CN116814211B

CN116814211B - Reactive sealant resin and preparation method and application thereof

Info

Publication number: CN116814211B
Application number: CN202310660345.9A
Authority: CN
Inventors: 陶小乐; 宋琦; 俞云; 刘伟明; 何丹薇; 何永富
Original assignee: Hangzhou Zhijiang Silicone Chemicals Co Ltd; Hangzhou Zhijiang New Material Co Ltd
Current assignee: Hangzhou Zhijiang Silicone Chemicals Co Ltd; Hangzhou Zhijiang New Material Co Ltd
Priority date: 2023-06-06
Filing date: 2023-06-06
Publication date: 2024-04-16
Anticipated expiration: 2043-06-06
Also published as: CN116814211A

Abstract

The invention provides a reactive sealant resin, a preparation method and application thereof. The preparation method comprises the following steps: (1) Reacting a hydroxyl-containing initiator, an epoxy compound and carbon dioxide to obtain polyether-polycarbonate polyol; (2) Reacting polyether-polycarbonate polyol with halogenated end capping agent containing double bonds to obtain double bond modified polyether-polycarbonate; (3) Reacting double bond modified polyether-polycarbonate with hydrogen-containing silane to obtain the reactive sealant resin; the epoxy compounds are ethylene oxide and propylene oxide. According to the preparation method, carbon dioxide is used as a part of raw materials, and carbonate chain links are introduced, so that the prepared reactive sealant resin has the characteristics of excellent comprehensive performance, high mechanical strength, high silane end capping rate and the like.

Description

Reactive sealant resin and preparation method and application thereof

Technical Field

The invention belongs to the technical field of sealants, and particularly relates to a reactive sealant resin, a preparation method and application thereof.

Background

Along with the modern development of urban buildings and the improvement of the requirements on building functions in China, the types of sealants for joints of building structures are more and more, and the development of reactive sealants including acrylic acid type, organosilicon type and polyurethane type is very rapid, wherein the organosilicon modified polyether reactive sealants combine the advantages of both organosilicon and flexible polyether, and have the characteristics of high curing speed and excellent comprehensive performance.

The curing mechanism of the organosilicon modified polyether reaction type sealant is that terminal alkoxy reacts with moisture in air under the action of a catalyst, and is hydrolyzed and condensed to form Si-O-Si bonds, so that a three-dimensional network structure with a crosslinked main chain is formed, and the structure endows the organosilicon modified polyether sealant with excellent water resistance, weather resistance, ageing resistance and other properties, but still has the defects of low strength, poor oxidation resistance, poor oil resistance, solvent resistance and the like.

CN111378107 a discloses a preparation method of a reactive sealant resin, which comprises the following steps: (1) The hydroxyl-containing initiator is polymerized with an epoxy compound under the action of a base catalyst to obtain polyether polyol; (2) Adding an alkoxide reagent and a halogenated end capping agent containing double bonds into the polyether polyol obtained in the step (1) to react so as to obtain a double bond end capped polyether crude product, and refining the obtained crude product to obtain modified polyether; (3) And (3) carrying out silane end-capping reaction on the modified polyether obtained in the step (2) and hydrogen-containing silane under the action of a hydrosilylation catalyst to obtain the target product reactive sealant resin. The reactive sealant resin provided by the technical scheme has excellent properties and good adhesiveness and paintability.

CN110862797a discloses a silane-terminated polyether sealant and a preparation method thereof, the preparation method of the silane-terminated polyether sealant comprises the steps of adding short/long chain silane-terminated polyether polyols prepared from polyether polyols with different molecular weights and diisocyanate compounds, plasticizer, calcium carbonate and gas-phase white carbon black into a planetary stirring kettle, and stirring and mixing uniformly; then adding a silane coupling agent and an organosilicon defoamer, vacuumizing, stirring and mixing uniformly; and (3) adding an organotin catalyst after the vacuum environment is relieved, vacuumizing again, and stirring and mixing uniformly to obtain the silane-terminated polyether sealant. The silane-terminated polyether sealant provided by the technical scheme has high tensile strength and elongation at break, excellent weather resistance, durability and high deformation displacement resistance.

CN106833481a discloses an environment-friendly organic silicon modified polyether sealant and a preparation method thereof, wherein the sealant comprises the following raw materials: difunctional polyether polyol, allyl polyether, polyisocyanate, catalyst and organosiloxane; the preparation method comprises the following steps: (1) Firstly, adding difunctional polyether polyol and polyisocyanate into a reaction kettle, and heating to 80-90 ℃ for reaction to enable the NCO mass fraction to reach 0.8-1.05%; (2) Adding allyl polyether, and carrying out heat preservation reaction to ensure that the mass fraction of NCO is 0; (3) Adding part of catalyst and organic siloxane, performing heat preservation reaction to obtain an organic silicon modified polyether sealant prepolymer, and then adding the rest catalyst to obtain the environment-friendly organic silicon modified polyether sealant. The preparation method provided by the technical scheme is simple and easy to operate, and the prepared sealant is high in bonding strength, good in sealing effect, outstanding in ageing resistance, adjustable in curing speed, free of VOC, environment-friendly and odorless.

