Biomass-sourced phosphorus-containing dicarboxylic acid and / or anhydride and polyester thereof, and preparation method and application of biomass-sourced phosphorus-containing dicarboxylic acid and / or anhydride and polyester

Abstract

The invention discloses biomass-sourced phosphorus-containing dicarboxylic acid and / or anhydride and polyester thereof, and a preparation method and application of the biomass-sourced phosphorus-containing dicarboxylic acid and / or anhydride and polyester. The preparation method comprises the following steps: carrying out substitution reaction on furfuryl alcohol and diphenyl chlorophosphate in the presence of organic alkali to obtain an intermediate product A, and then carrying out addition polycondensation reaction on the intermediate product A and unsaturated dicarboxylic acid and / or anhydride thereof to obtain biomass-sourced phosphorus-containing dicarboxylic acid and / or anhydride thereof, the prepared phosphorus-containing dicarboxylic acid and / or anhydride thereof can be used for preparing polyester. The preparation process is simple and convenient, the yield is high, the biomass-derived furfuryl alcohol is adopted as the raw material, the source is wide, and the method is green and environment-friendly; halogen-free flame-retardant dicarboxylic acid (anhydride) prepared from furfuryl alcohol is used for preparing structural flame-retardant resin, and the flame-retardant effect is good.

Description

Technical Field

[0001] The invention relates to the technical field of polyester preparation, and in particular to a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof, polyester, and a preparation method and application thereof. Background Art

[0002] Polyester is a widely used type of polymer. For example, high molecular weight polyethylene terephthalate is a typical thermoplastic polyester polyol, which is widely used in the fields of plastics and fibers. Carboxyl-terminated polyester oligomers can be used in powder coatings. Unsaturated polyester oligomers are important raw materials for thermosetting resins. Hydroxyl-terminated polyester oligomers are important raw materials for the synthesis of polyurethane resins. Dicarboxylic acids (anhydrides) are important monomers in polymer synthesis and can be used to prepare polyesters.

[0003] Polymer materials are extremely flammable due to the characteristics of their molecular structure and chemical composition, and they produce a large amount of toxic gases and smoke during the combustion process, which significantly hinders their further application in daily production and life. In order to expand the scope of application of polymer materials, especially to meet the requirements of some special fields, it is necessary to modify the polymer to be flame retardant and maintain the comprehensive application performance of the polymer. With the advancement of flame retardant technology and the further improvement of environmental protection and safety requirements, the use of halogen-containing flame retardant systems has been gradually restricted; at the same time, the use of additive flame retardant systems has become increasingly restricted due to the migration of small molecule flame retardants, which affects the durability of flame retardancy, or the negative impact of flame retardants as additives on polymer properties. Therefore, the design and synthesis of intrinsic flame retardant resins is an effective means to improve the flame retardant properties of materials and expand the scope of application of materials.

[0004] At present, the development of synthetic materials using renewable biomass materials as raw materials to replace petrochemical raw materials has gradually become a pursuit of people. Furfuryl alcohol is an important chemical raw material, which can be derived from furfural obtained by biological fermentation and is a biomass-derived chemical raw material. At present, there is no report on the preparation of halogen-free flame-retardant dicarboxylic acids (anhydrides) using furfuryl alcohol. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a biomass-derived phosphorus-containing dicarboxylic acid and / or its anhydride, polyester, and a preparation method and application thereof.

[0006] In a first aspect, the present invention provides a method for preparing a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof, which is achieved by adopting the following technical scheme.

[0007] A method for preparing a biomass-derived phosphorus-containing dicarboxylic acid and / or its anhydride comprises the following steps: subjecting furfuryl alcohol and diphenyl chlorophosphate to a substitution reaction in the presence of an organic base to obtain an intermediate product A, and then subjecting the intermediate product A to an addition polycondensation reaction with an unsaturated dicarboxylic acid and / or its anhydride to obtain the biomass-derived phosphorus-containing dicarboxylic acid and / or its anhydride.

[0008] Furthermore, the molar ratio of furfuryl alcohol, diphenyl chlorophosphate, and unsaturated dicarboxylic acid and / or its anhydride is 1:1:1.

[0009] Furthermore, the unsaturated dicarboxylic acid and / or its anhydride is selected from one or more of maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic acid, endomethylenetetrahydrophthalic anhydride, cyclohex-1-ene-1,2-dicarboxylic acid, and cyclohex-1-ene-1,2-dicarboxylic anhydride.

