Patent Description:
Since the <NUM>, with the modernization of urban construction and the emergence of higher requirements for building functions, the variety and quantity of high-performance sealants for sealing seams of building structures in China have been increasing. The first used in construction is polysulfide sealants, followed by acrylic sealants, silicone sealants and polyurethane sealants, and the development of sealants is rapid. Among the above-mentioned sealants, the silicone sealants are in the fastest development, have advantages of fast curing speed, high temperature resistance and excellent weather resistance, but also have disadvantages such as low strength and surface unpaintability. The polyurethane sealants have advantages of high strength, good oil and solvent resistance and good abrasion resistance, but have disadvantages of ease for foaming in the curing process, poor weather resistance and dependence on primers for adhesion. The development of the market has put forward the demand for sealants with comprehensive functions and better economy to effectively improve and enhance the adaptability and reliability of sealants.

The curing mechanism of reactive sealants is that an alkoxy-terminated group reacts with water in the air under the action of a catalyst to remove small molecular alcohol and the main chain is crosslinked to form a three-dimensional network structure, and thus the reactive sealants gain advantages of both silicone and polyurethane. In recent years, this type of reactive sealant has received more and more attention and has been widely applied in Europe and the United States. Because of its wide range of adhesion and adaptability to substrates, such a reactive sealant is used in various fields such as construction, automotive, rail transportation, container, equipment manufacturing and industry, which also indicates its broad application prospect.

The base polymer of end-capping reactive sealants is a siloxane-terminated polyether, which can be achieved mainly by the following methods.

<CIT> discloses a cold-setting resin composition, comprising a hydrolyzable silyl-modified substance of an end (meth)allyl group-containing polyoxyalkylene ether which is obtained by subjecting an alkylene oxide to addition polymerization to a (meth)allyl group-containing active hydrogen compound such as allyl alcohol by using cesium hydroxide as a catalyst and then bonding the resulting polymer with a bifunctional binder such as methylene dichloride, in which the polyoxyalkylene ether has >=<NUM>,<NUM> number-average molecular weight per end (meth)allyl group and <=<NUM> dispersion degree (Mw/Mn) of molecular weight.

<CIT> provides a curable composition improved in elongation and strength after curing and a cured product obtained by curing the curable composition. A curable composition containing reactive silicon group-containing polyoxyalkylene-based polymer (A) having more than <NUM> reactive silicon group on average at one terminal portion, and reactive silicon group-containing (meth)acrylate-based polymer (B) having not less than <NUM> reactive silicon group on average per one molecule, which is represented by the formula (<NUM>): -SiRX<NUM> (<NUM>); wherein R is a hydrocarbon group having <NUM>-<NUM> carbon atoms and optionally having substituent(s) which is/are a hetero atom-containing group or a halogen atom, and X is a hydroxyl group or a hydrolyzable group.

<CIT> provides a curable composition which has good curability and good tensile properties (high elongation), and contains a smaller amount of a dibutyltin compound which is regarded as toxic. The curable composition of the present invention comprises the following components (A) and (B) at a weight ratio of (A)/(B) of <NUM>/<NUM> to <NUM>/<NUM>, (A) a reactive silyl group-containing organic polymer having, as a silicon-containing group cross-linkable by siloxane bond formation, a group represented by the formula (<NUM>), and (B) a reactive silyl group-containing organic polymer having, as a silicon-containing group cross-linkable by siloxane bond formation, a moiety represented by the formula (<NUM>).

<CIT> discloses a curable composition, containing <NUM> pts. of a polyoxyalkylene polymer having a reactive silyl group with a number average molecular weight of higher than <NUM>,<NUM> and <NUM>,<NUM> or less, and <NUM>-<NUM> pts. of a polyoxyalkylene polymer having a reactive silyl group with a number average molecular weight of <NUM>,<NUM> or more and <NUM>,<NUM> or less.

<CIT> discloses a sealant composition that includes a reactive silyl group-containing organic polymer, and gives a cured product having a low modulus and not having wrinkles or cracks on the surface even though the sealant includes as a curing catalyst a tetravalent tin compound, which is presumed to reduce recovery. The sealant composition is a one-component curable sealant composition including: a linear organic polymer (A) having a number average molecular weight of <NUM>,<NUM> to <NUM>,<NUM>, and having an ethanol-elimination reactive silyl group at a molecular terminal; a tetravalent tin compound (B); and a plasticizer (C).

In view of deficiencies in the existing art, the object of the present disclosure is to provide a method for preparing a reactive sealant resin to better prepare a reactive sealant resin.

To achieve the object of the present disclosure, the present disclosure adopts the following technical solution.

A method for preparing a reactive sealant resin is provided. The invention as claimed is directed to a method for preparing a reactive sealant resin, comprising:.

In step (<NUM>) of the present disclosure, the hydroxyl-containing initiator, the alkali catalyst and the epoxy compound (also referred to as a polymerized monomer) used for preparing the first polyether polyol are all commonly used raw materials known in the art for preparing the polyether polyol. In step (<NUM>), the hydroxyl-containing initiator may be a small-molecule monohydric alcohol or a small-molecule polyol having a molecular weight of not greater than <NUM>, and, for example, may be one or more of methanol, ethanol, ethylene glycol, <NUM>,<NUM>-propylene glycol, <NUM>,<NUM>-propylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, mannitol, sucrose, glucose or xylitol, preferably <NUM>,<NUM>-propylene glycol and/or glycerol.