Although the improvement of the preparation process and the modification of the sealant by adding isocyanate can improve the mechanical property of the organosilicon modified polyether reaction type sealant to a certain extent, the raw material for preparing the isocyanate is highly toxic phosgene, seriously harms the physical health of people and has a great threat to the environment.

Therefore, it is necessary to develop a reactive sealant resin with the advantages of environment-friendly and easy operation of the preparation method, high mechanical strength, better oxidation resistance, oil resistance and solvent resistance and a preparation method thereof.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a reactive sealant resin, and a preparation method and application thereof. The preparation method is environment-friendly and easy to operate, and the prepared reactive sealant resin has the characteristics of excellent comprehensive performance, good oxidation resistance, high mechanical strength, high silane end capping rate and the like.

To achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a method for preparing a reactive sealant resin, the method comprising the steps of:

(1) And (3) reacting the hydroxyl-containing initiator, the epoxy compound and carbon dioxide to obtain the polyether-polycarbonate polyol.

(2) And (3) reacting the polyether-polycarbonate polyol with a halogenated end-capping agent containing double bonds to obtain the double bond modified polyether-polycarbonate.

(3) And (3) reacting the double bond modified polyether-polycarbonate with hydrogen-containing silane to obtain the reactive sealant resin.

The epoxy compounds in the step (1) are ethylene oxide and propylene oxide.

In the preparation method, hydroxyl-containing initiator, epoxy compound, carbon dioxide, halogenated end-capping agent containing double bonds and hydrogen-containing silane are used as raw materials, and the preparation, double bond modification and silane end-capping process of polyether-polycarbonate polyol are used for preparing the reactive sealant resin containing carbonate structures.

In the invention, the epoxy compounds are ethylene oxide and propylene oxide, because the hydroxyl end groups of the prepared polyether-polycarbonate polyol are secondary hydroxyl groups when only propylene oxide is used as the epoxy compound, the reactivity is low, and the terminal group conversion rate is low when double bond modified polyether-polycarbonate polyol is carried out.

Preferably, the polyether-polycarbonate polyol of step (1) has a number average molecular weight of 6000 to 280000g/mol, for example 6000g/mol, 10000g/mol, 50000g/mol, 80000g/mol, 100000g/mol, 150000g/mol, 180000g/mol, 200000g/mol, 250000g/mol or 280000g/mol, etc., preferably 8000 to 210000g/mol.

Preferably, the polyether-polycarbonate polyol has a functionality of 2 or 3, preferably 2.

Preferably, the polyether-polycarbonate polyol has a molecular weight distribution of 1.1 to 2.5, for example 1.1, 1.2, 1.3, 1.5, 1.6, 1.8, 1.9, 2.0, 2.2, 2.3 or 2.5, etc., preferably 1.2 to 2.0.

Preferably, the molar ratio of polyether mer to polycarbonate mer in the polyether-polycarbonate polyol is from 1:0.1 to 1, for example from 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1, preferably from 1:0.2 to 0.5.

Preferably, the hydroxyl-containing starter of step (1) comprises a small molecule polyol and/or a polymer polyol.

Preferably, the hydroxyl-containing starter has a number average molecular weight of 600 or less, for example 10, 50, 100, 150, 200, 250, 300, 400, 500 or 600, etc.

Preferably, the hydroxyl-containing initiator comprises any one or a combination of at least two of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, polyethylene glycol, polypropylene glycol, glycerol or trimethylolpropane.

Preferably, the hydroxyl-containing initiator is polyethylene glycol and/or polypropylene glycol.

Preferably, the epoxy compounds are ethylene oxide and propylene oxide, wherein the mass percent of ethylene oxide is less than or equal to 10%, excluding 0, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc.

Preferably, the reaction of step (1) is carried out under the action of a bimetallic catalyst.

Preferably, the bimetallic catalyst comprises zinc-cobalt double metal cyanide.

Preferably, the mass ratio of the bimetallic catalyst to the epoxy compound is 1:100-2000, for example 1:100, 1:300, 1:500, 1:700, 1:1000, 1:1300, 1:1500, 1:1800 or 1:2000, etc.

Preferably, the mass ratio of the hydroxyl initiator to the epoxy compound is 0.5-2:8-12, such as 0.5:8, 0.5:10, 0.5:12, 1:9, 1:10, 1:11, 1.5:8, 1.5:9, 1.5:11, 1.5:12, 2:8, 2:11 or 2:12, etc.

Preferably, the reaction of step (1) comprises the steps of: mixing hydroxyl-containing initiator, bimetallic catalyst, propylene oxide and part of carbon dioxide, performing early reaction, releasing unreacted carbon dioxide, adding ethylene oxide, and performing later reaction.

In the invention, carbon dioxide is discharged in the later reaction, and ethylene oxide is added, so that active oxygen anions in a reaction system can continuously attack the ethylene oxide to carry out ring-opening reaction, and further the polyether-polycarbonate polyol with primary hydroxyl as terminal hydroxyl is obtained.

Preferably, the temperature of the preliminary reaction is 40 to 120 ℃, for example 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, or the like, preferably 50 to 100 ℃, and the time of the preliminary reaction is 1 to 10 hours, for example 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or the like, preferably 2 to 8 hours.

Preferably, the pressure of the carbon dioxide during the preliminary reaction is always maintained at 0.5 to 4.0MPa, for example, 0.5MPa, 0.8MPa, 1.0MPa, 1.5MPa, 1.8MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa or 4MPa, etc., preferably 1 to 3MPa.

