Hydroxyl-terminated polyesterimide polyol, preparation method thereof and application of hydroxyl-terminated polyesterimide polyol in flexibilizer

Abstract

The invention relates to the field of epoxy resin, in particular to hydroxyl-terminated polyesterimide polyol as well as a preparation method and application thereof, and the hydroxyl-terminated polyesterimide polyol has a structural formula as follows: formula (I), the structural formula of R is shown in the specification; the hydroxyl-terminated polyesterimide polyol can react with polyisocyanate, a chain extender and a sealing agent to prepare the terminated high-temperature-resistant polyurethane flexibilizer, and the terminated high-temperature-resistant polyurethane flexibilizer can solve the high-temperature-resistant toughness and strength problems of the chip packaging adhesive at the same time. Therefore, the corresponding epoxy resin system is suitable for high-integration circuit board packaging at the present stage.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of epoxy resin, more particularly, it relates to a hydroxyl-terminated polyester-imine polyol, a preparation method thereof and application thereof in toughening agent. BACKGROUND

[0002] In the chip packaging application, the chip packaged by epoxy glue has the functions of insulation, sealing, shock resistance and the like, and plays a protective role for the chip. However, with the development of high-frequency and high-speed integrated circuits towards integration and miniaturization, the traditional epoxy glue cannot be applied to the packaging of highly integrated chips due to its poor temperature resistance, poor toughness and easy cracking.

[0003] In the related art, the toughening technology of epoxy resin mainly uses polyurethane, rubber, fatty acid and the like as the toughening agent, which can effectively increase the toughness, but has no significant effect on the improvement of heat resistance or has a negative effect. For example, the method of using polytetramethylene ether glycol as a flexible chain and reacting with isocyanate monomer and then using a blocking agent for end capping, which will reduce the high temperature resistance of the epoxy resin material.

[0004] Therefore, how to solve the problems of high temperature resistance, toughness and strength of the chip packaging glue is a technical problem to be solved by those skilled in the art. In summary, the hydroxyl-terminated polyester-imine polyol, the preparation method thereof and the application thereof are provided, which can be applied to the packaging of highly integrated circuit boards at the present stage. SUMMARY

[0005] The present application provides a hydroxyl-terminated polyester-imine polyol, a preparation method thereof and application thereof in toughening agent. The hydroxyl-terminated polyester-imine polyol and the toughening agent thereof can give the epoxy resin matrix excellent high strength and high temperature resistance without damaging the modulus of the epoxy resin matrix.

[0006] In a first aspect, the present application provides a hydroxyl-terminated polyester-imine polyol, the structural formula of which is as follows: Formula (I); the structural formula of R is: .

[0007] In a second aspect, the present application provides a synthesis method of a hydroxyl-terminated polyester-imine polyol, the hydroxyl-terminated polyester-imine polyol being polymerized from a polyol monomer, a polyacid monomer, trimellitic anhydride (TMA) and methylenedianiline (MDA).

[0008] Preferably, the following steps are included: adding the polyol monomer, the polyacid monomer, a catalyst, TMA and MDA at room temperature, and heating to 200-220℃ during the feeding process, controlling the column top temperature at 80-105℃ during the process, then vacuumizing, gradually increasing the vacuum degree, reducing pressure to evaporate the reaction by-products, and keeping warm for 1-3h.

[0009] Preferably, the polyol monomer, polyacid monomer, catalyst, TMA and MDA feeding ratio is (30-70): (3-35): (0.07-0.15): (10-30): (5-15).

[0010] Preferably, the polyol monomer is selected from one or more of ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol / neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,8-octanediol, 2,4-diethyl-1,3-octanediol, trimethyl-1,6-hexanediol, 1,7-heptanediol, 4-propyl-1,8-octanediol, 1,9-nonanediol, polyoxypropylene polyols with a molecular weight of 200-2000, neopentyl glycol mono(hydroxypivalate), 2-ethyl-1,3-propanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol.