The alkali catalyst may be one or more of an alkali metal, an alkali metal hydride, an alkali metal hydroxide, an alkali metal alkoxide, a composite metal cyanide or a phosphazene catalyst, preferably a composite metal cyanide such as zinc hexacyanocobaltate. In the reaction system of step (<NUM>), the content of the alkali catalyst may be <NUM> ppm to <NUM> ppm, preferably <NUM> ppm to <NUM> ppm, more preferably <NUM> ppm to <NUM> ppm.

The epoxy compound may be one or more of ethylene oxide, propylene oxide, epoxy isobutane or tetrahydrofuran, preferably ethylene oxide and/or propylene oxide, more preferably propylene oxide or a mixture of ethylene oxide and propylene oxide in which the content of the ethylene oxide is not more than 15wt%.

In an embodiment, in step (<NUM>), the reaction temperature for preparing the polyether polyol is <NUM> to <NUM>, preferably <NUM> to <NUM>; the reaction pressure is <NUM> MPa to <NUM> MPa, for example, <NUM> MPa, <NUM> MPa or <NUM> MPa, preferably <NUM> MPa to <NUM> MPa.

According to the method of the present disclosure, preferably, the first polyether polyol has a molecular weight of <NUM>/mol to <NUM>/mol and a functionality of <NUM> to <NUM>; further preferably, the first polyether polyol has a molecular weight of <NUM>/mol to <NUM>/mol and a functionality of <NUM> to <NUM>.

The preparation of the polyether polyol is well known in the art. In the present disclosure, preferably, in step (<NUM>), the first polyether polyol is obtained by a n-stage polymerization, wherein n ≥ <NUM>, for example, <NUM>, <NUM>, <NUM> or <NUM>. In the present disclosure, "by a n-stage polymerization" means that after the polymerization of the previous stage is completed, a certain amount of epoxide is added to continue the polymerization of a new stage, and so on until the polymerization of n stages is completed. It is to be understood by those skilled in the art that the larger the target molecular weight of the final polyether, the larger n may be set. For example, when the target molecular weight of the final polyether is not less than <NUM>/mol, preferably n ≥ <NUM>. It has been found that compared with one-step polymerization, the staged polymerization can effectively reduce the molecular weight difference between the polyether polyol molecules in the target product, resulting in a polyether polyol having a narrow molecular weight distribution. The target molecular weights of each polymerization stage are sequentially set to M1,. At this point, the polymerization route can be expressed as hydroxyl-containing initiator-M1-. -Mn, wherein Mn is the target molecular weight of the final product of polyether polyol. For example, when n = <NUM>, the polymerization route can be expressed as hydroxyl-containing initiator-M1-M2-M3-M4-M5. Preferably, M1 ≤ <NUM>/mol, and Mi - M(i - <NUM>) ≤ <NUM>/mol, for example, <NUM>/mol, <NUM>/mol, <NUM>/mol, <NUM>/mol or <NUM>/mol, that is, the target molecular weights of the adjacent stages are not suitably set with an excessively large difference so that the molecular weight distribution of the final product of polyether polyol can be reduced, wherein i is an integer between <NUM> and n, for example, when n = <NUM>, i is <NUM> or <NUM> and when n = <NUM>, i is <NUM>, <NUM> or <NUM>, and M0 represents the molecular weight of the initiator. Further preferably, when Mi ≤ <NUM>/mol, for example, <NUM>/mol, <NUM>/mol, <NUM>/mol or <NUM>/mol, Mi - M(i - <NUM>) ≤ <NUM>/mol, for example, <NUM>/mol, <NUM>/mol or <NUM>/mol, that is, when the target molecular weight is not greater than <NUM>/mol, the target molecular weight at the previous stage should not be suitably set so as to differ from this target molecular weight by more than <NUM>/mol, which facilitates the reduction of the molecular weight distribution of the final product of polyether polyol.

For example, the synthesis of the polyether polyol is carried out by a staged polymerization process by using a small-molecule polyol as an initiator to prepare a product of polyether polyol having narrow molecular weight distribution, low viscosity and high molecular weight. The polymerization route is as follows: a difunctional alcohol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol; or a trifunctional alcohol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol; or a tetra- or penta- or hexa-functional alcohol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol.

In the present disclosure, in order to obtain a narrow-distribution and low-viscosity product, a staged polymerization process is used, and the molecular weight of the intermediate is controlled by controlling the addition amount of raw materials to achieve the above-mentioned polymerization route. Specifically, when the average molecular weight of the epoxy compound added at each stage is X and the molecular weight of the hydroxyl-containing initiator is Y (when the hydroxyl-containing initiator is a mixture, the molecular weight is calculated as an average molecular weight), the molar amount of the epoxy compound to be added at the ith stage is Z times the molar amount of the initiator, which satisfies the following relationship: Z = (Mi - M (i - <NUM>))/X, wherein i is an integer between <NUM> to n, and when i = <NUM>, M0 is Y.

In the present disclosure, the polyether polyol is modified by Williamson reaction to obtain a crude product of double-bond-terminated polyether. The alkoxidation reagent used in the above-mentioned modification treatment may be a mixture of one or more of an alkali metal, an alkali metal hydride, an alkali metal hydroxide or an alkali metal alkoxide, preferably one or more of an alkali metal sodium, sodium hydride or sodium methoxide. The polyether modified compound used is a halide containing a double bond, preferably allyl chloride or methallyl chloride.