Preferably, the temperature of the post-reaction is 40 to 120 ℃, such as 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, or the like, preferably 50 to 100 ℃, and the time of the post-reaction is 1 to 10 hours, such as 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, or the like, preferably 2 to 8 hours.

Preferably, the mass percent of ethylene oxide is 10% or less, excluding 0, based on 100% of the total mass of propylene oxide and ethylene oxide.

Preferably, the halogenated blocking agent containing a double bond in step (2) comprises acryloyl chloride and/or methacryloyl chloride.

Preferably, the reaction of step (2) is carried out over a catalyst comprising pyridine.

In the invention, the catalyst is selected from pyridine, can be removed by means of decompression or water washing, is easy to clean, and can avoid catalyst residues.

Preferably, the reaction of step (2) is carried out in a solvent comprising any one or a combination of at least two of dichloromethane, chloroform, tetrahydrofuran or dimethyl carbonate.

Preferably, the solvent is any one or a combination of at least two of dichloromethane, chloroform and dimethyl carbonate.

In the invention, the viscosity of the double bond modified polyether-polycarbonate can be reduced by using the solvent, so that by-products such as pyridine hydrochloride and the like formed in the subsequent reaction process can be filtered and removed conveniently. When tetrahydrofuran is used as a solvent, water and tetrahydrofuran are mutually soluble, and cannot be separated after washing. The solvent is therefore further preferably any one or a combination of at least two of dichloromethane, chloroform and dimethyl carbonate.

Preferably, the molar ratio of the double bond containing halogenated capping agent to the polyether-polycarbonate polyol is from 2 to 8:1, for example from 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1 or 8:1, etc., preferably from 2 to 5:1.

In the present invention, the molar ratio of the double bond-containing halogenated blocking agent to the polyether-polycarbonate polyol is 2 to 8:1, and the functionality of the polyether-polycarbonate polyol is 2 or 3, so that the amount of the double bond-containing halogenated blocking agent used is 2 or 3 times that of the polyether-polycarbonate polyol, and the addition of a small excess of the double bond-containing halogenated blocking agent can shorten the blocking reaction time and increase the double bond blocking rate.

Preferably, the molar ratio of catalyst to polyether-polycarbonate polyol is from 1 to 3:1, e.g., 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, or 3:1, etc., preferably 2:1.

Preferably, the solvent is 20 to 120% by mass, for example 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 110% or 120% by mass, etc., preferably 50 to 100% by mass, based on 100% by mass of the polyether-polycarbonate polyol.

Preferably, the temperature of the reaction in step (2) is 10 to 60 ℃, e.g. 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃ or 60 ℃, etc., preferably 20 to 40 ℃, and the reaction time is 12 to 36 hours, e.g. 12 hours, 16 hours, 18 hours, 20 hours, 24 hours, 28 hours, 30 hours, 32 hours, 34 hours or 36 hours, etc., preferably 18 to 30 hours.

Preferably, the step (2) further comprises a refining step.

Preferably, the refining comprises the steps of: filtering to obtain a double bond modified polyether-polycarbonate crude product, adding water for cleaning, removing water by using a coalescing separator, and removing a solvent to obtain the double bond modified polyether-polycarbonate.

In the invention, the refining adopts a coalescence separation process to remove water, so that the technical problem of solid waste treatment in the preparation of the traditional polyether reaction type sealant resin is avoided.

Preferably, the method for removing the solvent includes reduced pressure distillation, wiped film evaporation or thin film evaporation.

Preferably, the time of the washing is 2 to 12 hours, for example 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, or the like.

Preferably, the mass ratio of water to double bond modified polyether-polycarbonate crude product is 0.3 to 3:1, for example 0.3:1, 0.5:1, 0.8:1, 1:1, 1.3:1, 1.5:1, 1.8:1, 2:1, 2.5:1, 0.3:1 or 3:1, etc., preferably 0.5 to 1.5:1.

Preferably, the hydrogen-containing silane of step (3) comprises any one or a combination of at least two of trimethoxysilane, triethoxysilane, methyldimethoxysilane or methyldiethoxysilane.

Preferably, the hydrogen-containing silane comprises methyldimethoxysilane and/or trimethoxysilane.

Preferably, the reaction of step (3) is carried out in the presence of a hydrosilylation catalyst.

Preferably, the hydrosilylation catalyst is a platinum metal catalyst.

In the invention, the platinum catalyst is an isopropanol solution of chloroplatinic acid, and the catalytic efficiency is high.

Preferably, the mass of the hydrosilylation catalyst is 0.1% -1% of the mass of the double bond modified polyether-polycarbonate, for example 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1% and the like.

Preferably, the molar ratio of the hydrosilane to the double bond modified polyether-polycarbonate of step (3) is 1 to 2:1, e.g., 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, etc. Preferably, the temperature of the reaction in step (3) is 60 to 130 ℃, e.g. 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or the like, and the reaction time is 2 to 7 hours, e.g. 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours or 7 hours or the like.

In a second aspect, the present invention provides a reactive sealant resin prepared by the preparation method as described in the first aspect.

In a third aspect, the present invention provides a reactive sealant comprising a reactive sealant resin as described in the second aspect.