[0010] Furthermore, the organic base is triethylamine or trimethylamine.

[0011] Furthermore, the organic base is fed in an equal molar number to diphenyl chlorophosphate.

[0012] Furthermore, the reaction temperature of the substitution reaction is 30°C-65°C.

[0013] Furthermore, the conditions for the addition polycondensation reaction are as follows: the intermediate product A and the unsaturated dicarboxylic acid and / or its anhydride are first heated to 160°C and reacted for 0.5 to 3 hours, then gradually heated to 220°C and reacted for 4 to 8 hours. When the temperature rises to 200°C, a titanate catalyst is added.

[0014] Preferably, a method for preparing a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof comprises the following steps:

[0015] S1. Dissolve furfuryl alcohol and diphenyl chlorophosphate in a mixed solvent, pass nitrogen protection, and heat to 30°C-65°C;

[0016] S2. Under stirring conditions, an organic base is added dropwise to the mixture in step S1, and the reaction temperature is maintained for 2-6 hours. After the reaction is completed, the mixture is cooled and filtered to obtain a mixed solvent containing the intermediate product A;

[0017] S3. Add unsaturated dicarboxylic acid and / or its anhydride to the mixed solvent containing the intermediate product A, stir and reflux at 85°C-115°C for 1-3.5 hours. After the reaction is completed, remove the solvent in the system to obtain biomass-derived phosphorus-containing dicarboxylic acid and / or its anhydride.

[0018] Furthermore, in step S1, the mixed solvent is benzene and toluene mixed in a mass ratio of 30:70 to 70:30.

[0019] Furthermore, in step S2, the organic base is triethylamine or trimethylamine.

[0020] Furthermore, in step S2, the organic base is fed in an equal molar number to diphenyl chlorophosphate.

[0021] Furthermore, the molar ratio of furfuryl alcohol, diphenyl chlorophosphate, and unsaturated dicarboxylic acid and / or its anhydride is 1:1:1.

[0022] Furthermore, the unsaturated dicarboxylic acid and / or its anhydride is selected from one or more of maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic acid, endomethylenetetrahydrophthalic anhydride, cyclohex-1-ene-1,2-dicarboxylic acid, and cyclohex-1-ene-1,2-dicarboxylic anhydride.

[0023] In a second aspect, the present invention provides a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof, which is achieved by adopting the following technical solution.

[0024] A biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof prepared by the above preparation method.

[0025] In a third aspect, the present invention provides a use of a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof, which is achieved by adopting the following technical solution.

[0026] A use of the above biomass-derived phosphorus-containing dicarboxylic acid and / or its anhydride in the preparation of polyester.

[0027] Furthermore, the polyester includes flame retardant polyester polyol for polyurethane foam, polyester polyol for flame retardant powder coating or flame retardant unsaturated polyester resin.

[0028] In a fourth aspect, the present invention provides a method for preparing polyester, which is achieved by adopting the following technical scheme.

[0029] A method for preparing polyester comprises the following steps: subjecting polyol and carboxylic acid composition C to polycondensation reaction under the action of a catalyst to obtain polyester polyol; the carboxylic acid composition C comprises the above-mentioned phosphorus-containing dicarboxylic acid and / or its anhydride.

[0030] Furthermore, the polyol includes conventional diols, triols, and tetraols; diols include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol; triols include trimethylolpropane and glycerol; and tetraols include pentaerythritol.

[0031] Furthermore, the polycondensation reaction catalyst is a conventional titanate catalyst, such as isopropyl titanate, and its dosage is 0.01% to 0.08% of the total amount of reactants.

[0032] A method for preparing polyester comprises the following steps: subjecting a polyol and a carboxylic acid composition D to a condensation polymerization reaction under the action of a catalyst, adding a mixed solvent prepared in the above step S2 and containing an intermediate product A after the condensation polymerization reaction, and removing the solvent after the heat preservation reaction to obtain a polyester; the carboxylic acid composition D comprises the unsaturated dicarboxylic acid and / or its anhydride.

[0033] Furthermore, the polyol includes conventional diols, triols, and tetraols; diols include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, diethylene glycol, triethylene glycol, and dipropylene glycol; triols include trimethylolpropane, glycerol, etc.; and tetraols include pentaerythritol.

