Polyether ester polymer as well as preparation method and application thereof in sealant

Abstract

The invention belongs to the technical field of adhesives, and particularly relates to a polyether ester polymer as well as a preparation method and application thereof in sealants. The number average molecular weight of the polyether ester polymer is 6000 to 30000; the preparation method comprises the following steps: S1, mixing polyether polyol and itaconic acid, and carrying out esterification reaction to prepare a polyether ester polymer containing double bonds; s2, the polyether ester polymer containing the double bonds reacts with alkoxy silane, so that the double bonds are terminated, and the polyether ester polymer is prepared. The polyether ester polymer disclosed by the invention can be applied to the field of adhesives, the prepared sealant has excellent mechanical properties and high temperature resistance, meanwhile, the production process is safe and environment-friendly, and the polyether ester polymer has industrial feasibility.

Description

Technical Field

[0001] The invention belongs to the technical field of adhesives, and in particular relates to a polyether ester polymer, a preparation method thereof and application of the same in sealants. Background Art

[0002] At present, the consumption of adhesives in my country has reached 7 million tons, most of which are silicone sealants. However, with the increasing awareness of environmental protection, environmentally friendly adhesives represented by MS adhesives have gradually emerged. According to statistics from the China Adhesives and Adhesive Tapes Industry Association, in 2020, my country's silane-modified (MS) adhesives achieved a high growth rate of nearly 40%. The MS adhesive industry has truly entered a period of explosive growth, and the industry prospects are bright.

[0003] MS glue has the performance advantages of both silicone sealants and polyurethane sealants, and does not contain formaldehyde and isocyanate. It has outstanding environmental protection characteristics such as no solvent, non-toxic and odorless, and low VOC release. It is widely used in the construction and home improvement industries and industrial fields. However, because the main structure of its cured product is a polyether structure, conventional silane-modified polyether has poor temperature resistance, and chain segment cleavage will occur under high temperature and high humidity conditions. When MS glue is used in outdoor equipment, it is very easy to crack and debond, which will greatly shorten the service life of outdoor equipment. In addition, the MS resin used in MS glue has a long process in the preparation process, which involves a double bond end-capping step and uses allyl chloride with a strong odor, and produces a large amount of hazardous waste.

[0004] In view of this, it is worthwhile to continue to develop sealants that can ensure the safety and environmental protection of the production process, have industrial feasibility and are resistant to high temperatures. Summary of the invention

[0005] The purpose of the present invention is to provide a polyether ester polymer and a preparation method thereof and application in sealants in response to some technical problems existing in the existing adhesive preparation process. By selecting a polyether ester polymer containing an ester bond and having curing properties, it can be applied to the adhesive field and the prepared sealant can have excellent mechanical properties and high temperature resistance, while ensuring that the production process is safe, environmentally friendly and has industrial feasibility.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] In a first aspect, a polyetherester polymer is provided, wherein the number average molecular weight of the polyetherester polymer is 6000-30000 (e.g., 6500, 7000, 8000, 10000, 12000, 14000, 15000, 16000, 20000, 25000, 28000), preferably 10000-18000.

[0008] According to the polyether ester polymer provided by the present invention, in some embodiments, the chemical structural formula of the polyether ester polymer is as shown below:

[0009]

[0010] In the formula,

[0011] R is a structure in which a hydroxyl group is removed from water or a small molecule alcohol, wherein the small molecule alcohol is selected from one or more of glycerol, trimethylolpropane, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, pentaerythritol and sorbitol;

[0012] R' is independently an alkyl group or an alkoxy group (for example, R' connected to an oxygen atom can be a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group; R' not connected to an oxygen atom can be a methoxy group, an ethoxy group, or a propoxy group), a+b=2, wherein a is 0 or 1;

[0013] The range of values ​​of x and y depends on the molecular weight of the polyether polyol used in the polyether ester polymer; R +44x+58y indicates the molecular weight of polyether polyol, 1000≤M R +44x+58y≤6000, where M R represents the molecular weight of the small molecule alcohol;

[0014] The value range of n depends on the number average molecular weight of the polyether ester polymer; (n+1)*[M R +44x+58y]+n*130.1-2n*18+n*M SiOR’ represents the number average molecular weight of the polyether ester polymer, 6000≤(n+1)*[M R +44x+58y]+n*130.1-2n*18+n*M SiOR’ ≤30000,M SiOR’ It represents the molecular weight of alkoxysilane.