Compared with the prior art, the invention has the following beneficial effects:

the preparation method of the reactive sealant resin provided by the invention is characterized in that polyether-polycarbonate polyol is prepared by taking carbon dioxide as a part of raw materials, and the prepared reactive sealant resin containing carbonate chain links is prepared through double bond modification and silane end capping processes, so that the preparation method is green, environment-friendly and easy to operate. The reactive sealant resin has the characteristics of high mechanical strength, high silane end capping rate and the like, is convenient to use, has excellent comprehensive performance, can be directly used for preparing the sealant, and also has the characteristics of high viscosity, short surface drying time, good adhesiveness and the like.

Detailed Description

The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.

In the following examples and comparative examples, all reagents used were analytically pure unless otherwise specified.

Example 1

The embodiment provides a reactive sealant resin and a preparation method thereof, wherein the preparation method of the reactive sealant resin is as follows.

(1) Preparation of polyether-polycarbonate polyol: adding a hydroxyl-containing initiator (polypropylene glycol with the number average molecular weight of 400) into a high-pressure reaction kettle, adding a bimetallic catalyst (zinc-cobalt double metal cyanide), adding propylene oxide, then charging carbon dioxide, controlling the reaction temperature to be 60 ℃ under the pressure of 3MPa, and carrying out constant-temperature reaction for 6 hours;

and then discharging unreacted carbon dioxide, adding ethylene oxide, controlling the reaction temperature to be 60 ℃, reacting for 4 hours at constant temperature, and removing unreacted epoxy compounds through a scraper evaporator after the reaction is finished to prepare the polyether-polycarbonate polyol.

Wherein, the mass ratio of the hydroxyl initiator to the epoxy compound is 1:10, the epoxy compound comprises ethylene oxide and propylene oxide, the mass ratio of the bimetallic catalyst to the epoxy compound is 1:1000, and the mass of the ethylene oxide accounts for 5 percent of the total mass of the epoxy compound.

(2) Preparation of double bond modified polyether-polycarbonate: mixing polyether-polycarbonate polyol and halogenated end capping agent (methacryloyl chloride) containing double bonds according to a molar ratio of 1:2, adding pyridine as a catalyst, adding methylene dichloride as a solvent (the mass of the solvent is 50% of that of the polyether-polycarbonate polyol) according to a molar ratio of 1:1, controlling the reaction temperature to be 30 ℃, and carrying out constant-temperature reaction for 24 hours.

Refining: filtering after the reaction is finished to obtain a double bond modified polyether-polycarbonate crude product, adding water for cleaning, wherein the mass ratio of the water to the double bond modified polyether-polycarbonate crude product is 1:1, stirring and mixing for 2 hours, separating water (and salt dissolved in water) in the double bond modified polyether-polycarbonate crude product by adopting a coalescing separator, and removing a reaction solvent by reduced pressure distillation to obtain the double bond modified polyether-polycarbonate.

(3) Preparation of a reactive sealant resin: mixing double bond modified polyether-polycarbonate, hydrogen-containing silane (trimethoxysilane) and a platinum metal catalyst (1% isopropyl alcohol solution of chloroplatinic acid), wherein the molar ratio of the hydrogen-containing silane to the double bond modified polyether-polycarbonate is 1.5:1, the mass of the platinum metal catalyst is 0.5% of the mass of the double bond modified polyether-polycarbonate, heating to 70 ℃, and reacting at constant temperature for 4 hours to obtain the reactive sealant resin.

Example 2

(1) Preparation of polyether-polycarbonate polyol: adding a hydroxyl-containing initiator (polyethylene glycol with the number average molecular weight of 500) into a high-pressure reaction kettle, adding a bimetallic catalyst (zinc-cobalt double metal cyanide), adding propylene oxide, then charging carbon dioxide, controlling the reaction temperature to be 60 ℃ under the pressure of 3MPa, and carrying out constant-temperature reaction for 8 hours;

Wherein, the mass ratio of the hydroxyl initiator to the epoxy compound is 2:10, the epoxy compound comprises ethylene oxide and propylene oxide, the mass ratio of the bimetallic catalyst to the epoxy compound is 1:1800, and the mass of the ethylene oxide accounts for 7 percent of the total mass of the epoxy compound.

(2) Preparation of double bond modified polyether-polycarbonate: mixing polyether-polycarbonate polyol and halogenated end capping agent (acryloyl chloride) containing double bonds according to a molar ratio of 1:3.5, adding pyridine as a catalyst, wherein the molar ratio of the catalyst to the polyether-polycarbonate polyol is 1.5:1, adding dimethyl carbonate as a solvent (the mass of the solvent is 60% of that of the polyether-polycarbonate polyol), controlling the reaction temperature to 25 ℃, and reacting at constant temperature for 24 hours.

Refining: filtering after the reaction is finished to obtain a double bond modified polyether-polycarbonate crude product, adding water for cleaning, stirring and mixing for 3 hours, separating water (and salt dissolved in water) in the double bond modified polyether-polycarbonate crude product by adopting a coalescing separator, and removing a reaction solvent by reduced pressure distillation to obtain the double bond modified polyether-polycarbonate.

