A polyester, and a method for preparing and using the same

Abstract

The present application relates to a kind of polyester and its preparation method and application, the raw material of the polyester preparation includes the following components: polyester polyol, azide compound, reaction aid, alkynyl compound and catalyst;The azide compound includes bis (p-nitrophenyl) azide phosphoric acid ester.In the present application, the conversion rate of the polyester to the hydroxyl group (such as primary hydroxyl group) of polyester polyol is high, different functional groups can be introduced in end group, which can greatly improve the reaction selectivity of polyester and expand the application range of polyester on the basis of retaining the excellent performance of polyester itself, for example, on the basis of not affecting the self-learning performance, the reaction time with isocyanate can be improved, which helps to expand the production operation range, and is beneficial to the manufacture of large size materials;And the raw material of the polyester preparation is safe and not easy to explode, suitable for large-scale use in factory.

Description

Technical Field

[0001] This invention relates to the field of polyester technology, and more particularly to a polyester, its preparation method, and its application. Background Technology

[0002] Due to their excellent material and chemical properties, polyester materials are increasingly widely used in the construction, automotive, apparel, and home appliance industries. However, due to limitations in raw materials and processes for polyester production, the types of polyesters with further reactive groups are relatively limited. The three types with the largest market production scale are polyester polyols, unsaturated polyesters, and polyester acrylates. Polyester polyols have terminal hydroxyl groups, unsaturated polyesters have double bonds on the main chain, and polyester acrylates have terminal acrylate groups.

[0003] In existing technologies, different functional groups are usually introduced during the polyester synthesis polycondensation stage to increase the variety of polyester functional groups.

[0004] CN108285524A discloses an anti-slip polyurethane elastomer raw material, its preparation method, and its application. The anti-slip polyurethane elastomer raw material comprises polyurethane raw material component A and polyurethane raw material component B. Polyurethane raw material component A contains polyether ester diol and polyester polyol; polyurethane raw material component B contains hydroxyl-terminated liquid rubber modified polyester polyol. The disclosed polyester polyol is obtained by esterification and polycondensation reaction of adipic acid, small molecule diol, and hydroxyl-terminated polybutadiene liquid rubber to obtain a polyester product with double bonds.

[0005] CN103087304A discloses a method for producing polyester polyols. The method involves first modifying natural oils with maleic anhydride, then reacting the modified oils with a small-molecule polyol, a dicarboxylic acid, or a carboxylic acid ester to obtain a polyester polyol product with high cyclopentane solubility.

[0006] In existing technologies, it is crucial to find ways to introduce different functional groups into the end groups to significantly improve the reaction selectivity of polyester and expand its application range while retaining its excellent properties. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a polyester, its preparation method, and its applications. The polyester exhibits a high conversion rate of hydroxyl groups in polyester polyols. Introducing different functional groups into the end groups can significantly improve the reaction selectivity and expand the application range of the polyester while retaining its excellent inherent properties. For example, without affecting its self-sustaining properties, it can increase the reaction time with isocyanates for fiber drawing, which helps to expand the scope of production and construction operations and is beneficial for manufacturing large-sized materials. Furthermore, the raw materials used in the preparation of the polyester are safe and non-explosive, making it suitable for large-scale factory use.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a polyester, wherein the raw materials for preparing the polyester include the following components: polyester polyol, azide compound, reaction aid, alkynyl compound and catalyst;

[0010] The azide compound includes bis(p-nitrophenyl)azidophosphate.

[0011] In this invention, bis(p-nitrophenyl) azidophosphate is introduced into the raw materials for preparing the polyester, which can improve the conversion rate of hydroxyl groups in the polyester polyol. Furthermore, by combining with alkynyl compounds, polyesters with different end functional groups are obtained. While retaining the excellent properties of the polyester itself, the reaction selectivity of the polyester is greatly improved and the application range of the polyester is expanded.

[0012] Preferably, the reaction aid comprises an alkenyl compound.

[0013] Preferably, the reaction aid comprises 1,8-diazabicyclo[5,4,0]undec-7-ene.

[0014] In this invention, the reaction aid is preferably 1,8-diazabicyclo[5,4,0]undec-7-ene because it can be used in combination with the azide compound to improve the conversion rate of hydroxyl groups in polyester polyols, and while retaining the excellent properties of polyester itself, it can significantly improve the reaction selectivity of polyester and expand the application range of polyester.