[0015] In a second aspect, a method for preparing a polyetherester polymer is provided, comprising the steps of:

[0016] S1: mixing polyether polyol and itaconic acid to carry out esterification reaction to prepare polyether ester containing double bonds;

[0017] S2: reacting the polyether ester containing double bonds with alkoxysilane to cap the double bonds, thereby obtaining the polyether ester polymer;

[0018] in,

[0019] The molecular weight of the polyether polyol is 1000-6000 (for example, 1200, 1400, 1500, 1600, 1800, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500), the initiator used in the polyether polyol is a small molecule alcohol and / or water, preferably selected from one or more of water, glycerol, trimethylolpropane, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, pentaerythritol and sorbitol; the epoxy compound used in the polyether polyol is a C2-C5 epoxy compound, preferably selected from one or more of ethylene oxide, propylene oxide and butylene oxide.

[0020] In some embodiments, the catalyst used in the polyether polyol is a basic catalyst, preferably one or more selected from KOH, NaOH, DMC catalyst system and phosphazene catalyst.

[0021] According to the preparation method provided by the present invention, the ratio range of polyether polyol and itaconic acid can be determined according to the molecular weight of the desired polyether ester polymer, for example, it can be adjusted according to the type of polyether polyol selected and the molecular weight of the finally obtained polyether ester polymer.

[0022] According to the preparation method provided by the present invention, the ratio range of the polyether ester polymer containing double bonds and the alkoxysilane can be determined according to the end-capping rate of the alkoxysilane in the finally obtained polyether ester polymer.

[0023] According to the preparation method provided by the present invention, the number average molecular weight of the obtained polyether ester polymer is 6000-30000 (for example, 6500, 7000, 8000, 10000, 12000, 14000, 15000, 16000, 20000, 25000, 28000), preferably 10000-18000.

[0024] According to the preparation method provided by the present invention, in some embodiments, the reaction in step S1 includes a normal pressure esterification reaction stage and a negative pressure esterification reaction stage.

[0025] In some embodiments, the process conditions of the atmospheric pressure esterification reaction stage include: the reaction temperature is 120-200°C (for example, 130°C, 140°C, 150°C, 160°C, 185°C, 195°C), preferably 150-180°C; the reaction time is 2-8h (for example, 2.5h, 3h, 4.5h, 5h, 6h, 7.5h), preferably 4-7h.

[0026] In some embodiments, the process conditions of the negative pressure esterification reaction stage include: reaction temperature of 150-210°C (for example, 155°C, 160°C, 175°C, 180°C, 195°C, 205°C), preferably 170-200°C; reaction time of 2-8h (for example, 2.5h, 3h, 4.5h, 5h, 6h, 7.5h), preferably 4-7h; negative pressure of 2-40KPaA (for example, 2.5KPaA, 3KPaA, 4KPaA, 6KPaA, 8KPaA, 10KPaA, 12KPaA, 16KPaA, 18KPaA, 20KPaA, 25KPaA, 30KPaA, 35KPaA), preferably 5-15KPaA.

[0027] In some embodiments, the catalyst used in the negative pressure esterification reaction stage is a titanium catalyst, preferably selected from tetrabutyl titanate and tetraisopropyl titanate. The amount of the catalyst can be 2 to 20 ppm (for example, 3 ppm, 4 ppm, 6 ppm, 8 ppm, 12 ppm, 14 ppm, 15 ppm, 18 ppm) of the total mass of the reactants in the system.

[0028] According to the preparation method provided by the present invention, the chemical structure of the polyether ester containing double bonds obtained in step S1 can be represented by the following general formula:

[0029]

[0030] In the formula,

[0031] R is a structure in which the hydroxyl group is removed from water or a small molecule polyol;

[0032] The range of values ​​of x and y depends on the molecular weight of the polyether polyol used; R +44x+58y indicates the molecular weight of polyether polyol, 1000≤M R +44x+58y≤6000, where M R represents the molecular weight of the small molecule polyol;

[0033] The value range of n depends on the molecular weight of the polyether ester containing double bonds or the molecular weight of the final product polyether ester polymer.

[0034] According to the preparation method provided by the present invention, in some embodiments, the alkoxysilane is selected from one or more of methyldimethoxysilane, methyldiethoxysilane, trimethoxysilane and triethoxysilane; in the polyether ester polymer, the end-capping rate of alkoxysilane is 50-95% (for example, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%).

[0035] According to the preparation method provided by the present invention, in some embodiments, the reaction in step S2 is carried out under the action of a platinum catalyst;

[0036] In some embodiments, the platinum catalyst is selected from a Custer catalyst and / or a chloroplatinic acid catalyst;

[0037] In some embodiments, the amount of the platinum catalyst used is 2 to 20 ppm (e.g., 3 ppm, 4 ppm, 6 ppm, 8 ppm, 12 ppm, 14 ppm, 15 ppm, 18 ppm), preferably 5 to 10 ppm, of the total mass of the reactants in step S2, wherein the amount of the platinum catalyst used is measured by mass of Pt.