In an embodiment, the molar ratio of the amount of the alkoxidation reagent to the hydroxyl equivalent of the polyether polyol (that is, the total molar amount of hydroxyl groups in the polyether polyol) is <NUM>:<NUM> to <NUM>:<NUM>, preferably <NUM>:<NUM> to <NUM>:<NUM>, for example, <NUM>:<NUM> or <NUM>:<NUM>; the molar ratio of the amount of the halide containing a double bond to the hydroxyl equivalent of the polyether polyol is <NUM>:<NUM> to <NUM>:<NUM>, preferably <NUM>:<NUM> to <NUM>:<NUM>, for example, <NUM>:<NUM> or <NUM>:<NUM>.

In an embodiment, the reaction temperature for modifying the polyether polyol to prepare the double-bond-terminated polyether is <NUM> to <NUM>, preferably <NUM> to <NUM>, for example, <NUM> or <NUM>; the reaction time is <NUM> hours to <NUM> hours, preferably <NUM> hours to <NUM> hours, for example, <NUM> hours, <NUM> hours or <NUM> hours.

The crude product of double-bond-terminated polyether obtained by modification needs to be further refined to remove impurities. During refining, the crude product is first neutralized by using a neutralizing agent, for example, to a pH of <NUM> to <NUM>, then water and an organic solvent are added, water (and dissolved salt) is separated by using a coalescing separator, and the organic solvent is further removed, for example, by distillation under reduced pressure using a usable device such as a thin-film evaporator, and finally, the product of modified polyether is obtained.

The neutralizing agent used may be one or more of hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or lactic acid, preferably acetic acid or lactic acid, and the amount of the neutralizing agent may be <NUM> wt% to <NUM> wt% of the amount of the crude product of polyether, preferably <NUM> wt% to <NUM> wt%, for example, <NUM> wt% or <NUM> wt%. The organic solvent is an alkane, a benzene compound or a nitrile compound, preferably n-hexane. The mass ratio of the organic solvent, water and crude product is (<NUM> to <NUM>) (for example, <NUM> or <NUM>):(<NUM> to <NUM>) (for example, <NUM>, <NUM> or <NUM>):<NUM>, preferably (<NUM> to <NUM>):(<NUM> to <NUM>):<NUM>.

In the present disclosure, the above-mentioned modified polyether and hydrogen-containing silane are subjected to a silane end-capping reaction under the action of a hydrosilylation catalyst (for example, Karstedt catalyst), and the end-capping reaction is commonly used for the preparation of reactive sealant resins. The hydrogen-containing silane may be one or more of trimethoxysilane, triethoxysilane, methyldimethoxysilane or methyldiethoxysilane, preferably methyldimethoxysilane and/or trimethoxysilane. In an embodiment, the molar ratio of the amount of the hydrogen-containing silane to the double bond equivalent of the modified polyether (that is, the total molar amount of double bond s in the modified polyether) is <NUM>:<NUM> to <NUM>:<NUM>, for example, <NUM>:<NUM> or <NUM>:<NUM>, preferably <NUM>:<NUM> to <NUM>:<NUM>; the reaction temperature is <NUM> to <NUM>, for example, <NUM> or <NUM>, preferably <NUM> to <NUM>; the reaction time is <NUM> hour to <NUM> hours, preferably <NUM> hours to <NUM> hours, for example, <NUM> hours.

According to the invention as claimed, the hydrosilylation catalyst is a supported metal platinum catalyst for catalyzing the hydrosilylation reaction, whose amount in the reaction system in step (<NUM>), based on the platinum content, is <NUM> ppm to <NUM> ppm, preferably <NUM> ppm to <NUM> ppm, for example, <NUM> ppm, <NUM> ppm or <NUM> ppm.

The supported metal platinum catalyst is obtained by subjecting a chloroplatinic acid solution to impregnation, reduction and drying with a polyurethane flexible foam as a carrier. The polyurethane flexible foam is prepared by subjecting a raw material including a second polyether polyol to a foaming reaction, wherein a polymerized monomer for preparing the second polyether polyol includes an epoxide containing a C=C double bond in the molecule, and the content of the epoxide in the polymerized monomer is <NUM> wt% to <NUM> wt%, preferably <NUM> wt% to <NUM> wt%, for example, <NUM> wt%. Preferably, the epoxide containing a C=C double bond is one or more of allyl glycidyl ether
<CHM>
, methallyl glycidyl ether, glycidyl acrylate or glycidyl methacrylate
<CHM>.

In an embodiment, the second polyether polyol is obtained by polymerizing the hydroxyl-containing initiator with the polymerized monomer including the epoxide containing a C=C double bond in the molecule under the action of an alkali catalyst. Preferably, the polymerized monomer consists of at least one of ethylene oxide or propylene oxide and the epoxide containing a C=C double bond in the molecule. Further preferably, during the addition of the polymerized monomer, the polymerized monomer last added does not contain the epoxide containing a C=C double bond in the molecule, for example, the epoxide containing a C=C double bond in the molecule is first added. The hydroxyl-containing initiator, the alkali catalyst, and the reaction conditions may be the same as those as described above. Preferably, the second polyether polyol has a molecular weight of <NUM>/mol to <NUM>/mol, for example, <NUM>/mol, <NUM>/mol, <NUM>/mol or <NUM>/mol, and a nominal functionality of <NUM> to <NUM>, preferably <NUM> to <NUM>, for example, <NUM> or <NUM>. The prepared second polyether polyol may be further refined to remove impurities. For example, the crude product of the prepared second polyether polyol (crude polyether) is neutralized, added with water, an adsorbent and a filter aid, and then filtered to obtain the refined second polyether polyol. In an embodiment, the neutralizing agent may be an aqueous solution of phosphoric acid, in which the amount of phosphoric acid is <NUM>% to <NUM>% of the total mass of the crude polyether and the amount of water is <NUM>% to <NUM>% of the total mass of the crude polyether. The adsorbent is magnesium silicate whose amount is <NUM>% to <NUM>% of the total mass of the crude polyether. The filter aid is diatomite whose amount is <NUM>% to <NUM>% of the total mass of the crude polyether.