[0015] Preferably, the polyester polyol has terminal hydroxyl groups.

[0016] Preferably, the raw materials for preparing the polyester polyol include polyol monomers and polyacids.

[0017] Preferably, the polyol monomer includes any one or a combination of at least two of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, methylpropanediol, 3-methyl-1,5-pentanediol, neopentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, polyethylene glycol, or polybutanediol. Typical but non-limiting combinations include: combinations of ethylene glycol, 1,3-propanediol, and 1,2-propanediol; combinations of 1,4-butanediol, diethylene glycol, and triethylene glycol; combinations of methylpropanediol, 3-methyl-1,5-pentanediol, neopentanediol, 1,6-hexanediol, glycerol, and trimethylolpropane; and combinations of 1,6-hexanediol, glycerol, trimethylolpropane, polyethylene glycol, and polybutanediol.

[0018] Preferably, the polyacid includes any one or a combination of at least two of succinic acid, adipic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, or trimellitic anhydride. Typical but non-limiting combinations include: a combination of succinic acid and adipic acid, a combination of sebacic acid, terephthalic acid, and phthalic anhydride, and a combination of sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, and trimellitic anhydride, etc.

[0019] Preferably, the catalyst comprises an addition catalyst.

[0020] Preferably, the catalyst further includes a polycondensation catalyst.

[0021] Preferably, the addition catalyst comprises any one or a combination of at least two of cuprous bromide, cuprous iodide, triethylamine, or pentamethyldiethylenetriamine, wherein typical but non-limiting combinations include: a combination of cuprous bromide and cuprous iodide, a combination of cuprous iodide, triethylamine, and pentamethyldiethylenetriamine, a combination of cuprous bromide, cuprous iodide, triethylamine, and pentamethyldiethylenetriamine, etc.

[0022] Preferably, the polycondensation catalyst comprises any one or a combination of at least two of stannous octoate, tetrabutyl titanate, or tetraisopropyl titanate, wherein typical but non-limiting combinations include: a combination of stannous octoate and tetrabutyl titanate, a combination of tetrabutyl titanate and tetraisopropyl titanate, a combination of stannous octoate, tetrabutyl titanate, and tetraisopropyl titanate, etc.

[0023] Preferably, the alkynyl compound comprises any one or a combination of at least two of the following: propynylamine, 4-ethynylaniline, vinylacetylene, isopropynylacetylene, 3-butyn-2-ol, 3-bromopropyne, 3-chloropropyne, 3-fluoropropyne, propyne-maleimide, propyneamide, trimethylsilylacetylene, alkynyl-terminated ethoxy compounds, or alkynyl-terminated propoxy compounds. Typical but non-limiting combinations include: combinations of propynylamine, 4-ethynylaniline, and vinylacetylene; combinations of isopropynylacetylene, 3-butyn-2-ol, 3-bromopropyne, and 3-chloropropyne; and combinations of 3-chloropropyne, 3-fluoropropyne, propyne-maleimide, propyneamide, and trimethylsilylacetylene.

[0024] Preferably, the raw materials for preparing the polyester comprise the following components in parts by weight:

[0025]

[0026] In this invention, the raw materials are used in combination at specific weight ratios. Specifically, the amount of azide compound and reaction aid added can be designed according to the amount of polyol monomer and polyacid added, so as to obtain a polyester with excellent performance.

[0027] In this invention, the polyol monomer is in the form of 30-70 parts by weight, such as 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, etc.

[0028] The weight fraction of the polyacid is 30-70 parts, for example 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, etc.

[0029] The azide compound is present in parts by weight of 0.1-40, for example, 0.5, 1, 2, 5, 10, 15, 20, 25, 30, 35, etc.

[0030] The reaction aid is present in parts by weight of 0.01-15 parts, for example, 0.05 parts, 0.1 parts, 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, etc.

[0031] The alkynyl compound is present in parts by weight of 0-100, but not equal to 0, for example, 5, 10, 20, 40, 60, 80, etc.

[0032] The catalyst is in the range of 0-0.3 parts by weight, but not equal to 0 parts, for example, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, etc.

[0033] Preferably, the molar ratio of the azide compound to the terminal hydroxyl groups of the polyester polyol is (1-1.2):1, wherein 1-1.2 can be 1.05, 1.1, 1.15, etc.

[0034] Preferably, the molar ratio of the reaction aid to the azide compound is (0.8-1.2):1, wherein 0.8-1.2 can be 0.85, 0.9, 0.95, etc., and more preferably 1:1.