[0011] Preferably, the polyacid monomer is selected from one or more of butanedioic acid, decanedioic acid, hexanedioic acid, pentanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, maleic anhydride, dodecanedioic acid, cis-butenedioic acid, trans-butenedioic acid, hydroxybutanedioic acid and dimer acid.

[0012] Preferably, the catalyst is selected from one or a mixture of both of butyl orthotitanate and zinc acetate.

[0013] In a third aspect, the application provides a hydroxyl-terminated polyester-imine polyol or the polyol obtained by any of the above preparation methods for a wide range of applications in the preparation of polyurethane toughening agents, polyurethane elastomers, polyurethane coatings and other polyurethane materials, high-performance insulation materials, photoresist raw materials.

[0014] In a fourth aspect, the application discloses a capped high-temperature-resistant polyurethane toughening agent, and the preparation raw materials include the above-mentioned hydroxyl-terminated polyester-imine polyol or the polyol obtained by any of the above preparation methods.

[0015] Preferably, the hydroxyl-terminated polyester-imine polyol is obtained by the reaction of the above-mentioned hydroxyl-terminated polyester-imine polyol or the polyol obtained by any of the above preparation methods, polyisocyanate, chain extender and blocking agent.

[0016] In summary, the application has the following beneficial effects:

[0017] 1. The hydroxyl-terminated polyester-imine polyol synthesized in this application is synthesized by one-step method using polyol monomers, polyacid monomers, TMA and MDA. The polyol has a special molecular structure. The highly conjugated system gives it greater planar rigidity, which limits the movement ability of the molecular chain to some extent. This makes the polyol effectively resist excessive deformation at high temperature, maintain good shape stability and mechanical properties, and exhibit excellent high temperature resistance. In addition, by adjusting the ratio of TMA and MDA, the polyol can maintain a certain flexibility while having high temperature resistance.

[0018] 2. The capped high temperature resistant polyurethane toughening agent synthesized in this application uses hydroxyl-terminated polyester-imine polyol as the main raw material. With the help of the structure-activity relationship between isocyanate group and polyester-imine polyol, the prepared toughening agent has excellent high temperature resistance and flexibility. The specific mechanism is as follows:

[0019] Enhanced intermolecular forces: The large Π bond on the benzene ring of the polyester-imine can have Π-Π stacking with other molecular chains, promoting the arrangement of molecular chains to be more compact. At the same time, the hydrogen atoms on the benzene ring can form hydrogen bonds with other polar groups in the polyurethane molecule, further strengthening the intermolecular forces. In a high temperature environment, these enhanced intermolecular forces can effectively inhibit the relative sliding of molecular chains. When the material is subjected to external force, the molecular chains can better coordinate to resist external force, thereby improving the high temperature toughness of the material.

[0020] Optimization of phase separation structure: By reasonably adjusting the ratio of isocyanate group and polyester-imine polyol, a more uniform and stable phase separation structure is formed between the soft segment and the hard segment. The hard segment phase is uniformly dispersed in the soft segment phase, playing the role of physical crosslinking point and limiting the movement of the soft segment. Under high temperature conditions, this stable phase structure can efficiently transfer stress, ensuring that the soft segment and the hard segment work together when the material is stressed, thereby improving the high temperature toughness of the material.

[0021] 3. The capped polyurethane toughening agent obtained in this application can be added to suitable epoxy resins and mixed and cured by appropriate process methods to achieve the toughening effect. Compared with other toughening agents, this toughening agent can improve the high temperature resistance and strength of the epoxy resin while ensuring the modulus of the resin matrix, so that it meets the application conditions in chip packaging glue. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 The infrared spectrum of the hydroxyl-terminated polyester-imine polyol obtained in Preparation Example 1. DETAILED DESCRIPTION

[0023] The following will be combined with the drawings Figure 1The application is further described in detail by the preparation examples and the examples.