The formulation and preparation method of the polyurethane flexible foam are well known to those skilled in the art, for which, for example, reference is made to the formulation and preparation method of the polyurethane flexible foam disclosed in the related documents such as <CIT>. In the embodiment, the polyurethane flexible foam may be obtained by foaming raw materials in the following weight parts.

The physical foaming agent is selected from one or more of 141b, dichloromethane or acetone.

The crosslinking agent is selected from one or more of diethanolamine, triethanolamine, glycerol or trimethylolpropane.

The foaming catalyst may be selected from tertiary amine catalysts, market brand No.: A1 or A33, including but not limited to the above-mentioned commercial catalysts. The gel catalyst may be selected from stannous octoate (T9) or stannous dilaurate (T12), including but not limited to the above-described commercial catalysts.

The antioxidant is selected from hindered phenolic products such as <NUM>, and the anti-yellowing agent is selected from phosphate products.

During the impregnation, the polyurethane flexible foam is added to the chloroplatinic acid solution, the impregnation is carried out at a reaction temperature of <NUM> to <NUM>, for example, <NUM>, <NUM> or <NUM>, then a reducing agent is added and reacted for <NUM> hours to <NUM> hours, for example, <NUM> hours, <NUM> hours or <NUM> hours, and after the reaction, the polyurethane flexible foam is taken out, washed with a solvent and dried to obtain the supported metal platinum catalyst for further use. In the process of the above-mentioned reaction, there is no limitation on the pressure, for example, the reaction may be carried out under atmospheric pressure or slightly positive pressure (not more than <NUM>% of atmospheric pressure). Preferably, the amount of substance of chloroplatinic acid in the impregnation solution is <NUM>*n to <NUM>*n (n is the amount of substance of double bonds contained in the added polyurethane flexible foam, calculated in terms of unsaturation).

The solvent used in the chloroplatinic acid solution may be one or more of toluene, xylene, methanol, ethanol or isopropanol, which is the same as the solvent used for washing. The reducing agent used may be one or more of the following: sodium bicarbonate, potassium bicarbonate, sodium carbonate or potassium carbonate, and the amount of the reducing agent used may be <NUM> % to <NUM> % of the mass of chloroplatinic acid.

The pressures described in the present disclosure are all the absolute pressure, and the molecular weights, unless otherwise specified, are all the number-average molecular weight.

Compared with the existing art, the present disclosure has the beneficial effects described below.

In the following Examples and Comparative Examples, unless otherwise specified, the reagents used are analytical pure, and the contents thereof are mass content.

In the test methods involved in Examples and Comparative Examples, the hydroxyl number was determined in accordance with Determination of hydroxyl number in GB/T <NUM>-<NUM>; the acid number was determined in accordance with Determination of acidity as acid number in GB/T <NUM>-<NUM>; the degree of unsaturation was determined in accordance with Determination of degree of unsaturation in GB/T <NUM>-<NUM>; the water content was determined in accordance with Plastics-Polyols for use in the production of polyurethan-Determination of water content in GB/T <NUM>-<NUM>, and the specific surface area of the foam catalyst was determined in accordance with Determination of the specific surface area of solids by gas adsorption using the BET method in GB/T <NUM>-<NUM>.

The foaming catalyst was A1 and A33 (purchased from Aladdin). The gel catalyst was selected from stannous octoate (T9) (purchased from Aladdin).

The antioxidant was selected from the hindered phenolic product <NUM> (purchased from BASF). The anti-yellowing agent was selected from the phosphate anti-yellowing agent <NUM> (purchased from Dongguan Tongda Chemical).

The physical foaming agent was dichloromethane. The crosslinking agent was diethanolamine.

The model of the GPC instrument was Waters-<NUM>-<NUM>-<NUM>, from Waters. The chromatographic column used was Agilent PL1113-<NUM> (<NUM> × <NUM>). The analytical test method was as follows: <NUM> of samples was added into a <NUM> sample bottle, diluted by adding tetrahydrofuran using a disposable dropper to a concentration of about <NUM>%, filtered through a <NUM> nylon membrane, and analyzed by GPC.

The model of the nuclear magnetic resonance chemical analyzer was AVANCEIII <NUM>, from Bruker. The analytical test condition was as follows: <NUM> BBO probe, experimental type PROTON, pulse sequence zg30, the number of scans <NUM>, and temperature <NUM>.

<NUM> of methanol (<NUM> mol) was added to a <NUM> kettle as an initiator, <NUM> of catalyst sodium hydroxide was added, and nitrogen gas replacement was carried out.

<NUM> of allyl glycidyl ether was added and reacted for <NUM> hour with the temperature raised to <NUM> and the pressure raised to <NUM> MPa. <NUM> of propylene oxide was then added and reacted until the pressure was no longer changed, and then <NUM> of ethylene oxide was added and reacted for a total of <NUM> hour until the reaction pressure was no longer changed. The reaction product was cured for <NUM> hour to obtain a crude product of polyether. Phosphoric acid as a neutralizing agent, water, magnesium silicate as an adsorbent and diatomite as a filter aid, which were <NUM>%, <NUM>%, <NUM>%, and <NUM>% of the total mass of the crude polyether, respectively, were added to the crude product of polyether and then filtered to obtain a refined second polyether polyol.