(3) Preparation of a reactive sealant resin: mixing double bond modified polyether-polycarbonate, hydrogen-containing silane (trimethoxysilane) and a platinum metal catalyst (1% isopropyl alcohol solution of chloroplatinic acid), wherein the molar ratio of the hydrogen-containing silane to the double bond modified polyether-polycarbonate is 2:1, the mass of the platinum metal catalyst is 0.5% of the mass of the double bond modified polyether-polycarbonate, heating to 70 ℃, and reacting at constant temperature for 4 hours to obtain the reactive sealant resin.

Example 3

(1) Preparation of polyether-polycarbonate polyol: adding a hydroxyl-containing initiator (1, 3-propylene glycol) into a high-pressure reaction kettle, adding propylene oxide into a bimetallic catalyst (zinc-cobalt double metal cyanide), then charging carbon dioxide into the mixture, controlling the reaction temperature to be 65 ℃ under the pressure of 2.6MPa, and carrying out constant-temperature reaction for 6 hours;

and then discharging unreacted carbon dioxide, adding ethylene oxide, controlling the reaction temperature to be 60 ℃, reacting for 3 hours at constant temperature, and removing unreacted epoxy compounds through a scraper evaporator after the reaction is finished to prepare the polyether-polycarbonate polyol.

Wherein, the mass ratio of the hydroxyl initiator to the epoxy compound is 0.5:12, the epoxy compound comprises ethylene oxide and propylene oxide, the mass ratio of the bimetallic catalyst to the epoxy compound is 1:900, and the mass of the ethylene oxide accounts for 5 percent of the total mass of the epoxy compound.

(2) Preparation of double bond modified polyether-polycarbonate: mixing polyether-polycarbonate polyol and halogenated end capping agent (methacryloyl chloride) containing double bonds according to a molar ratio of 1:4, adding pyridine as a catalyst, adding chloroform as a solvent (the mass of the solvent is 40% of that of the polyether-polycarbonate polyol) according to a molar ratio of 2:1, controlling the reaction temperature to be 30 ℃, and carrying out constant-temperature reaction for 24 hours.

Refining: filtering after the reaction is finished to obtain a double bond modified polyether-polycarbonate crude product, adding water for cleaning, wherein the mass ratio of the water to the double bond modified polyether-polycarbonate crude product is 0.8:1, stirring and mixing for 1.5h, separating water (and salt dissolved in the water) in the double bond modified polyether-polycarbonate crude product by adopting a coalescing separator, and removing a reaction solvent by reduced pressure distillation to obtain the double bond modified polyether-polycarbonate.

(3) Preparation of a reactive sealant resin: mixing double bond modified polyether-polycarbonate, hydrogen-containing silane (trimethoxysilane) and a platinum metal catalyst (1% isopropyl alcohol solution of chloroplatinic acid), wherein the molar ratio of the hydrogen-containing silane to the double bond modified polyether-polycarbonate is 2:1, the mass of the platinum metal catalyst is 0.3% of the mass of the double bond modified polyether-polycarbonate, heating to 70 ℃, and reacting at constant temperature for 4 hours to obtain the reactive sealant resin.

Example 4

(1) Preparation of polyether-polycarbonate polyol: adding a hydroxyl-containing initiator (ethylene glycol) into a high-pressure reaction kettle, adding propylene oxide into a bimetallic catalyst (zinc-cobalt double metal cyanide), then charging carbon dioxide into the mixture, controlling the reaction temperature to be 70 ℃, and carrying out constant-temperature reaction for 4 hours;

and then discharging unreacted carbon dioxide, adding ethylene oxide, controlling the reaction temperature to be 60 ℃, reacting for 2 hours at constant temperature, and removing unreacted epoxy compounds through a scraper evaporator after the reaction is finished to prepare the polyether-polycarbonate polyol.

Wherein the mass ratio of the hydroxyl initiator to the epoxy compound is 0.5:11, the epoxy compound comprises ethylene oxide and propylene oxide, the mass ratio of the bimetallic catalyst to the epoxy compound is 1:600, and the mass of the ethylene oxide accounts for 3% of the total mass of the epoxy compound.

(2) Preparation of double bond modified polyether-polycarbonate: mixing polyether-polycarbonate polyol and halogenated end capping agent (methacryloyl chloride) containing double bonds according to a molar ratio of 1:4.5, adding pyridine as a catalyst, adding methylene dichloride as a solvent (the mass of the solvent is 70% of that of the polyether-polycarbonate polyol) according to a molar ratio of 2.5:1, controlling the reaction temperature to be 35 ℃, and reacting at constant temperature for 24 hours.

(3) Preparation of a reactive sealant resin: mixing double bond modified polyether-polycarbonate, hydrogen-containing silane (trimethoxysilane) and a platinum metal catalyst (1% isopropyl alcohol solution of chloroplatinic acid), wherein the molar ratio of the hydrogen-containing silane to the double bond modified polyether-polycarbonate is 2:1, the mass of the platinum metal catalyst is 0.5% of the mass of the double bond modified polyether-polycarbonate, heating to 80 ℃, and reacting at constant temperature for 4 hours to obtain the reactive sealant resin.

Example 5

(1) Preparation of polyether-polycarbonate polyol: adding a hydroxyl-containing initiator (glycerol) into a high-pressure reaction kettle, adding propylene oxide into a bimetallic catalyst (zinc-cobalt double metal cyanide), then charging carbon dioxide into the mixture, controlling the reaction temperature to be 80 ℃, and carrying out constant-temperature reaction for 7 hours;

and then discharging unreacted carbon dioxide, adding ethylene oxide, controlling the reaction temperature to be 120 ℃, reacting for 1h at constant temperature, and removing unreacted epoxy compound through a scraper evaporator after the reaction is finished to prepare the polyether-polycarbonate polyol.

