Polyester polyol based on plant phenol diglycidyl ether as well as preparation method and application of polyester polyol

Abstract

The invention discloses polyester polyol based on plant phenol diglycidyl ether and a preparation method and application thereof.The preparation method comprises the steps that plant phenol diglycidyl ether and binary acid serve as raw materials and react under the action of a catalyst to obtain a polyester diol product, then diethanol amine is added, an epoxy ring-opening reaction is conducted, and the polyester polyol based on plant phenol diglycidyl ether is obtained. A polyester polyol target product containing 8 hydroxyl groups is generated. The synthesized polyester polyol has more benzene ring structures, a long-chain structure containing 15 carbons and 8 hydroxyl groups with higher reaction activity, 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 invention relates to the technical field of polyol synthesis, and in particular to a polyester polyol based on plant phenol diglycidyl ether, and a preparation method and application thereof. Background Art

[0002] Polyols are an important chemical raw material, widely used in textile, papermaking, coatings, adhesives, plastic foam and other industries. Among them, the largest use of polyols is the production of polyurethane foam plastics.

[0003] Polyurethane is a polymer material formed by the condensation reaction of polyols and polyisocyanates. It has strong plasticity and is widely used in textiles, construction, aviation, ships, automobiles and other fields.

[0004] However, the rigidity and flame retardancy of the existing polyurethane materials prepared by reacting polyols with polyisocyanates are poor, which limits their development to a certain extent. Summary of the invention

[0005] The present invention can solve the above-mentioned defects of polyurethane synthesized from existing polyols by providing a polyester polyol based on plant phenol diglycidyl ether, a preparation method and an application thereof.

[0006] In order to solve the above technical problems, the present invention provides a polyester polyol based on plant phenol diglycidyl ether, which at least includes a compound of the following structural formula:

[0007]

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

[0009] In order to solve the above technical problems, the present invention also provides a method for preparing a polyester polyol based on plant phenol diglycidyl ether, comprising the following steps:

[0010] (1) Synthesis of polyester diol: Plant phenol diglycidyl ether and dibasic acid are used as raw materials, heated under reflux reaction in the presence of a catalyst to generate polyester diol;

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

[0012]

[0013] Wherein, n is 0, 2, 4 or 6;

[0014] (2) Synthesis of polyester polyol: Cooling the material after the reaction in step (1) to 40-60° C., adding diethanolamine thereto, heating under reflux, and performing epoxy ring-opening reaction to generate the polyester polyol based on plant phenol diglycidyl ether.

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

[0016] In a preferred embodiment of the present invention, the added amount of the catalyst is 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 invention, the dibasic acid includes at least one of succinic acid, adipic acid, suberic acid or sebacic acid.

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

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

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

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

[0022] In order to solve the above technical problems, the present invention also provides an application of polyester polyol based on plant phenol diglycidyl ether, characterized in that it is used for synthesizing polyurethane.

[0023] The beneficial effects of the present invention are as follows: the present invention provides a polyester polyol based on plant phenol diglycidyl ether, a preparation method and an application thereof, wherein plant phenol diglycidyl ether, a dibasic acid and diethanolamine are used as raw materials, and the synthesized polyester polyol has a relatively large number of benzene ring structures, contains a 15-carbon long-chain structure and 8 hydroxyl groups with high reaction activity, has the advantages of high mechanical strength, strong hydrophobicity and high cross-linking density, and can effectively improve the water resistance, fire resistance and mechanical strength of polyurethane. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0025] The preferred embodiments of the present invention are described in detail below in conjunction with the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making a clearer and more definite definition of the protection scope of the present invention.

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

[0027]

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

[0029] The structural formula of the polyester polyol of the present invention contains a large number of benzene ring structures, which can effectively improve the rigidity, compression strength, heat resistance and flame retardancy of polyurethane; the 15-carbon long-chain structure contained therein has strong hydrophobicity and can improve water resistance; it has 8 hydroxyl groups with high reaction activity and can increase the crosslinking density with polyisocyanate, thereby effectively improving the mechanical properties of polyurethane.

[0030] The preparation method of the polyester polyol based on plant phenol diglycidyl ether comprises the following specific steps:

[0031] (1) Synthesis of polyester diol: Plant phenol diglycidyl ether and dibasic acid are used as raw materials, heated under reflux reaction in the presence of a catalyst to generate polyester diol;

[0032] Specifically, plant phenol diglycidyl ether and dibasic acid are added into a four-necked flask at a molar ratio of 1.9-2.2:1, stirring is started, condensation reflux is carried out, the temperature is raised to 80-90°C, a catalyst accounting for 0.1-2% of the total mass of the plant phenol diglycidyl ether and the dibasic acid is added, stirring is performed evenly, the temperature is raised to 100-130°C, and the temperature is kept at reflux for 5-9 hours. After the epoxy equivalent weight (EEW) reaches the theoretical value, the polyester diol is synthesized.

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

[0034]

[0035] Wherein n is 0, 2, 4 or 6.

[0036] The dibasic acid includes at least one of succinic acid, adipic acid, suberic acid or sebacic acid.

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

[0038] (2) Synthesis of polyester polyol: Cooling the material after the reaction in step (1) to 40-60° C., adding diethanolamine thereto, heating under reflux, and performing epoxy ring-opening reaction to generate the polyester polyol based on plant phenol diglycidyl ether.

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

[0040] The technical contents of the present invention are described in detail below through specific embodiments.