Through a determination, the water content and the acid number of the product were qualified (water content < <NUM>% and acid number < <NUM> mgKOH/g, the same below); the hydroxyl number was <NUM> mgKOH/g (theoretical hydroxyl number would be <NUM> mgKOH/g), which proves that the molecular weight of the product had reached the calculated molecular weight of <NUM>; the determined degree of unsaturation was <NUM> mmol/g (theoretical degree of unsaturation would be <NUM> mmol/g).

The formulation of the polyurethane flexible foam was as follows:.

In the above-mentioned formulation, the constituents except for isocyanate (TDI) were uniformly mixed in advance and cooled to room temperature, and then isocyanate was added at room temperature to the above mixture and stirred quickly. After that, the mixture was poured into a foaming mold and then de-molded after the foaming and aging in the foaming mold were completed to obtain a foam having a density of <NUM>/m<NUM>, a white appearance and good air permeability. The degree of unsaturation of the product was determined to be <NUM> mmol/g.

<NUM> of the foam was cut into small pieces of <NUM><NUM> and dispersed after adding chloroplatinic acid (<NUM> mmol) and <NUM> of toluene, and then <NUM> of sodium bicarbonate was added. The above materials reacted for <NUM> hours at <NUM>. After the reaction, the foam was washed with <NUM> of toluene and dried for <NUM> hour at <NUM> to prepare the final supported metal platinum catalyst. The specific surface area of the catalyst was <NUM><NUM>/g.

To verify the catalyst, <NUM> of allyl polyether (with a molecular weight of <NUM>, a double bond functionality of <NUM>, and a degree of unsaturation of <NUM> mmol/g) was added to a <NUM> reaction flask and heated to <NUM>. After the above supported metal platinum catalyst was added to the reactor, <NUM> of a hydrogen-containing silicone oil (with a molecular weight of <NUM>, a silicon hydrogen bond content of <NUM> mmol/g) (silicon hydrogen : double bond = <NUM>:<NUM>) was added to the reactor and reacted for <NUM> hour. After the reaction, the catalyst was taken out, cooled and discharged. The degree of unsaturation of the reaction solution was determined to be in a trace amount, indicating that the reaction efficiency was extremely high.

The above-mentioned silane end-capping reaction was repeated <NUM> times. After the completion of each reaction, the foam was washed with the same solvent as that used for preparing the catalyst to verify the cycle life test. It was found that the reaction yield did not change substantially (the difference between the reaction yields did not exceed ± <NUM>% of the average yield value).

<NUM> of ethanol (<NUM>. 05mol) and <NUM> of triglyceride (<NUM> mol) were added to a <NUM> kettle as an initiator, <NUM> of catalyst potassium hydroxide was added, and nitrogen gas replacement was carried out.

<NUM> of methallyl glycidyl ether and <NUM> of glycidyl acrylate were added and reacted for <NUM> hours with the temperature raised to <NUM> and the pressure raised to <NUM> MPa. After the reaction pressure was no longer changed, the reaction product was cured for <NUM> hours to obtain a crude product of polyether. Phosphoric acid as a neutralizing agent, water, magnesium silicate as an adsorbent and diatomite as a filter aid, which were <NUM>%, <NUM>%, <NUM>%, and <NUM>% of the total mass of the crude polyether, respectively, were added to the crude product of polyether and then filtered to obtain a refined second polyether polyol.

Through a determination, the water content and the acid number of the product were qualified; the hydroxyl number of the above-mentioned product was <NUM> mgKOH/g (theoretical hydroxyl number would be <NUM> mgKOH/g), which proves that the molecular weight of the product had reached the calculated molecular weight of <NUM>; the determined degree of unsaturation was <NUM> mmol/g (theoretical degree of unsaturation would be <NUM> mmol/g).

A foam having a density of <NUM>/m<NUM>, a white appearance and good air permeability was prepared. The degree of unsaturation of the product was determined to be <NUM> mmol/g.

<NUM> of the foam was cut into small pieces of <NUM><NUM> and dispersed after adding chloroplatinic acid (<NUM> mol) and <NUM> of a mixed solvent containing <NUM>% xylenen and <NUM>% methanol, and then <NUM> of potassium bicarbonate was added. The above materials reacted for <NUM> hours at <NUM>. After the reaction, the foam was washed with <NUM> of the above-mentioned solvent and dried for <NUM> hours at <NUM> to prepare the final supported metal platinum catalyst. The specific surface area of the catalyst was <NUM><NUM>/g.

<NUM> of ethylene glycol monomethyl ether, <NUM> of <NUM>,<NUM>-propylene glycol monomethyl ether, <NUM> of diethylene glycol monomethyl ether, <NUM> of ethylene glycol, <NUM> of <NUM>,<NUM>-propylene glycol/<NUM>,<NUM>-propylene glycol, <NUM> of neopentyl glycol and <NUM> of sorbitan were added to a <NUM> kettle as an initiator, <NUM> of catalyst sodium methoxide was added, and nitrogen gas replacement was carried out.

<NUM> of methallyl glycidyl ether and <NUM> of glycidyl acrylate were added and reacted for <NUM> hours with the temperature raised to <NUM> and the pressure raised to <NUM> MPa. <NUM> of propylene oxide was then added and reacted for a total of <NUM> hours until the reaction pressure was no longer changed. The reaction product was cured for <NUM> hours to obtain a crude product of polyether. Phosphoric acid as a neutralizing agent, water, magnesium silicate as an adsorbent and diatomite as a filter aid, which were <NUM>%, <NUM>%, <NUM>%, and <NUM>% of the total mass of the crude polyether, respectively, were added to the crude product of polyether and then filtered to obtain a refined second polyether polyol.