Wherein the mass ratio of the hydroxyl initiator to the epoxy compound is 0.5:10, the epoxy compound comprises ethylene oxide and propylene oxide, the mass ratio of the bimetallic catalyst to the epoxy compound is 1:1600, and the mass of the ethylene oxide accounts for 1% of the total mass of the epoxy compound.

(2) Preparation of double bond modified polyether-polycarbonate: mixing polyether-polycarbonate polyol and halogenated end capping agent (acryloyl chloride) containing double bonds according to a molar ratio of 1:5, adding pyridine as a catalyst, wherein the molar ratio of the catalyst to the polyether-polycarbonate polyol is 3:1, adding chloroform as a solvent (the mass of the solvent is 20% of that of the polyether-polycarbonate polyol), controlling the reaction temperature to be 10 ℃, and carrying out constant-temperature reaction for 36h.

Refining: filtering after the reaction is finished to obtain a double bond modified polyether-polycarbonate crude product, adding water for cleaning, wherein the mass ratio of the water to the double bond modified polyether-polycarbonate crude product is 3:1, stirring and mixing for 2 hours, separating water (and salt dissolved in water) in the double bond modified polyether-polycarbonate crude product by adopting a coalescing separator, and removing a reaction solvent by reduced pressure distillation to obtain the double bond modified polyether-polycarbonate.

(3) Preparation of a reactive sealant resin: mixing double bond modified polyether-polycarbonate, hydrogen-containing silane (triethoxysilane) and a platinum metal catalyst (1% of isopropyl alcohol solution of chloroplatinic acid), wherein the molar ratio of the hydrogen-containing silane to the double bond modified polyether-polycarbonate is 2:1, the mass of the platinum metal catalyst is 0.1% of the mass of the double bond modified polyether-polycarbonate, heating to 60 ℃, and reacting at constant temperature for 7 hours to obtain the reactive sealant resin.

Example 6

(1) Preparation of polyether-polycarbonate polyol: adding a hydroxyl-containing initiator (polyethylene glycol with the number average molecular weight of 600) into a high-pressure reaction kettle, adding a bimetallic catalyst (zinc-cobalt double metal cyanide), adding propylene oxide, then charging carbon dioxide, controlling the reaction temperature to be 50 ℃ under the pressure of 3MPa, and carrying out constant-temperature reaction for 6 hours;

and then discharging unreacted carbon dioxide, adding ethylene oxide, controlling the reaction temperature to be 40 ℃, reacting for 4 hours at constant temperature, and removing unreacted epoxy compounds through a scraper evaporator after the reaction is finished to prepare the polyether-polycarbonate polyol.

Wherein, the mass ratio of the hydroxyl initiator to the epoxy compound is 2:8, the epoxy compound comprises ethylene oxide and propylene oxide, the mass ratio of the bimetallic catalyst to the epoxy compound is 1:2100, and the mass of the ethylene oxide accounts for 10 percent of the total mass of the epoxy compound.

(2) Preparation of double bond modified polyether-polycarbonate: mixing polyether-polycarbonate polyol and halogenated end capping agent (acryloyl chloride) containing double bonds according to a molar ratio of 1:3, adding pyridine as a catalyst, wherein the molar ratio of the catalyst to the polyether-polycarbonate polyol is 2.5:1, adding dimethyl carbonate as a solvent (the mass of the solvent is 120 percent of that of the polyether-polycarbonate polyol), controlling the reaction temperature to be 60 ℃, and carrying out constant-temperature reaction for 12 hours.

Refining: filtering after the reaction is finished to obtain a double bond modified polyether-polycarbonate crude product, adding water for cleaning, stirring and mixing for 10 hours, separating water (and salt dissolved in water) in the double bond modified polyether-polycarbonate crude product by a coalescing separator, and removing a reaction solvent by reduced pressure distillation to obtain the double bond modified polyether-polycarbonate.

(3) Preparation of a reactive sealant resin: mixing double bond modified polyether-polycarbonate, hydrogen-containing silane (methyl diethoxysilane) and a platinum metal catalyst (1% of isopropyl alcohol solution of chloroplatinic acid), wherein the molar ratio of the hydrogen-containing silane to the double bond modified polyether-polycarbonate is 1:1, the mass of the platinum metal catalyst is 1% of that of the double bond modified polyether-polycarbonate, heating to 130 ℃, and reacting at constant temperature for 2 hours to obtain the reactive sealant resin.

Example 7

(1) Preparation of polyether-polycarbonate polyol: adding a hydroxyl-containing initiator (polypropylene glycol with the number average molecular weight of 400) into a high-pressure reaction kettle, adding a bimetallic catalyst (zinc-cobalt double metal cyanide), adding propylene oxide, then charging carbon dioxide, controlling the reaction temperature to be 60 ℃ under the pressure of 3MPa, and carrying out constant-temperature reaction for 43h;

Wherein the mass ratio of the hydroxyl initiator to the epoxy compound is 2:9, the epoxy compound comprises ethylene oxide and propylene oxide, the mass ratio of the bimetallic catalyst to the epoxy compound is 1:1400, and the mass of the ethylene oxide accounts for 5% of the total mass of the epoxy compound.