[0038] In some embodiments, the reaction process conditions of step S2 include: the reaction temperature is 50-120°C (for example, 55°C, 65°C, 70°C, 80°C, 90°C, 105°C, 115°C), preferably 60-100°C; the reaction time is 0.5-5h (for example, 1h, 1.5h, 2.5h, 3h, 3.5h, 4.5h), preferably 2-4h.

[0039] According to the preparation method provided by the present invention, the number average molecular weight of the polyether ester polymer finally obtained is 6000-30000, preferably 10000-18000.

[0040] In a third aspect, there is provided a use of the polyether ester polymer as described above or the polyether ester polymer prepared by the preparation method as described above in the preparation of a sealant.

[0041] The specific operation steps and process conditions for using the polyetherester polymer in preparing the sealant can be conventionally selected in the art and are not limited here.

[0042] In a fourth aspect, a sealant composition is provided, comprising: a component A and a component B;

[0043] The A component comprises the polyether ester polymer as described above or the polyether ester polymer prepared by the preparation method as described above; the B component comprises a catalyst, which is an organic tin compound, preferably selected from one or more of dibutyltin dilaurate, dioctyltin diacetate, stannous octoate and diorganotin bis(β-diketonate), more preferably stannous octoate.

[0044] According to the sealant composition provided by the present invention, in some embodiments, the component A further comprises one or more of a first plasticizer, nano-calcium carbonate, a thixotropic agent, an ultraviolet absorber and an antioxidant.

[0045] The first plasticizer may be diisononyl phthalate.

[0046] The thixotropic agent may be polyamide wax.

[0047] The ultraviolet absorber may be Tinuvin326.

[0048] The antioxidant may be Irganox1076.

[0049] In some embodiments, the B component further includes one or more of a second plasticizer, nano calcium carbonate and heavy calcium carbonate.

[0050] The second plasticizer may be PPG 3000.

[0051] According to the sealant composition provided by the present invention, in some embodiments, in the component A, the weight proportions of the various raw materials are as follows:

[0052] Polyether ester polymer, 100 parts,

[0053] The first plasticizer, 40-60 parts (e.g., 45 parts, 50 parts, 55 parts),

[0054] Nano calcium carbonate, 60-100 parts (e.g., 70 parts, 80 parts, 90 parts),

[0055] Thixotropic agent, 5-15 parts (e.g., 6 parts, 10 parts, 14 parts),

[0056] UV absorber, 0.5-2 parts (e.g., 1 part, 1.5 parts),

[0057] Antioxidant, 0.5-2 parts (e.g., 1 part, 1.5 parts);

[0058] In the B component, the weight parts of each raw material are as follows:

[0059] Second plasticizer, 100 parts,

[0060] Nano calcium carbonate, 40-60 parts (e.g., 45 parts, 50 parts, 55 parts),

[0061] Heavy calcium, 80-120 parts (e.g., 90 parts, 100 parts, 110 parts),

[0062] Catalyst, 30-50 parts (eg, 35 parts, 40 parts, 45 parts).

[0063] Herein, the operation and process conditions for dispersing and mixing the raw materials in component A may be conventional operations in the art; and the operation and process conditions for dispersing and mixing the raw materials in component B may be conventional operations in the art; no further details will be given here.

[0064] In a fifth aspect, a sealant is provided, which is formed by the sealant composition as described above. Herein, the operation of curing the sealant composition to form the sealant may be a conventional choice in the art, and will not be described in detail here.

[0065] The polyether ester polymer of the present invention contains ester bonds and has curing properties. When used to prepare sealant, the cured sealant can have high temperature resistance.

[0066] The preparation method of the polyether ester polymer of the present invention cleverly utilizes the esterification reaction of itaconic acid and polyether polyol to introduce double bond groups into polymer segments, and the double bond groups in the polymer segments can be subjected to hydrosilylation with hydrogen-containing alkoxysilane again, and alkoxy groups with curing properties are introduced, so that the polymer is endowed with bonding properties and high temperature resistance at the same time, and the application of the method in the adhesive field can improve the mechanical properties and high temperature resistance of the sealant. In addition, the preparation method of the polyether ester polymer only involves two-step reactions, and the reaction conditions are relatively mild, the production process is safe and environmentally friendly, and it has industrial feasibility. DETAILED DESCRIPTION

[0067] In order to understand the technical features and content of the present invention in detail, the preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are described in the embodiments, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments described herein. For those who do not specify specific conditions in the embodiments, they are carried out according to normal conditions or the conditions recommended by the manufacturer.

[0068] The test methods involved are as follows:

[0069] 1. Number average molecular weight of polyetherester polymer

[0070] The number average molecular weight was measured by gel permeation chromatography (EC2000), wherein the chromatographic column used was ShodexGPC KF 802 (exclusion limit 5000, inner diameter 8 mm, length 300 mm); the mobile phase was tetrahydrofuran; and the detector was RT1230 differential refractometer.