[0024] The raw materials and / or equipment used in the preparation examples, examples and tests of the present application are conventional raw materials and equipment available on the market, except for the special description below:

[0025]

[0026] Preparation Example 1

[0027] A hydroxyl-terminated polyester-imine polyol has the following structure: Formula (I); the structure of R is: and is prepared by the following preparation steps:

[0028] The polyol monomer, polybasic acid monomer, catalyst, TMA and MDA are added into a reaction kettle at room temperature, and the temperature is raised to 220°C during the feeding process, and the column top temperature is controlled at 102°C during the process; The polyol monomer is polyoxypropylene glycol 400; the polybasic acid monomer is adipic acid; and the catalyst is butyl orthotitanate.

[0029] The feeding ratio of the polyol monomer, polybasic acid monomer, catalyst, TMA and MDA is 60.71:8.08:0.08:20.54:10.59.

[0030] Then vacuumize, and gradually increase the vacuum degree, distill the reaction by-products under reduced pressure, and keep warm for 2 hours to obtain the hydroxyl-terminated polyester-imine polyol.

[0031] The infrared spectrum thereof is shown in the following figure: Figure 1 From the figure, the characteristic absorption peaks of the hydroxyl-terminated polyester-imine polyol are found: 3471.34 cm -1 corresponding to the stretching vibration absorption peak of hydroxyl, 2970.04 cm -1 and 2868.05 cm -1 corresponding to the stretching vibration absorption peak of methyl, 1780.96 cm -1 and 1717.04 cm -1 corresponding to the asymmetric and symmetric stretching vibration peaks of imine ring structure-CO-N-CO-, 1692.37 cm -1 corresponding to the stretching vibration absorption peak of imide C=O, 1514.17 cm -1 corresponding to the stretching vibration absorption peak of benzene ring skeleton, 1365.02 cm -1 corresponding to the axial vibration peak of imide ring, 1216.00 cm -1 corresponding to the C-N stretching vibration absorption peak, 1093.45 cm -1Stretching vibration absorption peak corresponding to C-O-C of polyoxypropylene diol, 723.71 cm -1 C=O bending vibration absorption peak corresponding to imide.

[0032] In summary, the appearance of the above characteristic absorption peaks indicates the existence of imine ring structure in the structure, and it is determined that the hydroxyl-terminated polyester imine polyol can be synthesized by the above process. The hydroxyl value of the above hydroxyl-terminated polyester imine polyol is 56.8 mgKOH / g, [OH] / [COOH] is equal to 1.39, and the content of TMA and MDA is equal to 31.13%.

[0033] Preparation Example 2-5

[0034] A hydroxyl-terminated polyester imine polyol, which is different from Preparation Example 1 in that the feeding ratio of each material is different, and the specific selection is shown in the following table:

[0035] Table: Comparison table of feeding ratio of each material in Preparation Example 2-5

[0036] Preparation Example 6-10

[0037] A hydroxyl-terminated polyester imine polyol, which is different from Preparation Example 1 in that the specific selection of each material is different, and the specific selection is shown in the following table:

[0038] Table: Comparison table of selection of each material in Preparation Example 6-10

[0039] The hydroxyl-terminated polyester imine polyols obtained in the above Preparation Examples 2-10 are selected, and their hydroxyl value, [OH] / [COOH] and TMA & MDA content are tested, and the test results are recorded in the following table:

[0040] Table: Comparison table of properties of hydroxyl-terminated polyester imine polyols in Preparation Examples 2-10

[0041] From the above table, in order to obtain the hydroxyl-terminated polyester-imine polyol, the proportions of the polyol and the polybasic acid are preferably such that the [OH] groups are present in stoichiometric excess compared to the [COOH], and by adjusting the amounts of the polyol monomer, the polybasic acid monomer, TMA and MDA, hydroxyl-terminated polyester-imine polyols with different hydroxyl values and TMA and MDA contents can be obtained. In the preparation of the hydroxyl-terminated polyester-imine polyol, the mass ratio of TMA and MDA is controlled at 1.94:1. The imide ring structure formed by TMA and MDA has good high-temperature resistance, and the content of TMA and MDA in the chain segment is the dominant factor affecting the high-temperature resistance of the subsequently prepared polyurethane toughener. The higher the content of TMA and MDA, the better the high-temperature resistance. However, when the content of TMA and MDA is too high, the polyester-imine structure formed will rapidly reduce the flexibility. In order to improve the high-temperature resistance while ensuring good flexibility, the content of TMA and MDA should be within an appropriate range.