[0041] Example 1

[0042] Add 828g of plant phenol diglycidyl ether and 141.6g of adipic acid into a four-necked flask, start stirring, condense and reflux, heat to 90°C under nitrogen protection, add 1.5g of boron trifluoride benzylamine, heat to 100°C, keep warm and reflux for 7 hours, sample and detect EEW to 480-500, cool to 60°C, add 210.2g of diethanolamine, stir evenly, heat to 100°C, keep warm and reflux for 3 hours, and cool to room temperature after the reaction is completed to obtain the final product.

[0043] Example 2

[0044] Add 869.4g of plant phenol diglycidyl ether and 141.6g of adipic acid into a four-necked flask, start stirring, condense and reflux, heat to 90°C under nitrogen protection, add 1.5g of boron trifluoride benzylamine, heat to 110°C, keep warm and reflux for 7 hours, take samples to detect EEW to 500-520, cool to 60°C, add 220.7g of diethanolamine, stir evenly, heat to 100°C, keep warm and reflux for 3 hours, and cool to room temperature after the reaction is completed to obtain the final product.

[0045] Example 3

[0046] Add 828g of plant phenol diglycidyl ether and 141.6g of adipic acid into a four-necked flask, start stirring, condense and reflux, heat to 90°C under nitrogen protection, add 4g of boron trifluoride benzylamine, heat to 130°C, keep warm and reflux for 9 hours, sample and test EEW to 480-500, cool to 60°C, add 210.2g of diethanolamine, stir evenly, heat to 100°C, keep warm and reflux for 3 hours, and cool to room temperature after the reaction is completed to obtain the final product.

[0047] Example 4

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

[0049] Example 5

[0050] Add 828g of plant phenol diglycidyl ether and 202.2g of sebacic acid into a four-necked flask, start stirring, condense and reflux, heat to 90°C under nitrogen protection, add 4g of boron trifluoride benzylamine, heat to 130°C, keep warm and reflux for 9 hours, take samples to detect EEW to 510-530, cool to 60°C, add 210.2g of diethanolamine, stir evenly, heat to 100°C, keep warm and reflux for 3 hours, and cool to room temperature after the reaction is completed to obtain the final product.

[0051] The performance test results of the products obtained in Examples 1-5 are shown in Table 1. The infrared test results of the product prepared in Example 1 are shown in the attached figure. Figure 1 shown.

[0052] Table 1

[0053]

[0054] Attached Figure 1 The results show that: 1737cm -1 There is a strong absorption peak, confirming the formation of ester groups; 3522cm -1 There is an absorption peak at 910cm -1 There is no absorption peak at , which proves that the epoxy group has reacted completely and the reaction is completed.

[0055] Rigid polyurethane foam was prepared using the polyester polyols prepared in Examples 2 and 4 as raw materials, wherein Example 2 was a polyester polyol containing adipic acid theoretical structure, and Example 4 was a polyester polyol replaced 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 then the corresponding catalyst, flame retardant, silicone oil, water and cyclopentane were added according to the formula amount, and stirred and mixed at a rate of 2500r / min to obtain component A. Component A and component B (PM200) were poured into a foaming cup at a mass ratio of 1:1.2, and stirred at a speed of 2500r / min for 8s, and then allowed to foam freely, and the drawing and non-stick time were recorded. After being fully matured for 24h, the relevant performance tests were carried out.

[0058] Table 2

[0059]

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

[0061] Table 3

[0062]

[0063] It can be seen from the test results in Table 3 that, when the hydroxyl values ​​of the polyols are similar, the compressive strength of the polyurethane rigid foam prepared using the polyester polyol product prepared by the present invention is improved, the vertical flame time is shortened, and the fire resistance is improved.

[0064] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

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

2. A method for preparing a polyester polyol based on plant phenol diglycidyl ether as claimed in claim 1, characterized in that: The steps include: (1) Synthesis of polyester diol: Plant phenol diglycidyl ether and dibasic acid are used as raw materials, heated under reflux reaction in the presence of a catalyst to generate polyester diol; The structural formula of the plant phenol diglycidyl ether is: Wherein, n is 0, 2, 4 or 6; (2) Synthesis of polyester polyol: cooling the material after the reaction in step (1) to 40-60° C., adding diethanolamine thereto, heating under reflux, and performing epoxy ring-opening reaction to generate the polyester polyol based on plant phenol diglycidyl ether.

3. The method for preparing 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 to the dibasic acid is 1.9-2.2:

1.

4. The method for preparing a polyester polyol based on plant phenol diglycidyl ether according to claim 3, characterized in that: The added amount of the catalyst is 0.1-2% of the total mass of the plant phenol diglycidyl ether and the dibasic acid.

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

6. A method for preparing a 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 ethyl ether, hydrogen fluoride, triphenylphosphine or a tertiary amine.

7. The method for preparing a polyester polyol based on plant phenol diglycidyl ether according to claim 2, characterized in that: In step (1), the process conditions of the heating reflux reaction are: temperature 100-130° C., time 5-9 h.

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

1.

9. The method for preparing a polyester polyol based on plant phenol diglycidyl ether according to claim 2, characterized in that: In step (2), the conditions for the epoxy ring-opening reaction are: temperature 100-110° C., time 2-3 h.

10. An application of the polyester polyol based on plant phenol diglycidyl ether as claimed in claim 1, characterized in that: Used in the synthesis of polyurethane.

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