[0035] Preferably, the molar ratio of the alkynyl compound to the azide compound is (0.8-1.2):1, wherein 0.8-1.2 can be 0.85, 0.9, 0.95, etc., and more preferably 1:1.

[0036] Preferably, the polycondensation catalyst is present in a weight ratio of 0-0.1 parts, but not equal to 0 parts, for example, 0.02 parts, 0.04 parts, 0.06 parts, 0.08 parts, etc.

[0037] Preferably, the addition catalyst is present in a weight fraction of 0.01-0.2 parts, such as 0.02 parts, 0.04 parts, 0.06 parts, 0.08 parts, 0.1 parts, 0.12 parts, 0.14 parts, 0.16 parts, 0.18 parts, etc.

[0038] In a second aspect, the present invention provides a method for preparing the polyester described in the first aspect, the method comprising the following steps:

[0039] The polyester is obtained by reacting polyester polyol, azide compound, reaction aid and alkynyl compound in the presence of a catalyst.

[0040] Preferably, the reaction includes first reacting the polyester polyol, the azide compound, and the reaction aid to obtain a polyester with azide-terminated groups, and then reacting the polyester with azide-terminated groups with an alkynyl compound to obtain the polyester.

[0041] Preferably, the temperature of the first reaction is 60-130℃, such as 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, etc.

[0042] Preferably, the time for the first reaction is 6-24 hours, such as 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, etc.

[0043] Preferably, the temperature of the second reaction is 60-100℃, such as 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, etc.

[0044] Preferably, the second reaction takes 4-20 hours, such as 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, etc.

[0045] Preferably, the method for preparing the polyester polyol includes the following steps:

[0046] The polyester polyol is obtained by polycondensation reaction of polyol monomer and polyacid under the action of a catalyst.

[0047] Preferably, the temperature of the polycondensation reaction is 200-250℃, such as 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃, etc.

[0048] Preferably, the polycondensation reaction takes 4-18 hours (e.g., 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, etc.) until the acid value is below 3 mg KOH / g (e.g., 2.5 mg KOH / g, 2.0 mg KOH / g, 1.5 mg KOH / g, 1.0 mg KOH / g, 0.5 mg KOH / g, etc.) and the hydroxyl value is 20 mg KOH / g to 400 mg KOH / g (e.g., 50 mg KOH / g, 100 mg KOH / g, 150 mg KOH / g, 200 mg KOH / g, 250 mg KOH / g, 300 mg KOH / g, 350 mg KOH / g, etc.).

[0049] As a preferred technical solution, the preparation method includes the following steps:

[0050] (1) Polyol monomers and polyacids are subjected to polycondensation reaction at 200-250°C under the action of a polycondensation catalyst to obtain the polyester polyol;

[0051] (2) The polyester polyol, azide compound and reaction aid are reacted for the first time at 60-130°C under the action of a catalyst to obtain a polyester with azide group at the end. Then, the polyester with azide group at the end is reacted with an alkynyl compound for the second time at 60-100°C under the action of an addition catalyst to obtain the polyester.

[0052] Thirdly, the present invention provides an application of the polyester described in the first aspect in construction, automobiles, clothing or home appliances.

[0053] Compared with the prior art, the present invention has the following beneficial effects:

[0054] In this invention, the polyester exhibits a high conversion rate of hydroxyl groups (e.g., primary hydroxyl groups) in polyester polyols. Introducing different functional groups into the end groups can significantly improve the reaction selectivity and expand the application range of the polyester while retaining its excellent properties. For example, without affecting its self-learning properties, it can increase the reaction and fiber drawing time with isocyanates, which helps to expand the scope of production and construction operations and is beneficial for manufacturing large-sized materials. Furthermore, the raw materials for preparing the polyester are safe and non-explosive, making it suitable for large-scale use in factories. Detailed Implementation

[0055] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0056] Example 1

[0057] This embodiment provides a polyester, which is a terminal amine polyester. The raw materials for preparing the polyester include the following components: polyol monomer, polyacid, azide compound, reaction aid, alkynyl compound, polycondensation catalyst and addition catalyst. The preparation method of the polyester includes the following steps:

[0058] (1) Diethylene glycol / phthalic anhydride / tetrabutyl titanate was added to the reactor at a molar ratio of 1.4 / 1 / 0.0001. The temperature was raised to 220°C under nitrogen protection and maintained at this temperature for 16 hours. During the reaction, the condensation water and small molecule polyol were separated and removed by a fractionation tower connected to the reactor. The reaction was stopped when the acid value was lower than 3 mg KOH / g to obtain polyester polyol.