[0071] 2. The end-capping rate of polyetherester polymers was measured by H-NMR spectroscopy.

[0072] 3. Mechanical properties of sealant

[0073] The mechanical properties of sealants are tested in accordance with GB / T 16776 "Silicone structural sealants for construction" and GB / T 14683 "Silicone and modified silicone building sealants".

[0074] 4. Heat resistance of sealant

[0075] The cured sealant was subjected to a heat treatment, and the treatment conditions included: a temperature of 120° C. and a time of 168 h; thereafter, the relevant mechanical property tests were performed according to the method described in the above point 3.

[0076] The sources of raw materials involved are as follows:

[0077] The polyether polyols used in the examples are all homemade products. According to the different types of catalysts, the preparation methods of the polyether polyols are as follows:

[0078] (1) Using DMC bimetallic catalyst process: After mixing the finished small molecule polyether with the DMC catalyst, the temperature is raised to 130-150°C, and a small amount of PO is first added to activate the catalyst; thereafter, PO is continuously added to react until the product reaches the target molecular weight, and after aging for 1 hour, the unreacted PO is removed to obtain the finished polyether polyol; the polyether polyol used in Examples 1-3 is prepared according to this method; wherein the finished small molecule polyether used is C2004 (i.e., propylene glycol is used as the initiator, and PO is used as the polymerization monomer to carry out homopolymerization reaction until the product molecular weight is 400).

[0079] (2) KOH catalyst process: small molecule polyols (such as glycerol, propylene glycol, sorbitol, etc.) are mixed with KOH and heated to dehydrate, and then PO or a mixture of PO / EO is slowly added to react until the product reaches the target molecular weight. After aging for 2 hours to remove unreacted PO and / or EO, ​​acid solution is added for neutralization and crystallization into salt, and then the catalyst is removed to obtain the finished polyether polyol. The polyether polyols used in Examples 4-6 are prepared according to this method.

[0080] The above two processes for preparing polyether polyols are well known in the industry. By referring to the above preparation process, polyether polyols with different molecular weights can be prepared according to demand.

[0081] Itaconic acid, silane, and platinum catalyst were all purchased from Aladdin. The remaining raw materials were commercially available unless otherwise specified.

[0082] Example 1

[0083] The preparation process of polyetherester polymer with curing characteristics is:

[0084] S1: Add 3950g of polyether polyol-I (propylene glycol as initiator, PO as monomer for homopolymerization, molecular weight of 6000) and 68g of itaconic acid into a 5L stainless steel polyester reactor, replace with nitrogen three times, heat to 80°C, start the esterification reaction at normal pressure, then raise the temperature to 200°C within 1h, and keep the temperature for 4h to complete the esterification reaction at normal pressure; then, add 20ppm of tetraisopropyl titanate, raise the material temperature to 210°C, control the vacuum degree of the system to 2KPaA, react for 7h to complete the esterification reaction at negative pressure, and obtain 4kg of polyether ester polymer containing double bonds;

[0085] S2: The polyether ester polymer containing double bonds obtained in step S1 is transferred to an addition reactor, and 8 ppm of Custer catalyst is added; the reaction temperature is controlled at 110°C, 63 g of trimethoxysilane is added, and the reaction is kept warm for 4 hours. After vacuum removal of unreacted silane monomers, the temperature is lowered to 60°C and the material is discharged to obtain a polyether ester polymer-I with a molecular weight of 30,000 and a silane termination rate of 95%.

[0086] Preparation of sealant

[0087] 100 parts by weight of the polyether ester polymer-I prepared above, 50 parts by weight of a plasticizer (diisononyl phthalate), 90 parts by weight of nano calcium carbonate, 10 parts by weight of a thixotropic agent (polyamide wax), 1.5 parts by weight of a UV absorber (Tinuvin 326), and 1.5 parts by weight of an antioxidant Irganox 1076 were added to a high-speed disperser for dispersion and mixing. A large amount of heat was generated during the dispersion process. The temperature was controlled at about 70° C. and the speed was 5000 rpm for high-speed dispersion for 1 hour to obtain component A.

[0088] 100 parts by mass of plasticizer PPG 3000, 50 parts by mass of nano calcium carbonate CCS 18, 100 parts by mass of heavy calcium GF 2240, and 40 parts by mass of stannous octoate were added to a high-speed disperser, dispersed and mixed, and dispersed at a high speed of 5000 rpm for 1 hour to obtain component B.

[0089] The component A and component B obtained above were uniformly mixed in a mass ratio of 10:1, and then cured at room temperature for 48 hours to obtain a sealant.