[0042] In addition, from the above table, by adjusting the types of the polyol monomer and the polybasic acid monomer, hydroxyl-terminated polyester-imine polyols with different structures can be obtained. The ratio and type of the polyol monomer and the polybasic acid monomer are the dominant factors and effective control means affecting the mechanical properties of the subsequently prepared polyurethane toughener. In the present application, butyl titanate and zinc acetate can be used as catalysts for the preparation of the hydroxyl-terminated polyester-imine polyol. Subsequently, only Example 1 is a typical preparation of the capped polyurethane toughener.

[0043] Performance test

[0044] The capped polyurethane toughener prepared in each example and comparative example was taken as the detection object, and then mixed with epoxy resin, curing agent and accelerator to obtain a test sample-epoxy resin cured product. The tensile strength, elongation at break and impact toughness of the epoxy resin cured product before and after high temperature treatment at 200℃ were tested. The preparation steps of the test sample and the specific detection conditions are as follows:

[0045] Test sample preparation

[0046] The capped polyurethane toughener and the epoxy resin were first heated to 80℃ and stirred uniformly, then cooled to 40℃, and then the curing agent and the accelerator were added in sequence. The mixture was ground in a three-roll grinder to obtain a uniformly mixed material. After ultrasonic vibration treatment, a prepolymer was obtained. The prepolymer was cast in a mold, the temperature was raised to 120℃ for curing for 2h, and then the temperature was further raised to 150℃ for curing for 3h. The epoxy resin cured product was obtained. The selection and amount of each component are as follows:

[0047]

[0048] Detection conditions

[0049] Tensile strength, elongation at break test method: sample preparation was carried out according to the method described in GB / T 2567-2008, and tensile test was carried out at room temperature 23±2℃, and the load applied on the sample and the elongation of the sample were measured respectively, and then the tensile strength and elongation at break of the sample were calculated.

[0050] Impact toughness test method: sample preparation was carried out according to the method described in GB / T 2567-2008, and impact test was carried out at room temperature 23±2℃ using a simply supported beam impact instrument, and the impact strength of the sample was measured respectively, and the toughness and strength of the composition were characterized, and the above tests were carried out 3 times in parallel for each group, and the average value was taken as the final determination value.

[0051] Example 1

[0052] A capped high-temperature-resistant polyurethane toughening agent was prepared by the following preparation process:

[0053] 1) In a reaction kettle, 74.38 g of the hydroxyl-terminated polyester-imine polyol in Preparation Example 1 was dehydrated at 100℃ under vacuum (negative pressure 0.1 MPa) for 1 hour with minimum stirring;

[0054] 2) After cooling to 40℃, 16.77 g of IPDI and 0.015 g of DBTL were added, and the reaction was carried out at 70℃ with stirring for 2 hours under nitrogen atmosphere to obtain an isocyanate-terminated polymer;

[0055] 3) When the NCO content in the polymer was 3.47%, 1.36 g of 1,4-butanediol was added to the isocyanate-terminated polymer obtained in 2) under nitrogen atmosphere, and the reaction was carried out at 70℃ with moderate stirring for 1 hour;

[0056] 4) When the NCO content in the polymer was 2.05%, 6.80 g of p-tert-butylphenol and 0.015 g of catalyst were continuously added, and the reaction was carried out at 90℃ with vigorous stirring for 3 hours, and 0.66 g of blocking agent was added, and the reaction was continued for 2h to obtain a blocked polymer, and to complete the blocking of isocyanate, the polymer was placed in a 70℃ oven overnight, and the NCO content of the final product was less than 0.1%.