(2) Preparation of double bond modified polyether-polycarbonate: mixing polyether-polycarbonate polyol and halogenated end capping agent (methacryloyl chloride) containing double bonds according to a molar ratio of 1:3.5, adding pyridine as a catalyst, adding methylene dichloride as a solvent (the mass of the solvent is 50% of that of the polyether-polycarbonate polyol) according to a molar ratio of 2:1, controlling the reaction temperature to be 30 ℃, and reacting at constant temperature for 24 hours.

Example 8

This example provides a reactive sealant resin and a method for producing the same, which differ from example 1 only in that ethylene oxide is added after the remaining carbon dioxide is evolved, the mass of ethylene oxide accounting for 15% of the total mass of the epoxy compound, and the other conditions are the same as in example 1.

Comparative example 1

This comparative example provides a reactive sealant resin and a method for preparing the same, which is different from example 7 in that propylene oxide is added instead of ethylene oxide after the remaining carbon dioxide is evolved, and the other conditions are the same as in example 7.

Comparative example 2

This comparative example provides a reactive sealant resin and a method for producing the same, differing from example 7 in that carbon dioxide is not added, and other conditions are the same as example 7.

The polyether-polycarbonate polyols, double bond modified polyether-polycarbonates and reactive sealant resins provided in the examples and comparative examples were tested as follows.

Number average molecular weight and molecular weight distribution: the number average molecular weight and molecular weight distribution of the polyether-polycarbonates were tested by gel permeation chromatography (PL GPC 220), test procedure: 10mg of the sample was weighed, 1mL of tetrahydrofuran was added, and after filtration through a 0.22 μm nylon filter membrane, gel permeation chromatography was performed.

Structural test of links and end groups: the structure of the chain links and the end groups of the reactive sealant resin was tested by nuclear magnetic resonance spectroscopy, and the equipment was Bruker AVANCEIII 400MHz.

Calculation of the molar ratio of polyether mer to polycarbonate mer: ¹ in the H NMR spectrum, 5.0ppm and 4.2ppm belong to proton peaks on the methine and methylene groups of the polycarbonate chain segments, and 3.5 to 3.8ppm belong to proton peaks of the ether chain segments. And calculating the mole ratio of the polyether chain links to the polycarbonate chain links according to the integral area ratio of the relevant proton peaks in the spectrogram.

Double bond termination ratio: the test was carried out with reference to the determination of the degree of unsaturation of part 6 of the GB/T12008.6-2010 plastic polyether polyol.

Silane end-capping test: ¹ the silane end-capping ratios were calculated from the ratios of the peak areas for the H NMR spectra of 0.1ppm and 7.2ppm for the end-silane methylhydrogens and methoxyhydrogens. Hydroxyl value test: the test was performed with reference to the determination of the hydroxyl number of part 3 of the GB/T12008.3-2009 plastic polyether polyol.

Acid value test: the test was carried out with reference to the determination of the acid number of part 5 of the GB/T12008.5-2010 plastic polyether polyol.

The test results are shown in Table 1.

TABLE 1

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In Table 1, "-" represents that no test was performed.

The reactive sealant resins provided in examples and comparative examples were subjected to the following performance tests.

Mechanical properties: the molded bars were tested using a universal tensile tester.

Tensile shear strength test: the measurement of tensile shear strength of the adhesive (rigid material to rigid material) was performed with reference to GB/T7124/2008.

And (3) surface dry time test: reference GB/T13477.5 building sealant test method part 5: measurement of the tack free time was measured.

The test results are shown in Table 2.

TABLE 2

From the performance test data in tables 1 and 2, it is known that the reactive sealant resin provided in examples 1-8 has a tensile strength of 3.7-4.9 MPa, an elongation at break of 300% -370%, a tack free time of 15-20 min, a tensile shear strength of 2.1-2.8 MPa, and has the characteristics of good oxidation resistance, high mechanical strength, and high silane end capping rate.

When the amount of ethylene oxide added was too large (example 8) as compared with example 1, the molecular weight of the resulting reactive sealant resin was decreased, the silane end-capping rate was decreased, and the tensile strength and tensile shear strength were decreased, which proved to be better by adding a specific proportion of ethylene oxide.

When propylene oxide is added instead of ethylene oxide (comparative example 1) after unreacted carbon dioxide is released, the reactivity of the terminal group is reduced, resulting in lower double bond capping efficiency and siloxane capping efficiency, lower tensile strength and tensile shear strength, and increased open time, as compared with example 7.

When carbon dioxide is not added (comparative example 2), the double bond capping efficiency and the siloxane capping efficiency are low, and the resulting reactive sealant resin does not contain polycarbonate chain segments, and has reduced tensile strength and tensile shear strength, increased tack-free time, and reduced oxidation resistance, as compared with example 7.