[0090] Example 2

[0091] The preparation process of polyetherester polymer with curing characteristics is:

[0092] S1: Add 3941g of polyether polyol-II (propylene glycol as initiator, PO as monomer for homopolymerization, molecular weight of 5000) and 81.2g of itaconic acid into a 5L stainless steel polyester reactor, replace with nitrogen three times, heat to 80°C, start the esterification reaction at normal pressure, then raise the temperature to 190°C within 1h, and keep the temperature for 6h to complete the esterification reaction at normal pressure; then, add 20ppm of tetraisopropyl titanate, raise the material temperature to 200°C, control the vacuum degree of the system to 5KPaA, react for 4h to complete the esterification reaction at negative pressure, and obtain 4kg of polyether ester polymer containing double bonds;

[0093] S2: The polyether ester polymer containing double bonds obtained in step S1 is transferred to an addition reactor, and 15 ppm of Custer catalyst is added; the reaction temperature is controlled at 120°C, 68 g of trimethoxysilane is added, and the reaction is kept warm for 2 hours. After vacuum removal of unreacted silane monomers, the temperature is lowered to 60°C and the material is discharged to obtain a polyether ester polymer-II with a molecular weight of 25,000 and a silane termination rate of 85%.

[0094] Preparation of sealant

[0095] The sealant was prepared by referring to the process of Example 1, except that polyether ester polymer-II was used instead of polyether ester polymer-I in Example 1.

[0096] Example 3

[0097] The preparation process of polyetherester polymer with curing characteristics is:

[0098] S1: Add 3929g of polyether polyol-I (propylene glycol as initiator, PO as monomer for homopolymerization, molecular weight of 4000) and 98.6g of itaconic acid into a 5L stainless steel polyester reactor, replace with nitrogen three times, heat to 80°C, start the esterification reaction at normal pressure, then raise the temperature to 120°C within 1h, and keep the temperature for 7h to complete the esterification reaction at normal pressure; then, add 20ppm of tetraisopropyl titanate, raise the material temperature to 150°C, control the vacuum degree of the system to 40KPaA, react for 6h to complete the esterification reaction at negative pressure, and obtain 4kg of polyether ester polymer containing double bonds;

[0099] S2: The polyether ester polymer containing double bonds obtained in step S1 is transferred to an addition reactor, and 5 ppm of Custer catalyst is added; the reaction temperature is controlled at 90°C, 98 g of triethoxysilane is added, and the reaction is kept warm for 5 hours. After vacuum removal of unreacted silane monomers, the temperature is lowered to 60°C and the material is discharged to obtain a polyether ester polymer-III with a molecular weight of 18,000 and a silane termination rate of 75%.

[0100] Preparation of sealant

[0101] The sealant was prepared by referring to the process of Example 1, except that polyether ester polymer-III was used instead of polyether ester polymer-I in Example 1.

[0102] Example 4

[0103] The preparation process of polyetherester polymer with curing characteristics is:

[0104] S1: 3903g of polyether polyol-III (glycerol is used as the initiator, PO / EO is used as the comonomer for copolymerization, the EO content is 15wt%, and the molecular weight is 3000) and 134.3g of itaconic acid are added to a 5L stainless steel polyester reactor. After nitrogen replacement three times, the temperature is raised to 80°C to start the atmospheric pressure stage esterification reaction, and then the temperature is raised to 180°C within 1 hour, and the temperature is kept for 2 hours to complete the atmospheric pressure stage esterification reaction; then, 20ppm of tetraisopropyl titanate is added, and the material temperature is raised to 200°C, the vacuum degree of the system is controlled to 3KPaA, and the negative pressure stage esterification reaction is completed after 2 hours of reaction, and 4kg of polyether ester polymer containing double bonds is obtained;

[0105] S2: The polyether ester polymer containing double bonds obtained in step S1 is transferred to an addition reactor, and 20 ppm of chloroplatinic acid is added; the reaction temperature is controlled at 50°C, 79 g of methyldimethoxysilane is added, and the reaction is kept warm for 4 hours. After the unreacted silane monomer is removed by vacuum, the material is discharged to obtain a polyether ester polymer-IV with a molecular weight of 15,000 and a silane capping rate of 65%.

[0106] Preparation of sealant

[0107] The sealant was prepared by referring to the process of Example 1, except that polyether ester polymer-IV was used instead of polyether ester polymer-I in Example 1.

[0108] Example 5

[0109] The preparation process of polyetherester polymer with curing characteristics is:

[0110] S1: Add 3840g of polyether polyol-V (propylene glycol as initiator, PO as monomer for homopolymerization, molecular weight of 2000) and 208.2g of itaconic acid into a 5L stainless steel polyester reactor, replace with nitrogen three times, heat to 80°C, start the esterification reaction at normal pressure, then raise the temperature to 190°C within 1h, and keep the temperature for 5h to complete the esterification reaction at normal pressure; then, add 20ppm of tetraisopropyl titanate, raise the material temperature to 200°C, control the vacuum degree of the system to 15KPaA, react for 6h to complete the esterification reaction at negative pressure, and obtain 4kg of polyether ester polymer containing double bonds;

[0111] S2: The polyether ester polymer containing double bonds obtained in step S1 is transferred to an addition reactor, and 8 ppm of chloroplatinic acid catalyst is added; the reaction temperature is controlled at 80°C, 127 g of methyldimethoxysilane is added, and the reaction is kept warm for 2 hours. After the unreacted silane monomer is removed by vacuum, the material is discharged to obtain a polyether ester polymer-V with a molecular weight of 13,000 and a silane termination rate of 72%.