[0057] Comparative Example 1

[0058] A polyurethane type epoxy resin toughening agent was prepared by the following preparation process:

[0059] 1) 74.38 g of Terathane 2000 polytetramethylene ether glycol was put into a reaction kettle, and dehydrated at 100℃ under vacuum (negative pressure 0.1 MPa) for 1 hour with minimum stirring;

[0060] 2) After cooling to 40 °C, 16.77 g of IPDI and 0.015 g of DBTL were added, and the reaction was carried out at 70 °C under a nitrogen atmosphere with stirring for 2 hours to obtain an isocyanate-terminated polymer;

[0061] 3) When the NCO content of the polymer was 3.42%, 1.36 g of 1,4-butanediol was added to the isocyanate-terminated polymer obtained in 2) under a nitrogen atmosphere, and the reaction was carried out at 70 °C with moderate stirring for 1 hour;

[0062] 4) When the NCO content of the polymer was 2.02%, 6.80 g of p-tert-butylphenol and 0.015 g of DBTL were further added, and the reaction was carried out at 90 °C with more vigorous stirring for 3 hours, 0.66 g of p-tert-butylphenol was added, and the reaction was further carried out for 2 hours, thereby obtaining a blocked polymer. To complete the blocking of the isocyanate, the polymer was placed in an oven at 70 °C overnight, and the NCO content of the final product was less than 0.1%.

[0063] The toughening agent in Example 1 and Comparative Example 1 above was extracted, and the epoxy resin cured product was prepared according to the above steps and conditions. The tensile strength, elongation at break, and impact toughness of the cured product before and after high temperature treatment at 200 °C were tested, and each group was tested in triplicate. The test results were averaged and recorded in the table below.

[0064] Table: Performance comparison table of Example 1 and Comparative Example 1

[0065] As can be seen from the above table, the blocked high-temperature-resistant polyurethane toughening agent obtained in Example 1 has a tensile strength of 85.1 MPa, an elongation at break of 10.2%, and an impact toughness of 40.7 KJ / m 2 ;

[0066] Compared with Comparative Example 1 and the blank group, the tensile strength changes by +8.68% and +2.04%, respectively, the elongation at break changes by -32.89% and +126.67%, respectively, and the impact toughness increases by 25.62% and 78.51%, respectively. It can be seen that the obtained blocked high-temperature-resistant polyurethane is extremely suitable for use as a toughening agent.

[0067] As can be seen from the above table, the epoxy resin composition obtained from the blocked high-temperature-resistant polyurethane toughening agent in Example 1 has a tensile strength of 77.0 MPa after high temperature aging, which is only 9.52% lower than before high temperature aging, an elongation at break of 8.2%, which is 19.61% lower than before high temperature aging, and an impact toughness of 33.2 KJ / m 2 , which is only 18.43% lower than before high temperature aging.

[0068] From the data of Comparative Example 1 and the blank group, it can be seen that the tensile strength after high temperature aging is decreased by 32.82% and 20.86% respectively, the elongation at break is decreased by 55.92% and 33.33% respectively, and the impact toughness is decreased by 67.28% and 39.91% respectively, compared with that before high temperature aging. It can be seen that the attenuation of tensile strength, elongation at break and impact toughness of the epoxy resin composition using only the capped high-temperature-resistant polyurethane toughening agent in the application is much smaller than that of Comparative Example 1 blank group.

[0069] Based on the above data, the theoretical basis and reasons are as follows:

[0070] 1) The hydroxyl-terminated polyester-imine polyol synthesized by the one-step method of polyol monomer, polybasic acid monomer, TMA and MDA in the application mainly gives the system more excellent high-temperature resistance and flexibility through its special TMA and MDA ratio;

[0071] 2) The capped high-temperature-resistant polyurethane toughening agent synthesized by the hydroxyl-terminated polyester-imine polyol in the application as the main raw material improves the chain length of the capped polyurethane through the structure-activity relationship of isocyanate group and polyester-imine polyol, so that it can give the epoxy resin excellent high strength and high-temperature-resistant toughness without damaging the modulus of the epoxy resin matrix, thereby meeting the application in the present stage of highly integrated circuit board packaging adhesive.