Through a determination, the water content and the acid number of the product were qualified; the hydroxyl number was <NUM> mgKOH/g (theoretical hydroxyl number would be <NUM> mgKOH/g), which proves that the molecular weight of the product had reached the calculated molecular weight of <NUM>; the determined degree of unsaturation was <NUM> mmol/g (theoretical degree of unsaturation would be <NUM> mmol/g).

<NUM> of the foam was cut into small pieces of <NUM><NUM> and dispersed after adding chloroplatinic acid (<NUM> mol) and <NUM> of a mixed solvent containing <NUM>% ethanol and <NUM>% isopropanol, and then <NUM> of potassium bicarbonate was added. The above materials reacted for <NUM> hours at <NUM>. After the reaction, the foam was washed with <NUM> of the above-mentioned solvent and dried for <NUM> hours at <NUM> to prepare the final supported metal platinum catalyst. The specific surface area of the catalyst was <NUM><NUM>/g.

<NUM> of water, <NUM> of ethylene glycol, <NUM> of <NUM>,<NUM>-propylene glycol, <NUM> of neopentyl glycol, <NUM> of trimethylolpropane, <NUM> of sorbitan, and <NUM> of glucose were added to a <NUM> kettle as an initiator, <NUM> of catalyst potassium methoxide was added, and nitrogen gas replacement was carried out.

<NUM> of methallyl glycidyl ether and <NUM> of glycidyl methacrylate were added and reacted for <NUM> hours with the temperature raised to <NUM> and the pressure raised to <NUM> MPa. <NUM> of ethylene oxide was added and reacted for a total of <NUM> hours until the reaction pressure was no longer changed. The reaction product was cured for <NUM> hours to obtain a crude product of polyether. Phosphoric acid as a neutralizing agent, water, magnesium silicate as an adsorbent and diatomite as a filter aid, which were <NUM>%, <NUM>%, <NUM>%, and <NUM>% of the total mass of the crude polyether, respectively, were added to the crude product of polyether and then filtered to obtain a refined second polyether polyol.

Through a determination, the water content and the acid number of the product were qualified; the hydroxyl number was <NUM> mgKOH/g (theoretical hydroxyl number would be <NUM> mgKOH/g), which proves that the molecular weight of the product had reached the calculated molecular weight of <NUM>; the determined degree of unsaturation was <NUM> mmol/g.

<NUM> of the foam was cut into small pieces of <NUM><NUM> and dispersed after adding chloroplatinic acid (<NUM> mol) and <NUM> of a mixed solvent containing <NUM>% ethanol and <NUM>% isopropanol, and then <NUM> of sodium carbonate was added. The above materials reacted for <NUM> hours at <NUM>. After the reaction, the foam was washed with <NUM> of the above-mentioned solvent and dried for <NUM> hours at <NUM> to prepare the final supported metal platinum catalyst. The specific surface area of the catalyst was <NUM><NUM>/g.

The process conditions of Example <NUM> were basically the same as those of Example <NUM> except that propylene oxide was used instead of ethylene oxide and potassium carbonate was used as a reducing agent. The specific surface area of the catalyst was <NUM><NUM>/g.

In the following Examples <NUM> to <NUM>, when the first polyether polyol was prepared, the average molecular weight of the epoxide added at each stage was X and the molecular weight of the hydroxyl-containing initiator was Y, the molar amount of the epoxide to be added at the ith stage was Z times the molar amount of the small-molecule polyol initiator, which satisfied the following relationship: Z = (Mi - M (i - <NUM>))/X, wherein i was an integer between <NUM> to n, and M0 was Y when i = <NUM>.

An appropriate amount of <NUM>,<NUM>-propanediol was added to a reaction kettle, and zinc hexacyanocobaltate was used as a catalyst, whose amount was <NUM> ppm (based on the total weight of the reaction system during the reaction, the same below). The reaction temperature was controlled at <NUM> and the reaction pressure was <NUM> MPa. Propylene oxide was added to prepare a first polyether polyol according to a polymerization route of <NUM>,<NUM>-propanediol-<NUM>/mol-<NUM>/mol-<NUM>/mol. Through GPC analysis, it was determined that the polyether molecular weight was <NUM>/mol, the molecular weight distribution was <NUM> and the viscosity was <NUM> cp at <NUM>.

The first polyether polyol obtained in the preceding step was used as a raw material and heated to <NUM>, then a catalyst metal sodium whose amount was in a molar ratio of <NUM>:<NUM> to the hydroxyl equivalent of the polyether polyol was added, and then allyl chloride whose amount was in a molar ratio of <NUM>:<NUM> to the hydroxyl equivalent of the polyether polyol was added. The above materials reacted for <NUM> hours at constant temperature to obtain a crude product of double-bond-terminated modified polyether. Subsequently, acetic acid, n-hexane solvent and water, which were <NUM>%, <NUM>% and <NUM>% of the mass of the crude product of modified polyether, respectively, were added, stirred and mixed for <NUM> hours. Water was separated using a coalescing separator, and then the organic solvent was removed by distillation under reduced pressure using a thin film evaporator to obtain a refined product of modified polyether. After the obtained product was analyzed by NMR and GPC, the double bond termination rate was > <NUM>%, the viscosity was <NUM> cp at <NUM>, and the molecular weight distribution was <NUM>.