[0059] (2) Cool down to 80°C, add bis(p-nitrophenyl) azidophosphate and 1,8-diazabicyclo[5,4,0]undec-7-ene at a molar ratio of 1.1 / 1 with the hydroxyl group of the polyester polyol, and maintain this temperature for 18 hours. When the hydroxyl value is lower than 5 mg KOH / g, add propargylamine, cuprous bromide and pentamethyldiethylenetriamine at a molar ratio of 1 / 0.001 / 0.001 with the azido group, and maintain this temperature for 16 hours to obtain the polyester, which can react with isocyanate to produce polyurea products.

[0060] Example 2

[0061] This embodiment provides a polyester, which is a vinyl-terminated polyester. The raw materials for preparing the polyester include the following components: polyol monomer, polyacid, azide compound, reaction aid, alkynyl compound, polycondensation catalyst, and addition catalyst. The preparation method of the polyester includes the following steps:

[0062] (1) Diethylene glycol / adipic acid / tetrabutyl titanate was added to the reactor in a molar ratio of 1.3 / 1 / 0.0001. The temperature was raised to 220°C under nitrogen protection and maintained at this temperature for 14 hours. During the reaction, the condensation water and small molecule polyol were separated and removed by a fractionation tower connected to the reactor. The reaction was stopped when the acid value was lower than 3 mg KOH / g to obtain polyester polyol.

[0063] (2) Cool down to 80°C, add bis(p-nitrophenyl) azidophosphate and 1,8-diazabicyclo[5,4,0]undec-7-ene at a molar ratio of 1.1 / 1 with the hydroxyl group of the polyester polyol, and maintain this temperature for 18 hours. When the hydroxyl value is lower than 5 mg KOH / g, add vinyl acetylene, cuprous bromide and pentamethyldiethylenetriamine at a molar ratio of 1 / 0.001 / 0.001 with the azido group, and maintain this temperature for 16 hours to obtain the polyester, which can be used to produce thermosetting plastic products through double bond crosslinking.

[0064] Example 3

[0065] This embodiment provides a polyester, which is a secondary hydroxyl crystalline polyester. The raw materials for preparing the polyester include the following components: polyol monomer, polyacid, azide compound, reaction aid, alkynyl compound, polycondensation catalyst and addition catalyst. The preparation method of the polyester includes the following steps:

[0066] (1) 1,4-Butanediol / adipic acid / tetrabutyl titanate were added to the reactor at a molar ratio of 1.1 / 1 / 0.0001. The temperature was raised to 220°C under nitrogen protection and maintained at this temperature for 18 hours. During the reaction, the condensation water and small molecule polyol were separated and removed by a fractionation tower connected to the reactor. The reaction was stopped when the acid value was lower than 3 mg KOH / g to obtain polyester polyol.

[0067] (2) Cool down to 80°C, add bis(p-nitrophenyl) azidophosphate and 1,8-diazabicyclo[5,4,0]undec-7-ene at a molar ratio of 1.1 / 1 with the hydroxyl group of the polyester polyol, and maintain this temperature for 18 hours. When the hydroxyl value is lower than 5 mg KOH / g, add 3-butyn-2-ol, cuprous bromide and pentamethyldiethylenetriamine at a molar ratio of 1 / 0.001 / 0.001 with the azido group, and maintain this temperature for 16 hours to obtain the polyester, which still has some alcohol hydroxyl groups, and can be used to produce crystalline polyurethane products with slow reaction systems.

[0068] Example 4

[0069] This embodiment provides a polyester, which is a bromine-terminated polyester. The raw materials for preparing the polyester include the following components: polyol monomer, polyacid, azide compound, reaction aid, alkynyl compound, polycondensation catalyst, and addition catalyst. The preparation method of the polyester includes the following steps:

[0070] (1) Ethylene glycol / adipic acid / tetrabutyl titanate was added to the reactor in a molar ratio of 1.2 / 1 / 0.0001. The temperature was raised to 220°C under nitrogen protection and maintained at this temperature for 14 hours. During the reaction, the condensation water and small molecule polyol were separated and removed by a fractionation tower connected to the reactor. The reaction was stopped when the acid value was lower than 3 mg KOH / g to obtain polyester polyol.