[0034] The polycondensation reaction catalyst is a conventional titanate catalyst, such as isopropyl titanate, and its usage is 0.01% to 0.08% of the total amount of reactants.

[0035] This application has the following beneficial effects.

[0036] (1) The preparation process of the present invention is simple and has a high yield. Furfuryl alcohol from biomass is used as a raw material, which is not only widely available but also environmentally friendly.

[0037] (2) The present invention utilizes furfuryl alcohol to prepare a halogen-free flame-retardant dicarboxylic acid (anhydride), which is used to prepare a structural flame-retardant resin with good flame-retardant effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 The figure is a schematic diagram of the preparation method of the phosphorus-containing dicarboxylic acid and / or its anhydride of the present invention (taking maleic anhydride as an example). DETAILED DESCRIPTION

[0039] The present patent application is further described below in conjunction with embodiments.

[0040] Unless otherwise specified, the experimental methods used in the following preparation examples and examples are all conventional methods; the materials, reagents, etc. used in the following preparation examples and examples are all commercially available unless otherwise specified.

[0041] The CAS NO of diphenyl chlorophosphate selected in this application is 2524-64-3.

[0042] Example 1

[0043] 2.68g of diphenyl chlorophosphate and 0.98g of furfuryl alcohol were dissolved in 50ml of a mixed solvent of benzene / toluene (mass ratio 50:50), nitrogen was passed through and the temperature was raised to 35°C, and 1.01g of triethylamine was slowly added dropwise. After the addition was completed, the reaction was continued at 55°C for 5.5 hours, and the temperature was lowered and filtered to obtain a filtrate A.

[0044] The filtrate A was added back into the three-necked flask, 0.98 g of maleic anhydride was added, the temperature was raised to 100°C, and the reaction was refluxed for 2.5 hours. After the reaction was completed, the reaction solution was transferred to a rotary evaporator, and after removing the benzene / toluene mixed solvent, 4.25 g of phosphorus-containing dicarboxylic anhydride product B was obtained, with a yield of 99.4%.

[0045] Polyester polyols for polyurethane foam can be synthesized using one of the following two methods:

[0046] Scheme 1: Example 1 Reaction product B 42.5g, terephthalic acid 50.2g, diethylene glycol 74.3g, glycerol 9.2g, isopropyl titanate 0.05g. The above reaction product was heated to 160°C in a three-necked flask under nitrogen protection for 1 hour, and then gradually heated to 210°C for 5 hours to obtain a light yellow transparent viscous liquid C with a hydroxyl value of 210mgKOH / g and a viscosity (25°C) of 13000mPa.s.

[0047] Scheme 2: 0.1g maleic anhydride, 0.5g terephthalic acid, 7.43g diethylene glycol, 0.92g glycerol, 0.005g isopropyl titanate. The above reaction product was heated to 160°C in a three-necked flask under nitrogen protection for 1 hour, and then gradually heated to 210°C for 5 hours. The reactants were cooled to 120°C, and the filtrate A of the first step of Example 1 was added, and the reaction was refluxed for 1.5 hours. After the reaction was completed, the solvent was removed in vacuum to obtain a slightly yellow transparent viscous liquid C with a hydroxyl value of 210mgKOH / g and a viscosity (25°C) of 13000mPa.s.

[0048] After obtaining the polyester polyol for polyurethane foam, the following foaming formula is used for foaming:

[0049] Reaction product C 50.0g 635 polyether 35.0g Phthalic Anhydride Polyester 20.0g 405 Amine Ether 5.0g HFC-245fa 14.0g water 1.8g Foam leveler 2.0g PC-8 2.6g PC-46 0.3g PMDI 120g

[0050] The prepared rigid polyurethane foam has an overall density of 35kg / m 3 The combustion oxygen index [OI] was measured according to ASTM D2863 and was 26.5.

[0051] Example 2

[0052] 2.68g of diphenyl chlorophosphate and 0.98g of furfuryl alcohol were dissolved in 50ml of a mixed solvent of benzene / toluene (mass ratio 50:50), nitrogen was passed through and the temperature was raised to 45°C, and 1.01g of triethylamine was slowly added dropwise. After the addition was completed, the reaction was continued at 45°C for 4.5 hours, and the temperature was lowered and filtered to obtain a filtrate A.