[0112] Preparation of sealant

[0113] The sealant was prepared by referring to the process of Example 1, except that polyether ester polymer-V was used instead of polyether ester polymer-I in Example 1.

[0114] Example 6

[0115] The preparation process of polyetherester polymer with curing characteristics is:

[0116] S1: Add 3857g of polyether polyol-VI (ethylene glycol as initiator, PO / EO as comonomer for copolymerization, EO content of 35wt%, molecular weight of 2000) and 198g of itaconic acid into a 5L stainless steel polyester reactor, replace with nitrogen three times, heat to 80°C, start the esterification reaction at normal pressure, then raise the temperature to 150°C within 1h, and keep the temperature for 4h to complete the esterification reaction at normal pressure; then, add 20ppm of tetraisopropyl titanate, raise the material temperature to 160°C, control the vacuum degree of the system to 10KPaA, react for 7h to complete the esterification reaction at negative pressure, and obtain 4kg of polyether ester polymer containing double bonds;

[0117] S2: The polyether ester polymer containing double bonds obtained in step S1 is transferred to an addition reactor, and 2 ppm of Custer catalyst is added; the reaction temperature is controlled at 70°C, 105 g of methyldimethoxysilane is added, and the reaction is kept warm for 5 hours. After the unreacted silane monomer is removed by vacuum, the material is discharged to obtain a polyether ester polymer-VI with a molecular weight of 10,000 and a silane termination rate of 60%.

[0118] Preparation of sealant

[0119] The sealant was prepared by referring to the process of Example 1, except that polyether ester polymer-VI was used instead of polyether ester polymer-I in Example 1.

[0120] Example 7

[0121] The preparation process of polyetherester polymer with curing characteristics is:

[0122] S1: Add 3714g of polyether polyol-VII (sorbitol is used as an initiator, PO / EO is used as a comonomer for copolymerization, the EO content is 20%, and the molecular weight is 1000) and 395g of itaconic acid into a 5L stainless steel polyester reactor, replace the nitrogen three times, and heat it to 80°C to start the atmospheric pressure stage esterification reaction, then raise the temperature to 120°C within 1 hour, and keep the temperature for 8 hours to complete the atmospheric pressure stage esterification reaction; then, add 20ppm of tetraisopropyl titanate, and raise the material temperature to 180°C, control the vacuum degree of the system to 20KPaA, and react for 8 hours to complete the negative pressure stage esterification reaction, and obtain 4kg of polyether ester polymer containing double bonds;

[0123] S2: The polyether ester polymer containing double bonds obtained in step S1 is transferred to an addition reactor, and 12 ppm of chloroplatinic acid catalyst is added; the reaction temperature is controlled at 80°C, 224 g of methyldiethoxysilane is added, and the reaction is kept warm for 3 hours. After vacuum removal of unreacted silane monomers, the material is discharged to obtain a polyether ester polymer-VII with a molecular weight of 6000 and a silane termination rate of 50%.

[0124] Preparation of sealant

[0125] The sealant was prepared by referring to the process of Example 1, except that polyether ester polymer-VII was used instead of polyether ester polymer-I in Example 1.

[0126] Comparative Example 1

[0127] The preparation process of polyetherester polymer is:

[0128] S1: Add 3778g of polyether polyol-V (propylene glycol as initiator, PO as monomer for homopolymerization, molecular weight of 2000) and 231.3g of itaconic acid into a 5L stainless steel polyester reactor, replace with nitrogen three times, heat to 80°C, start the esterification reaction at normal pressure, then raise the temperature to 200°C within 1h, and keep the temperature for 7h to complete the esterification reaction at normal pressure; then, add 40ppm of tetraisopropyl titanate, raise the material temperature to 210°C, control the vacuum degree of the system to 10KPaA, react for 7h to complete the esterification reaction at negative pressure, and obtain 4kg of polyether ester polymer containing double bonds;

[0129] S2: The polyether ester polymer containing double bonds obtained in step S1 is transferred to an addition reactor, and 12 ppm of chloroplatinic acid catalyst is added; the reaction temperature is controlled at 100° C., 155 g of methyldimethoxysilane is added, and the reaction is kept warm for 5 hours. After vacuum removal of unreacted silane monomers, the material is discharged to obtain a polyether ester polymer-I' with a molecular weight of 36,000 and a silane termination rate of 72%.