[0071] (2) Cool down to 80°C, add bis(p-nitrophenyl) azidophosphate and 1,8-diazabicyclo[5,4,0]undec-7-ene at a molar ratio of 1.1 / 1 with the hydroxyl group of the polyester polyol, and maintain this temperature for 18 hours. When the hydroxyl value is lower than 5 mg KOH / g, add 3-bromopropyne, cuprous bromide and pentamethyldiethylenetriamine at a molar ratio of 1 / 0.001 / 0.001 with the azido group, and maintain this temperature for 16 hours to obtain the polyester, which can be generated into a block copolymer product by controlled free radical polymerization.

[0072] Example 5

[0073] This embodiment provides a polyester, which is a maleimide-based polyester. The raw materials for preparing the polyester include the following components: polyol monomer, polyacid, azide compound, reaction aid, alkynyl compound, polycondensation catalyst, and addition catalyst. The preparation method of the polyester includes the following steps:

[0074] (1) Diethylene glycol / sebacic acid / tetrabutyl titanate molar ratio of 1.5 / 1 / 0.0001 was added to the reaction vessel. The temperature was raised to 220°C under nitrogen protection and maintained at this temperature for 18 hours. During the reaction, the condensation water and small molecule polyol were separated and removed by the fractionation tower connected to the reaction vessel. The reaction was stopped when the acid value was lower than 3 mg KOH / g to obtain polyester polyol.

[0075] (2) Cool down to 80°C, add bis(p-nitrophenyl) azidophosphate and 1,8-diazabicyclo[5,4,0]undec-7-ene at a molar ratio of 1.1 / 1 with the hydroxyl group of the polyester polyol, and maintain this temperature for 18 hours. When the hydroxyl value is lower than 5 mg KOH / g, add propyne-maleimide, cuprous bromide and pentamethyldiethylenetriamine at a molar ratio of 1 / 0.001 / 0.001 with the azido group, and maintain this temperature for 16 hours to obtain the polyester, which can be coupled with bovine serum albumin via thiol coupling.

[0076] Example 6

[0077] This embodiment provides a polyester, which is a silicone-based polyester. The raw materials for preparing the polyester include the following components: polyol monomer, polyacid, azide compound, reaction aid, alkynyl compound, polycondensation catalyst, and addition catalyst. The preparation method of the polyester includes the following steps:

[0078] (1) Diethylene glycol / terephthalic acid / phthalic anhydride / tetrabutyl titanate were added to the reactor in a molar ratio of 3 / 1 / 1 / 0.0002. The temperature was raised to 220°C under nitrogen protection and maintained at this temperature for 18 hours. During the reaction, the condensation water and small molecule polyols generated were separated and removed by a fractionation tower connected to the reactor. The reaction was stopped when the acid value was lower than 3 mg KOH / g to obtain polyester polyol.

[0079] (2) Cool down to 80°C, add bis(p-nitrophenyl) azidophosphate and 1,8-diazabicyclo[5,4,0]undec-7-ene at a molar ratio of 1.1 / 1 with the hydroxyl group of the polyester polyol, and maintain this temperature for 18 hours. When the hydroxyl value is lower than 5 mg KOH / g, add trimethylsilylacetylene, cuprous bromide and pentamethyldiethylenetriamine at a molar ratio of 1 / 0.001 / 0.001 with the azido group, and maintain this temperature for 16 hours to obtain the polyester.

[0080] Example 7

[0081] This embodiment provides a polyester, which is a polyester-ether block copolymer. The raw materials for preparing the polyester include the following components: polyol monomer, polyacid, azide compound, reaction aid, alkynyl compound, polycondensation catalyst, and addition catalyst. The preparation method of the polyester includes the following steps:

[0082] (1) Ethylene glycol / adipic acid / tetrabutyl titanate was added to the reactor in a molar ratio of 1.3 / 1 / 0.0001. The temperature was raised to 220°C under nitrogen protection and maintained at this temperature for 14 hours. During the reaction, the condensation water and small molecule polyol were separated and removed by a fractionation tower connected to the reactor. The reaction was stopped when the acid value was lower than 3 mg KOH / g to obtain polyester polyol.