[0053] The filtrate A was added back into the three-necked flask, and 1.52 g of tetrahydrophthalic anhydride was added, and the temperature was raised to 110°C, and the reaction was refluxed for 3.5 hours. After the reaction was completed, the reaction solution was transferred to a rotary evaporator, and after removing the benzene / toluene mixed solvent, 4.75 g of phosphorus-containing dicarboxylic anhydride product B was obtained, with a yield of 98.5%.

[0054] Polyester polyols for polyurethane foam are synthesized as follows:

[0055] Example 2 Reaction product B 47.9g, phthalic anhydride 44.5g, triethylene glycol 29.0g, diethylene glycol 53.8g, ethylene glycol 6.2g, isopropyl titanate 0.03g. The above reaction product was heated to 160°C in a three-necked flask under nitrogen protection for 1.5 hours, and then gradually heated to 210°C for 5.5 hours to obtain a light yellow transparent viscous liquid C with a hydroxyl value of 230mgKOH / g and a viscosity (25°C) of 10500mPa.s.

[0056] After obtaining the polyester polyol for polyurethane foam, the following foaming formula is used for foaming:

[0057]

[0058]

[0059] The prepared rigid polyurethane foam has an overall density of 32kg / m 3 The combustion oxygen index [OI] was measured according to ASTM D2863 and was 29.5.

[0060] Example 3

[0061] 2.68g of diphenyl chlorophosphate and 0.98g of furfuryl alcohol were dissolved in 50ml of a mixed solvent of benzene / toluene (mass ratio 50:50), nitrogen was passed through and the temperature was raised to 65°C, and 1.01g of triethylamine was slowly added dropwise. After the addition was completed, the reaction was continued at 65°C for 2.5 hours, and the temperature was lowered and filtered to obtain a filtrate A.

[0062] The filtrate A was added back into the three-necked flask, 1.64 g of methylene tetrahydrophthalic anhydride was added, the temperature was raised to 110°C, and the reaction was refluxed for 3.0 hours. After the reaction was completed, the reaction solution was transferred to a rotary evaporator, and after removing the benzene / toluene mixed solvent, 4.85 g of phosphorus-containing dicarboxylic anhydride product B was obtained, with a yield of 98.2%.

[0063] Unsaturated polyester resin for glass fiber reinforced plastic composite materials is synthesized by the following method:

[0064] Example 3 Reaction product B 49.2g, phthalic anhydride 92.6g, maleic acid 23.2g, isophthalic acid 16.6g, ethylene glycol 43.6g, diethylene glycol 10.9g, neopentyl glycol 20.9g, isopropyl titanate 0.05g. The above reaction products were heated to 160°C in a three-necked flask under nitrogen protection for 1.5 hours, then gradually heated to 210°C for 5.5 hours, and then cooled to room temperature to obtain resin C. Add styrene 15.5g and divinylbenzene 6.5g to resin C, stir evenly, and then add 0.06g of AIBN initiator. Apply this resin to a glass mesh cloth (glass cloth specification: 125g / m 2 , resin coating amount is 300g / m 2 ), and heated and cured to obtain a glass fiber reinforced plastic composite material. The oxygen index [OI] of the composite material was measured according to ASTM D2863 and was 32.5.

[0065] Example 4

[0066] 2.68g of diphenyl chlorophosphonate and 0.98g of furfuryl alcohol were dissolved in 50ml of a mixed solvent of benzene / toluene (mass ratio 50:50), nitrogen was passed through and the temperature was raised to 55°C, and 1.01g of triethylamine was slowly added dropwise. After the addition was completed, the reaction was continued at 55°C for 3.0 hours, and the temperature was lowered and filtered to obtain a filtrate A.

[0067] The filtrate A was added back into the three-necked flask, 1.16 g of maleic acid was added, the temperature was raised to 110°C, and the reaction was refluxed for 3.0 hours. After the reaction was completed, the reaction solution was transferred to a rotary evaporator, and after removing the benzene / toluene mixed solvent, 4.42 g of phosphorus-containing dicarboxylic acid product B was obtained, with a yield of 99.1%.