[0072] In addition, it should be particularly pointed out that: the capped high-temperature-resistant polyurethane toughening agent can also be prepared from the hydroxyl-terminated polyester-imine polyols of other groups in Preparation Example 2-10, but considering that its performance is related to the type, hydroxyl value, [OH] / [COOH] ratio, content of TMA and MDA of the polyol and polybasic acid, and it is expected by those skilled in the art, therefore, only Preparation Example 1 is taken as an example, which should not be regarded as not supported in the specification.

[0073] As for IPDI, DBTL, 1,4-butanediol, p-tert-butylphenol, other similar additives can also be replaced, in fact, any similar additive can be replaced by those skilled in the art as needed, but considering that the addition effect can be expected by those skilled in the art under the premise of unchanged reaction principle, the present application is better to control a single variable, therefore, no one-by-one test is carried out, which should not be regarded as a limitation on the protection scope of the present application.

[0074] Example 1 (B-C)

[0075] In addition, in order to verify that the capped high-temperature-resistant polyurethane toughening agent obtained in Example 1 is applicable to most epoxy resin matrices, and can give them excellent high strength and high-temperature-resistant toughness, thereby meeting the application in the present stage of highly integrated circuit board packaging adhesive;

[0076] Still taking the capped high-temperature-resistant polyurethane toughening agent in Example 1 as the test object, only the selection of the epoxy resin in the preparation of the test sample was replaced, and was divided into B, C, blank B, and blank C four groups. The specific raw material usage is shown in the following table:

[0077] Table: Test sample preparation raw material selection

[0078] Then the tensile strength, elongation at break, and impact toughness of the corresponding epoxy resin cured product before and after high temperature treatment at 200°C were tested again. Each group was tested in triplicate, and the average value was recorded in the following table:

[0079] Table: Performance comparison table in Example 1-(B-C)

[0080] As can be seen from the above table, the capped high-temperature-resistant polyurethane toughening agent obtained in Example 1 can still impart excellent high strength and high-temperature toughness to the epoxy resin matrix when the epoxy resin compositions B and C are prepared according to the above method.

[0081] As can be seen from the above table, the tensile strength of Example 1-B changed by +2.44%, the elongation at break increased by +97.37%, and the impact toughness increased by +76% compared with the blank control group B. It can be seen that the obtained capped high-temperature-resistant polyurethane is extremely suitable as a toughening agent, and is also suitable for glycidyl amine type epoxy resins (such as AG80 in the example).

[0082] The tensile strength of the epoxy resin composition B obtained from the capped high-temperature-resistant polyurethane toughening agent in Example 1 was 92.3 MPa before high-temperature aging, the elongation at break was 7.5%, and the impact toughness was 30.8 KJ / m 2 ; the tensile strength was 89.0 MPa after high-temperature aging, which decreased by only 3.58% compared with before high-temperature aging, the elongation at break was 6.5%, which decreased by 13.33% compared with before high-temperature aging, and the impact toughness was 27.4 KJ / m 2 , which decreased by only 11.04% compared with before high-temperature aging.

[0083] As can be seen from the above table, the tensile strength of Example 1-C changed by only +1.66%, the elongation at break increased by +124.07%, and the impact toughness increased by +58.16% compared with the blank control group C. It can be seen that the obtained capped high-temperature-resistant polyurethane is extremely suitable as a toughening agent, and is also suitable for silicone-modified epoxy resins (such as ES-3201S in the example).

[0084] It can also be known from the above table that the tensile strength of the epoxy resin composition C obtained by using the capped high-temperature-resistant polyurethane toughening agent in Example 1 before high-temperature aging is 85.5 MPa, the elongation at break is 12.1%, and the impact toughness is 44.6 KJ / m 2 ; the tensile strength after high-temperature aging is 79.0 MPa, which only decreases by 7.60% compared with that before high-temperature aging, the elongation at break is 10.4%, which decreases by 14.05% compared with that before high-temperature aging, and the impact toughness is 35.6 KJ / m 2 , which only decreases by 20.18% compared with that before high-temperature aging.