The modified polyether obtained in the preceding step was used as a raw material and heated to <NUM>, the supported metal platinum catalyst of Example <NUM> was added, whose amount was <NUM> ppm (by platinum content, based on the total mass of the reaction system during the reaction, the same below), and then methyldimethoxysilane whose amount was in a molar ratio of <NUM>:<NUM> to the double bond equivalent of the modified polyether was continuously added. The above material reacted at constant temperature for <NUM> hours to obtain a final product, that is, a reactive sealant resin. After the obtained product was analyzed by NMR and GPC, the silane termination rate was > <NUM>%, the viscosity was <NUM> cp at <NUM>, and the molecular weight distribution was <NUM>.

An appropriate amount of <NUM>,<NUM>-propanediol was added to a reaction kettle, and zinc hexacyanocobaltate was used as a catalyst, whose amount was <NUM> ppm. The reaction temperature was controlled at <NUM> and the reaction pressure was <NUM> MPa. Propylene oxide and ethylene oxide were added, wherein the amount of ethylene oxide was <NUM>% of the total mass of the epoxides, to prepare a first polyether polyol according to a polymerization route of <NUM>,<NUM>-propanediol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol. Through GPC analysis, it was determined that the polyether molecular weight was <NUM>,<NUM>/mol, the molecular weight distribution was <NUM> and the viscosity was <NUM> cp at <NUM>.

The first polyether polyol obtained in the preceding step was used as a raw material and heated to <NUM>, then a catalyst sodium hydride whose amount was in a molar ratio of <NUM>:<NUM> to the hydroxyl equivalent of the polyether polyol was added, and then methallyl chloride whose amount was in a molar ratio of <NUM>:<NUM> to the hydroxyl equivalent of the polyether polyol was added. The above materials reacted for <NUM> hours at the constant temperature to obtain a crude product of double-bond-terminated modified polyether. Subsequently, acetic acid, n-hexane solvent and water, which were <NUM>%, <NUM>% and <NUM>% of the mass of the crude product of modified polyether, respectively, were added, stirred and mixed for <NUM> hours. Water and the organic solvent were separated with reference to Example <NUM> to obtain a refined product of modified polyether. After the obtained product was analyzed by NMR and GPC, the double bond termination rate was > <NUM>%, the viscosity was <NUM> cp at <NUM>, and the molecular weight distribution was <NUM>.

The modified polyether obtained in the preceding step was used as a raw material and heated to <NUM>, the supported metal platinum catalyst of Example <NUM> was added, whose amount was <NUM> ppm, and then trimethoxysilane whose amount was in a molar ratio of <NUM>:<NUM> to the double bond equivalent of the modified polyether was continuously added. The above material reacted at constant temperature for <NUM> hours to obtain a final product, that is, a reactive sealant resin. After the obtained product was analyzed by NMR and GPC, the silane termination rate was > <NUM>%, the viscosity was <NUM> cp at <NUM>, and the molecular weight distribution was <NUM>.

An appropriate amount of glycerin was added to a reaction kettle, and zinc hexacyanocobaltate was used as a catalyst, whose amount was <NUM> ppm. The reaction temperature was controlled at <NUM> and the reaction pressure was <NUM> MPa. Propylene oxide was added to prepare a first polyether polyol according to a polymerization route of trifunctional alcohol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol. Through GPC analysis, it was determined that the polyether molecular weight was <NUM>/mol, the molecular weight distribution was <NUM> and the viscosity was <NUM> cp at <NUM>.

The first polyether polyol obtained in the preceding step was used as the raw material and heated to <NUM>, then a catalyst sodium methoxide whose amount was in a molar ratio of <NUM>:<NUM> to the hydroxyl equivalent of the polyether polyol was added, and then methallyl chloride whose amount was in a molar ratio of <NUM>:<NUM> to the hydroxyl equivalent of the polyether polyol was added. The above materials reacted for <NUM> hours at the constant temperature to obtain a crude product of double-bond-terminated modified polyether. Subsequently, acetic acid, n-hexane solvent and water, which were <NUM>%, <NUM>% and <NUM>% of the mass of the crude product of modified polyether, respectively, were added, stirred and mixed for <NUM> hours. Water and the organic solvent were separated with reference to Example <NUM> to obtain a refined product of modified polyether. After the obtained product was analyzed by NMR and GPC, the double bond termination rate was > <NUM>%, the viscosity was <NUM> cp at <NUM>, and the molecular weight distribution was <NUM>.

An appropriate amount of sorbitan was added to a reaction kettle, and zinc hexacyanocobaltate was used as a catalyst, whose amount was <NUM> ppm. The reaction temperature was controlled at <NUM> and the reaction pressure was <NUM> MPa. Propylene oxide was added to prepare a first polyether polyol according to a polymerization route of sorbitan-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol. Through GPC analysis, it was determined that the polyether molecular weight was <NUM>/mol, the molecular weight distribution was <NUM> and the viscosity was <NUM> cp at <NUM>.

The first polyether polyol obtained in the preceding step was used as a raw material and heated to <NUM>, then a catalyst metal sodium and sodium methoxide, whose amounts were in a molar ratio of <NUM>:<NUM>:<NUM> to the hydroxyl equivalent of the polyether polyol was added, and then methallyl chloride whose amount was in a molar ratio of <NUM>:<NUM> to the hydroxyl equivalent of the polyether polyol was added. The above materials reacted for <NUM> hours at the constant temperature to obtain a crude product of double-bond-terminated modified polyether. Subsequently, acetic acid, n-hexane solvent and water, which were <NUM>%, <NUM>% and <NUM>% of the mass of the crude product of modified polyether, respectively, were added, stirred and mixed for <NUM> hours. Water and the organic solvent were separated with reference to Example <NUM> to obtain a refined product of modified polyether. After the obtained product was analyzed by NMR and GPC, the double bond termination rate was > <NUM>%, the viscosity was <NUM> cp at <NUM>, and the molecular weight distribution was <NUM>.