[0068] Polyester polyols for polyurethane foam are synthesized as follows:

[0069] Example 4 Reaction product B 44.6g, adipic acid 29.2g, terephthalic acid 33.2g, diethylene glycol 17.8g, isopropyl titanate 0.05g. The above reaction product was heated to 160°C in a three-necked flask under nitrogen protection for 1.5 hours, and then gradually heated to 210°C for 5.5 hours to obtain polyester polyol C with a hydroxyl value of 78.2KOH / g and a viscosity (25°C) of 6500mPa.s.

[0070] After obtaining the polyester polyol for polyurethane foam, the following foaming formula is used for foaming:

[0071] Reaction product C 35.0g H350 polyether 15.0g 330 polyether 5.0g 303 polyether 10.0g 635 polyether 35g water 5.5g Foam leveler 1.0g TEP 10.0g A-1 0.3g Dabco33LV 0.8g PC-46 0.2g PMDI 135g

[0072] The prepared semi-rigid polyurethane foam has an overall density of 25.5 kg / m 3 The combustion oxygen index [OI] was measured according to ASTM D2863 and was 28.0.

[0073] The embodiments of this specific implementation method are all preferred embodiments of the present invention, and are not intended to limit the protection scope of the present invention. Therefore, any equivalent changes made based on the structure, shape, and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof, characterized in that: The following steps are involved: Furfuryl alcohol and diphenyl chlorophosphate are subjected to substitution reaction in the presence of an organic base to obtain an intermediate product A, and then the intermediate product A is subjected to addition polycondensation reaction with an unsaturated dicarboxylic acid and / or an anhydride thereof to obtain a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof.

2. The method for preparing a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof according to claim 1, characterized in that: The following steps are involved: S1. Dissolve furfuryl alcohol and diphenyl chlorophosphate in a mixed solvent, pass nitrogen protection, and heat to 30°C-65°C; S2. Under stirring conditions, an organic base is added dropwise to the mixture in step S1, and the reaction temperature is maintained for 2-6 hours. After the reaction is completed, the mixture is cooled and filtered to obtain a mixed solvent containing the intermediate product A; S3. Add unsaturated dicarboxylic acid and / or its anhydride to the mixed solvent containing the intermediate product A, stir and reflux at 85°C-115°C for 1-3.5 hours. After the reaction is completed, remove the solvent in the system to obtain biomass-derived phosphorus-containing dicarboxylic acid and / or its anhydride.

3. The method for preparing a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof according to claim 2, characterized in that: In step S1, the mixed solvent is benzene and toluene mixed in a mass ratio of 30:70 to 70:

30.

4. The method for preparing a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof according to claim 1 or 2, characterized in that: The molar ratio of furfuryl alcohol, diphenyl chlorophosphate, unsaturated dicarboxylic acid and / or its anhydride is 1:1:

1.

5. The method for preparing a biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof according to claim 1 or 2, characterized in that: The unsaturated dicarboxylic acid and / or its anhydride is selected from one or more of maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic acid, endomethylenetetrahydrophthalic anhydride, cyclohex-1-ene-1,2-dicarboxylic acid, and cyclohex-1-ene-1,2-dicarboxylic anhydride.

6. A biomass-derived phosphorus-containing dicarboxylic acid and / or anhydride thereof prepared by the preparation method according to any one of claims 1 to 5.

7. Use of the biomass-derived phosphorus-containing dicarboxylic acid and / or its anhydride according to claim 6 in the preparation of polyester.

8. The application according to claim 7, characterized in that: The polyester includes flame retardant polyester polyol for polyurethane foam, polyester polyol for flame retardant powder coating or flame retardant unsaturated polyester resin.

9. A method for preparing polyester, characterized in that: The following steps are involved: The polyol and the carboxylic acid composition C are subjected to a condensation reaction under the action of a catalyst to obtain a polyester polyol; the carboxylic acid composition C comprises the phosphorus-containing dicarboxylic acid and / or its anhydride as claimed in claim 6.

10. A method for preparing polyester, characterized in that: The following steps are involved: The polyol and the carboxylic acid composition D are subjected to a condensation reaction under the action of a catalyst, and after the condensation reaction, the mixed solvent containing the intermediate product A prepared in step S2 of claim 2 is added, and after the reaction is kept warm, the solvent is removed to obtain a polyester; the carboxylic acid composition D contains the unsaturated dicarboxylic acid and / or its anhydride.

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