[0085] Comprehensive data before and after high-temperature aging of Example 1-B, Example 1-C, blank control group B and blank control group C, it can be known that the capped high-temperature-resistant polyurethane toughening agent obtained in the application has good applicability in the epoxy resin curing system, can give the epoxy resin cured product excellent high strength and high-temperature-resistant toughness, and can meet the application in the present stage of highly integrated circuit board packaging glue.

[0086] This specific preparation example is only an explanation of the application, and is not a limitation of the application. Those skilled in the art can make modifications to the preparation example without creative contribution after reading the specification, but as long as it is within the scope of the claims of the application, it is protected by the patent law.

Claims

1. A hydroxyl-terminated polyesterimine polyol, characterized in that, The structure is as follows: Formula (I); The structural formula of R is: .

2. A method for synthesizing the hydroxyl-terminated polyesterimine polyol as described in claim 1, characterized in that, The hydroxyl-terminated polyesterimine polyol is polymerized from polyol monomers, polyacid monomers, trimellitic anhydride (TMA), and methylene diphenyl diamine (MDA).

3. The method for synthesizing hydroxyl-terminated polyesterimine polyols according to claim 2, characterized in that, Includes the following steps: Add polyol monomers, polyacid monomers, catalysts, TMA and MDA at room temperature, and raise the temperature to 200-220℃ during the feeding process, while controlling the column top temperature at 80-105℃. Then, evacuate the vacuum and gradually increase the vacuum degree to evaporate the reaction byproducts under reduced pressure. Keep the temperature for 1-3 hours to obtain the final product.

4. The method for synthesizing hydroxyl-terminated polyesterimine polyols according to claim 3, characterized in that, The feed ratio of the polyol monomer, polyacid monomer, catalyst, TMA and MDA is (30-70):(3-35):(0.07-0.15):(10-30):(5-15).

5. The method for synthesizing hydroxyl-terminated polyesterimine polyols according to claim 3, characterized in that, The polyol monomers are selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol / neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,8-octanediol, 2 One or more of the following: 4-diethyl-1,3-octanediol, trimethyl-1,6-hexanediol, 1,7-heptanediol, 4-propyl-1,8-octanediol, 1,9-nonanediol, polyoxypropylene polyols with a molecular weight of 200-2000, neopentyl glycol mono(hydroxyneopentyl ester), 2-ethyl-1,3-propanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 1,1-cyclohexanediethanol, 1,2-cyclohexanediethanol, 1,4-cyclohexanediethanol, trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, and glycerol.

6. The method for synthesizing hydroxyl-terminated polyesterimine polyols according to claim 3, characterized in that, The polyacid monomer is selected from one or more of succinic acid, sebacic acid, adipic acid, glutaric acid, pimelic acid, octanoic acid, azelaic acid, maleic anhydride, dodecanoic acid, maleic acid, maleic acid, maleic acid, maleic acid, trans-butenedioic acid, hydroxysuccinic acid, and dimer acids.

7. The method for synthesizing hydroxyl-terminated polyesterimine polyols according to claim 3, characterized in that, The catalyst is selected from one or a mixture of two of tetrabutyl titanate and zinc acetate.

8. The application of the hydroxyl-terminated polyesterimine polyol of claim 1 or the polyol obtained by any of the preparation methods of claims 2-7 in the preparation of polyurethane toughening agents, polyurethane elastomers, polyurethane coatings and other polyurethane materials, high-performance insulating materials, and photoresist raw materials.

9. A capped high-temperature resistant polyurethane toughening agent, characterized in that, The raw materials for preparation include the hydroxyl-terminated polyesterimide polyol of claim 1 or the hydroxyl-terminated polyesterimide polyol obtained by any of the preparation methods in claims 2-7.

10. A capped high-temperature resistant polyurethane toughening agent, characterized in that, It is prepared by reacting the hydroxyl-terminated polyesterimine polyol of claim 1 or the hydroxyl-terminated polyesterimine polyol obtained by any of the preparation methods in claims 2-7 with polyisocyanate, chain extender and blocking agent.

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