The modified polyether obtained in the preceding step was used as a raw material and heated to <NUM>, the supported metal platinum catalyst of Example <NUM> was added, whose amount was <NUM> ppm, and then a fixed amount of hydrogen-containing silane whose amount was in a molar ratio of <NUM>:<NUM> to the double bond equivalent of the modified polyether was continuously added. The above material reacted at constant temperature for <NUM> hours to obtain a final product, that is, a reactive sealant resin. After the obtained product was analyzed by NMR and GPC, the silane termination rate was > <NUM>%, the viscosity was <NUM> cp at <NUM>, and the molecular weight distribution was <NUM>.

An appropriate amount of glycerin was added to a reaction kettle, and zinc hexacyanocobaltate was used as a catalyst, whose amount was <NUM> ppm. The reaction temperature was controlled at <NUM> and the reaction pressure was <NUM> MPa. A fixed amount of propylene oxide was added to prepare a first polyether polyol according to a polymerization route of trifunctional alcohol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol-<NUM>/mol. Through GPC analysis, it was determined that the polyether molecular weight was <NUM>/mol, the molecular weight distribution was <NUM> and the viscosity was <NUM> cp at <NUM>.

The first polyether polyol obtained in the preceding step was used as a raw material and heated to <NUM>, then a catalyst sodium methoxide whose amount was in a molar ratio of <NUM>:<NUM> to the hydroxyl equivalent of the polyether polyol was added, and then allyl chloride whose amount was in a molar ratio of <NUM>:<NUM> to the hydroxyl equivalent of the polyether polyol was added. The above materials reacted for <NUM> hours at constant temperature to obtain a crude product of double-bond-terminated modified polyether. Subsequently, acetic acid, n-hexane solvent and water, which were <NUM>%, <NUM>% and <NUM>% of the mass of the crude product of modified polyether, respectively, were added, stirred and mixed for <NUM> hours. Water and the organic solvent were separated with reference to Example <NUM> to obtain a refined product of modified polyether. After the obtained product was analyzed by NMR and GPC, the double bond termination rate was > <NUM>%, the viscosity was <NUM> cp at <NUM>, and the molecular weight distribution was <NUM>.

The modified polyether obtained in the preceding step was used as a raw material and heated to <NUM>, the supported metal platinum catalyst of Example <NUM> was added, whose amount was <NUM> ppm, and then methyldimethoxysilane whose amount was in a molar ratio of <NUM>:<NUM> to the double bond equivalent of the modified polyether was continuously added. The above material reacted at constant temperature for <NUM> hours to obtain a final product, that is, a reactive sealant resin. After the obtained product was analyzed by NMR and GPC, the silane termination rate was > <NUM>%, the viscosity was <NUM> cp at <NUM>, and the molecular weight distribution was <NUM>.

An appropriate amount of polyether polyol whose molecular weight was <NUM> and used <NUM> mol of glycerin as an initiator was added to a reaction kettle, and zinc hexacyanocobaltate was used as a catalyst, whose amount was <NUM> ppm. The reaction temperature was controlled at <NUM> and the reaction pressure was <NUM> MPa. A fixed amount of propylene oxide (based on the target molecular weight <NUM> of the polyether polyol) was added to directly prepare a polyether polyol.

The polyether polyol was modified and refined by the same method as the method for preparing the modified polyether in Example <NUM> to obtain a double-bond-terminated modified polyether polyol. Through GPC analysis, it was determined that the polyether polyol was <NUM>/mol and the molecular weight distribution was <NUM>.

Claim 1:
A method for preparing a reactive sealant resin, comprising:
(<NUM>) preparation of a polyether polyol: under the action of an alkali catalyst, polymerizing a hydroxyl-containing initiator with an epoxide to obtain a first polyether polyol;
(<NUM>) polyether modification: adding an alkoxidation reagent and a halogenated end-capping agent containing a double bond to the first polyether polyol obtained in step (<NUM>) for reaction to obtain a crude product of double-bond-terminated polyether, and refining the obtained crude product to obtain a product of modified polyether; and
(<NUM>) silane end-capping: subjecting the modified polyether obtained in step (<NUM>) as a raw material and hydrogen-containing silane to a silane end-capping reaction under the action of a hydrosilylation catalyst to obtain a target product of a reactive sealant resin;
the alkali catalyst is one or more of an alkali metal, an alkali metal hydride, an alkali metal hydroxide, an alkali metal alkoxide, a composite metal cyanide or a phosphazene catalyst;
wherein the hydrosilylation catalyst is a supported metal platinum catalyst with an amount of <NUM> ppm to <NUM> ppm, based on the platinum content; the supported metal platinum catalyst is obtained by subjecting a chloroplatinic acid solution to impregnation, reduction and drying with a polyurethane flexible foam as a carrier; the polyurethane flexible foam is prepared by subjecting a raw material comprising a second polyether polyol to a foaming reaction, wherein a polymerized monomer for preparing the second polyether polyol comprises an epoxide containing a C=C double bond in the molecule, and the content of the epoxide in the polymerized monomer is <NUM> wt% to <NUM> wt%.