[0130] Preparation of sealant

[0131] The sealant was prepared by referring to the process of Example 1, except that polyether ester polymer-I' was used to replace polyether ester polymer-I in Example 1.

[0132] Comparative Example 2

[0133] The preparation process of polyetherester polymer is:

[0134] S1: Add 3874g of polyether polyol-V (propylene glycol as initiator, PO as monomer for homopolymerization, molecular weight of 2000) and 126g of itaconic acid into a 5L stainless steel polyester reactor, replace with nitrogen three times, heat to 80°C, start the esterification reaction at normal pressure, then raise the temperature to 170°C within 1h, and keep the temperature for 5h to complete the esterification reaction at normal pressure; then, add 15ppm of tetraisopropyl titanate, raise the material temperature to 200°C, control the vacuum degree of the system to 15KPaA, react for 6h to complete the esterification reaction at negative pressure, and obtain 4kg of polyether ester polymer containing double bonds;

[0135] S2: The polyether ester polymer containing double bonds obtained in step S1 is transferred to an addition reactor, and 7 ppm of chloroplatinic acid catalyst is added; the reaction temperature is controlled at 90°C, 77 g of methyldimethoxysilane is added, and the reaction is kept warm for 3 hours. After vacuum removal of unreacted silane monomers, the material is discharged to obtain a polyether ester polymer-II' with a molecular weight of 4300 and a silane termination rate of 72%.

[0136] Preparation of sealant

[0137] The sealant was prepared by referring to the process of Example 1, except that polyether ester polymer-II' was used to replace polyether ester polymer-I in Example 1.

[0138] Comparative Example 3

[0139] Preparation of sealant

[0140] The sealant was prepared by referring to the process of Example 1, except that: Kashiwabara S203H (silane-modified polyether) was used to replace the polyether ester polymer-I in Example 1.

[0141] According to the aforementioned method, the sealants obtained from Examples 1 to 7 and Comparative Examples 1 to 3 were subjected to mechanical property tests and heat resistance tests. The results are shown in Tables 1 to 2.

[0142] Table 1 Mechanical properties test results of sealant

[0143] sample Tensile strength / MPa 100% modulus / MPa Elongation at break % Shaw A Example 1 0.67 0.23 467 18 Example 2 0.74 0.35 436 22 Example 3 1.58 0.88 412 33 Example 4 1.79 1.19 405 41 Example 5 1.88 1.22 385 44 Example 6 2.07 1.45 352 48 Example 7 2.86 1.83 245 57 Comparative Example 1 0.55 0.22 198 12 Comparative Example 2 3.53 2.56 189 63 Comparative Example 3 1.82 1.14 367 42

[0144] Table 2 Test results of heat resistance of sealant

[0145]

[0146]

[0147] According to the results in Table 1, the number average molecular weights of the polyether ester polymers in Examples 1 to 7 are 30000, 25000, 18000, 15000, 13000, 10000, and 6000, respectively. The mechanical properties of the sealant are related to the molecular weight of the polyether ester polymer. When the molecular weight of the polyether ester polymer is controlled within a suitable range, the mechanical properties of the corresponding sealant are close to those of the sealant prepared using S203H. Among them, the molecular weight of the polyether ester polymer in Example 5 is substantially the same as that of S203H in Comparative Example 3, and its performance is also closest to that of S203H. The mechanical properties of the sealants obtained in Example 5 are close to those obtained in Comparative Example 3, and the heat resistance of the sealant in Example 5 is better than that of Comparative Example 3; this shows that the sealant prepared by using the polyether ester polymer of the present invention can replace the sealant prepared by using S203H, but at the same time, it can also avoid the defect that the heat resistance of the obtained sealant is poor due to the ether bond in its molecular chain when using S203H. The polyether ester polymer structure selected by the present invention introduces ester bonds, which can effectively improve the long-term heat resistance of the sealant product. At the same time, it can also ensure that the reaction conditions are relatively mild, the production process is safe and environmentally friendly, and has industrial feasibility.

[0148] Although polyether ester polymer was also selected in Comparative Example 1-2, its molecular weight was not controlled within an appropriate range. Compared with Example 1-7, the mechanical properties of the sealant obtained in Comparative Example 1-2 decreased significantly after heat treatment, and the long-term heat resistance was poor.

[0149] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the spirit of the present invention.

Claims

1. A polyetherester polymer, characterized in that The number average molecular weight of the polyether ester polymer is 6,000 to 30,000, preferably 10,000 to 18,000.

