in that, In step (1), the process condition of the heating and refluxing reaction is: temperature 100-130℃, time 5-9h.

8. A process for the preparation of a polyester polyol based on plant phenol diglycidyl ether according to claim 2, characterized in that, The molar ratio of the diethanolamine and plant phenol diglycidyl ether is 0.9-1:

1.

9. A process for the preparation of a polyester polyol based on plant phenol diglycidyl ether according to claim 2, characterized in that, In step (2), the condition of the epoxy ring-opening reaction is: temperature 100-110℃, time 2-3h.

10. Use of a plant phenol diglycidyl ether-based polyester polyol according to claim 1, characterized in that, For synthesizing polyurethane.

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