[0083] (2) Cool down to 80°C, add bis(p-nitrophenyl) azidophosphate and 1,8-diazabicyclo[5,4,0]undec-7-ene at a molar ratio of 1.1 / 1 with the hydroxyl group of the polyester polyol, and maintain this temperature for 18 hours. When the hydroxyl value is lower than 5 mg KOH / g, add acetylene-(PEG)400 (acetylene-terminated ethoxy compound), cuprous bromide and pentamethyldiethylenetriamine at a molar ratio of 1 / 0.001 / 0.001 with the azido group, and maintain this temperature for 16 hours to obtain the polyester, which can be used as a surfactant.

[0084] Example 8

[0085] The difference between this embodiment and Example 3 is that the 1,8-diazabicyclo[5,4,0]undec-7-ene is replaced with an equimolar amount of 7-methyl-1,5,7-triazabicyclo[4,4,0]dec-5-ene; all other aspects are the same as in Example 3.

[0086] Comparative Example 1

[0087] The difference between this comparative example and Example 3 is that the bis(p-nitrophenyl) azidophosphate is replaced with an equimolar amount of sodium azide; otherwise, they are the same as in Example 3.

[0088] Comparative Example 2

[0089] The difference between this comparative example and Example 3 is that the bis(p-nitrophenyl)azidophosphate is replaced with an equimolar amount of sodium azide, and the 1,8-diazabicyclo[5,4,0]undec-7-ene is replaced with an equimolar amount of ammonium chloride. All other aspects are the same as in Example 3.

[0090] Performance testing

[0091] The polyesters described in Examples 3 and 8 and Comparative Examples 1-2 were tested as follows:

[0092] (1) Conversion rate of primary hydroxyl groups in polyester polyols: The following hydrogen contents were detected by nuclear magnetic resonance hydrogen spectroscopy: 2H of methylene in -CH2OH in terminal hydroxyl polyester polyols, 2H of methylene in -CH2-N3 after primary hydroxyl groups are converted into azide groups, and H in 1,2,3-triazole groups after cycloaddition reaction.

[0093] (2) Reactivity (gel time): The polyester, 1,4-butanediol and diphenylmethane diisocyanate were reacted at 80°C in a molar ratio of 1:2:3, and the gel time was tested.

[0094] (3) Mechanical properties (hardness, tensile strength): Polyurethane elastomer was prepared by mixing the polyester, toluene diisocyanate and 3,3'-dichloro-4,4'-diaminodiphenylmethane in a molar ratio of 1:2:1. The hardness was tested according to GB / T 531-1999 and the tensile strength was tested according to GB / T 528-2009.

[0095] The test results are summarized in Table 1.

[0096] Table 1

[0097]

[0098] Analysis of the data in Table 1 shows that, within the preferred range (taking Example 3 as an example), the polyester of this invention achieves a conversion rate of over 83% for the primary hydroxyl groups of the polyester polyol, and a gel time of over 156 seconds. The prepared elastomer has a hardness between 92-95 Shore A and a tensile strength between 52-55 MPa, with little difference in mechanical properties. This is because the main structure of the polyester polyol remains unchanged, only the end-group chemical functional groups have changed. In this invention, the polyester raw materials are safe and suitable for large-scale factory use. The high conversion rate of the polyester for the primary hydroxyl groups of the polyester polyol, combined with the introduction of different functional groups at the end groups, can significantly improve the reaction selectivity and expand the application range of the polyester while retaining its excellent properties. For example, without affecting its self-cleaning properties, it can increase the gel time with isocyanate, which helps to expand the scope of production and construction operations and is beneficial for manufacturing large-size materials.

[0099] Analysis of Comparative Examples 1-2 and Example 3 shows that the performance of Comparative Examples 1-2 is inferior to that of Example 3, proving that the polyester described in this invention has better performance. Comparative Examples 1-2 achieved a conversion rate of over 50%, but sodium azide is an explosive material and is not suitable for large-scale use in factories.

[0100] Analysis of Examples 8 and 3 shows that the performance of Example 8 is not as good as that of Example 3, proving that the polyester formed by using 1,8-diazabicyclo[5,4,0]undec-7-ene as the reaction aid has better performance.