2. The polyetherester polymer according to claim 1, characterized in that The chemical structural formula of the polyetherester polymer is shown below: In the formula, R is a structure in which a hydroxyl group is removed from water or a small molecule alcohol, wherein the small molecule alcohol is selected from one or more of glycerol, trimethylolpropane, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, pentaerythritol and sorbitol; R' is independently an alkyl group or an alkoxy group, a+b=2, wherein a is 0 or 1; The range of values ​​of x and y depends on the molecular weight of the polyether polyol used in the polyether ester polymer; R +44x+58y indicates the molecular weight of polyether polyol, 1000≤M R +44x+58y≤6000, where M R represents the molecular weight of the small molecule alcohol; The value range of n depends on the number average molecular weight of the polyether ester polymer; (n+1)*[M R +44x+58y]+n*130.1-2n*18+n*M SiOR’ represents the number average molecular weight of the polyether ester polymer, 6000≤(n+1)*[M R +44x+58y]+n*130.1-2n*18+n*M SiOR’ ≤30000,M SiOR’ It represents the molecular weight of alkoxysilane.

3. A method for preparing a polyetherester polymer, characterized in that: The steps include: S1: mixing polyether polyol and itaconic acid to carry out esterification reaction to prepare polyether ester containing double bonds; S2: reacting the polyether ester containing double bonds with alkoxysilane to cap the double bonds, thereby obtaining the polyether ester polymer; in, The molecular weight of the polyether polyol is 1000-6000, the initiator used in the polyether polyol is a small molecule alcohol and / or water, preferably selected from one or more of water, glycerol, trimethylolpropane, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, pentaerythritol and sorbitol; the epoxy compound used in the polyether polyol is a C2-C5 epoxy compound, preferably selected from one or more of ethylene oxide, propylene oxide and butylene oxide.

4. The preparation method according to claim 3, characterized in that: The reaction in step S1 includes a normal pressure esterification reaction stage and a negative pressure esterification reaction stage; The process conditions of the atmospheric pressure esterification reaction stage include: reaction temperature of 120-200° C., preferably 150-180° C.; reaction time of 2-8 hours, preferably 4-7 hours; The process conditions of the negative pressure esterification reaction stage include: reaction temperature of 150-210°C, preferably 170-200°C; reaction time of 2-8h, preferably 4-7h; negative pressure of 2-40KPaA, preferably 5-15KPaA; The catalyst used in the negative pressure esterification reaction stage is a titanium catalyst, preferably selected from tetrabutyl titanate and tetraisopropyl titanate.

5. The preparation method according to claim 3 or 4, characterized in that: The alkoxysilane is selected from one or more of methyldimethoxysilane, methyldiethoxysilane, trimethoxysilane and triethoxysilane; in the polyetherester polymer, the end-capping rate of the alkoxysilane is 50-95%.

6. The preparation method according to any one of claims 3 to 5, characterized in that: The reaction in step S2 is carried out under the action of a platinum catalyst; The platinum catalyst is selected from a Custer catalyst and / or a chloroplatinic acid catalyst; The amount of the platinum catalyst used is 2 to 20 ppm, preferably 5 to 10 ppm, of the total mass of the reactants in step S2, wherein the amount of the platinum catalyst used is based on the mass of Pt; The reaction process conditions of step S2 include: reaction temperature of 50 to 120° C., preferably 60 to 100° C.; reaction time of 0.5 to 5 h, preferably 2 to 4 h.

7. Use of the polyether ester polymer according to claim 1 or 2 or the polyether ester polymer prepared by the preparation method according to any one of claims 3 to 6 in the preparation of sealants.

8. A sealant composition, characterized in that: include: A component and B component; The A component comprises the polyether ester polymer according to claim 1 or 2 or the polyether ester polymer prepared by the preparation method according to any one of claims 3 to 6; the B component comprises a catalyst, and the catalyst is an organic tin compound, preferably selected from one or more of dibutyltin dilaurate, dioctyltin diacetate, stannous octoate and diorganotin bis(β-diketonate), more preferably stannous octoate.

9. The sealant composition according to claim 8, characterized in that: The component A further comprises one or more of a first plasticizer, nano calcium carbonate, a thixotropic agent, an ultraviolet absorber and an antioxidant; The B component further comprises one or more of a second plasticizer, nano calcium carbonate and heavy calcium carbonate.

10. The sealant composition according to claim 9, characterized in that: In the A component, the weight parts of each raw material are as follows: Polyether ester polymer, 100 parts, First plasticizer, 40-60 parts, Nano calcium carbonate, 60-100 parts, Thixotropic agent, 5-15 parts, UV absorber, 0.5-2 parts, Antioxidant, 0.5-2 parts; In the B component, the weight parts of each raw material are as follows: Second plasticizer, 100 parts, Nano calcium carbonate, 40-60 parts, Heavy calcium, 80-120 parts, Catalyst, 30-50 parts.

11. A sealant, characterized in that: It is formed by the sealant composition according to any one of claims 8 to 10.

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