[0101] The present invention has been illustrated with the above embodiments to explain the detailed method of the present invention. However, the present invention is not limited to the detailed method described above, that is, it does not mean that the present invention must rely on the detailed method described above to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A polyester, characterized in that, The raw materials for preparing the polyester include the following components: polyester polyol, azide compound, reaction aid, alkynyl compound, and catalyst; The azide compound includes bis(p-nitrophenyl)azidophosphate; The reaction aids include alkenyl compounds; The alkynyl compounds include any one or a combination of at least two of the following: propyneamine, 4-ethynylaniline, vinylacetylene, isopropenylacetylene, 3-butyn-2-ol, 3-bromopropyne, 3-chloropropyne, 3-fluoropropyne, propyne-maleimide, propyneamide, trimethylsilylacetylene, alkynyl-terminated ethoxy compounds, or alkynyl-terminated propoxy compounds. The polyester is prepared by the following method, which includes the following steps: The polyester is obtained by reacting polyester polyol, azide compound, reaction aid and alkynyl compound in the presence of a catalyst.

2. The polyester according to claim 1, characterized in that, The reaction aid includes 1,8-diazabicyclo[5,4,0]undec-7-ene.

3. The polyester according to claim 1, characterized in that, The polyester polyol has terminal hydroxyl groups.

4. The polyester according to claim 1, characterized in that, The raw materials for preparing the polyester polyol include polyol monomers and polyacids.

5. The polyester according to claim 4, characterized in that, The polyol monomers include any one or a combination of at least two of the following: ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, methylpropanediol, 3-methyl-1,5-pentanediol, neopentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, polyethylene glycol, or polybutanediol.

6. The polyester according to claim 4, characterized in that, The polyacids include any one or a combination of at least two of succinic acid, adipic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, or trimellitic anhydride.

7. The polyester according to claim 1, characterized in that, The catalyst includes an addition catalyst.

8. The polyester according to claim 1, characterized in that, The catalyst also includes a polycondensation catalyst.

9. The polyester according to claim 7, characterized in that, The addition catalyst includes any one or a combination of at least two of cuprous bromide, cuprous iodide, triethylamine, or pentamethyldiethylenetriamine.

10. The polyester according to claim 8, characterized in that, The polycondensation catalyst includes any one or a combination of at least two of stannous octoate, tetrabutyl titanate, or tetraisopropyl titanate.

11. The polyester according to claim 4, characterized in that, The raw materials for preparing the polyester include the following components in parts by weight: 30-70 parts of polyol monomer 30-70 parts of polyacids Azide compounds 0.1-40 parts 0.01-15 parts of reaction aid Alkyne compounds: 0-100 parts, but not equal to 0 parts Catalyst: 0-0.3 parts, but not equal to 0 parts.

12. The polyester according to claim 8, characterized in that, In the catalyst, the polycondensation catalyst has a weight ratio of 0-0.1 parts, but is not equal to 0 parts.

13. The polyester according to claim 7, characterized in that, In the catalyst, the addition catalyst is present in parts by weight of 0.01-0.2 parts.

14. A method for preparing the polyester according to any one of claims 1-13, characterized in that, The preparation method includes the following steps: The polyester is obtained by reacting polyester polyol, azide compound, reaction aid and alkynyl compound in the presence of a catalyst.

15. The method for preparing polyester according to claim 14, characterized in that, The reaction includes first reacting polyester polyol, azide compound, and reaction aid to obtain polyester with azide-terminated groups, and then reacting the polyester with azide-terminated groups with an alkynyl compound to obtain the polyester.

16. The method for preparing polyester according to claim 15, characterized in that, The temperature of the first reaction is 60-130℃.

17. The method for preparing polyester according to claim 15, characterized in that, The temperature of the second reaction is 60-100℃.

18. The method for preparing polyester according to claim 14, characterized in that, The preparation method of the polyester polyol includes the following steps: The polyester polyol is obtained by polycondensation reaction of polyol monomer and polyacid under the action of a catalyst.

19. The method for preparing polyester according to claim 18, characterized in that, The temperature of the polycondensation reaction is 200-250℃.

20. The preparation method according to claim 14, characterized in that, The preparation method includes the following steps: (1) Polyol monomers and polyacids are subjected to polycondensation reaction at 200-250°C under the action of a polycondensation catalyst to obtain the polyester polyol; (2) The polyester polyol, azide compound and reaction aid are reacted for the first time at 60-130°C under the action of a catalyst to obtain a polyester with azide group at the end. Then, the polyester with azide group at the end is reacted with an alkynyl compound for the second time at 60-100°C under the action of an addition catalyst to obtain the polyester.

21. The use of the polyester according to any one of claims 1-13 in construction, automobiles, clothing or home appliances.

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