The applicant states that the present invention is described by way of the above examples as a reactive sealant resin, and a method of preparing and using the same, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced by relying on the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims

1. A method for preparing a reactive sealant resin, the method comprising the steps of:

(1) Mixing a hydroxyl-containing initiator, a bimetallic catalyst, propylene oxide and carbon dioxide, performing a pre-reaction, discharging unreacted carbon dioxide after the reaction is finished, adding ethylene oxide, and performing a post-reaction to obtain polyether-polycarbonate polyol;

(2) Reacting polyether-polycarbonate polyol with halogenated end capping agent containing double bonds to obtain double bond modified polyether-polycarbonate;

(3) Reacting double bond modified polyether-polycarbonate with hydrogen-containing silane to obtain the reactive sealant resin;

the epoxy compounds in the step (1) are ethylene oxide and propylene oxide, wherein the mass percent of the ethylene oxide is less than or equal to 10 percent, and the mass percent of the ethylene oxide is not included in 0;

in the polyether-polycarbonate polyol, the molar ratio of polyether chain links to polycarbonate chain links is 1:0.1-1;

the mass ratio of the hydroxyl-containing initiator to the epoxy compound is 0.5-2:8-12;

the molar ratio of the halogenated end-capping agent containing double bonds to the polyether-polycarbonate polyol is 2-8:1;

and (3) the molar ratio of the hydrogen-containing silane to the double bond modified polyether-polycarbonate is 1-2:1.

2. The method according to claim 1, wherein the polyether-polycarbonate polyol in step (1) has a number average molecular weight of 6000 to 280000 g/mol.

3. The method of claim 1, wherein the polyether-polycarbonate polyol has a functionality of 2 or 3.

4. The method of claim 1, wherein the polyether-polycarbonate polyol has a molecular weight distribution of 1.1 to 2.5.

5. The method according to claim 1, wherein the molar ratio of polyether segments to polycarbonate segments in the polyether-polycarbonate polyol is 1:0.2 to 0.5.

6. The method of claim 1, wherein the hydroxyl-containing starter of step (1) comprises a small molecule polyol and/or a polymer polyol.

7. The process according to claim 1, wherein the hydroxyl-containing initiator has a number average molecular weight of 600 or less.

8. The method according to claim 6, wherein the hydroxyl group-containing initiator comprises any one or a combination of at least two of ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, and trimethylolpropane.

9. The method according to claim 8, wherein the hydroxyl group-containing initiator is polyethylene glycol and/or polypropylene glycol.

10. The method of preparation of claim 1, wherein the bimetallic catalyst comprises zinc-cobalt double metal cyanide.

11. The preparation method of claim 1, wherein the mass ratio of the bimetallic catalyst to the epoxy compound is 1:100-2000.

12. The preparation method according to claim 1, wherein the temperature of the preliminary reaction is 40-120 ℃, and the time of the preliminary reaction is 1-10 hours.

13. The method according to claim 12, wherein the temperature of the preliminary reaction is 50 to 100 ℃.

14. The method according to claim 12, wherein the time of the preliminary reaction is 2 to 8 hours.

15. The method according to claim 1, wherein the pressure of the carbon dioxide is maintained at 0.5 to 4.0MPa throughout the pre-reaction.

16. The method according to claim 15, wherein the pressure of carbon dioxide is maintained at 1 to 3MPa throughout the pre-reaction.

17. The preparation method according to claim 1, wherein the temperature of the post reaction is 40-120 ℃, and the time of the post reaction is 1-10 hours.

18. The method according to claim 17, wherein the temperature of the post reaction is 50-100 ℃.

19. The method of claim 17, wherein the post reaction time is 2-8 hours.

20. The method according to claim 1, wherein the halogenated blocking agent having a double bond in step (2) comprises acryl chloride and/or methacryl chloride.

21. The process of claim 1, wherein the reaction of step (2) is carried out over a catalyst comprising pyridine.

22. The method of claim 1, wherein the reaction of step (2) is performed in a solvent comprising any one or a combination of at least two of dichloromethane, chloroform, tetrahydrofuran, or dimethyl carbonate.

23. The method according to claim 1, wherein the molar ratio of the halogenated blocking agent containing a double bond to the polyether-polycarbonate polyol is 2 to 5:1.

24. The method of claim 21, wherein the molar ratio of the catalyst to the polyether-polycarbonate polyol is 1-3:1.

25. The method of claim 24, wherein the molar ratio of catalyst to polyether-polycarbonate polyol is 2:1.

26. The method according to claim 22, wherein the solvent is 20 to 120% by mass based on 100% by mass of the polyether-polycarbonate polyol.

27. The method according to claim 26, wherein the solvent is 50 to 100% by mass based on 100% by mass of the polyether-polycarbonate polyol.

28. The preparation method according to claim 1, wherein the reaction temperature in the step (2) is 10-60 ℃ and the reaction time is 12-36 h.

29. The method of claim 28, wherein the temperature of the reaction in step (2) is 20-40 ℃.

30. The method of claim 28, wherein the reaction time in step (2) is 18 to 30 hours.

31. The method according to claim 1, wherein the step (2) further comprises a step of refining.

32. The method of preparing according to claim 31, wherein the refining comprises the steps of: filtering to obtain a double bond modified polyether-polycarbonate crude product, adding water for cleaning, removing water by using a coalescing separator, and removing a solvent to obtain the double bond modified polyether-polycarbonate.

33. The method of claim 32, wherein the time for cleaning is 2-12 hours.

34. The method of claim 32, wherein the mass ratio of water to double bond modified polyether-polycarbonate crude product is 0.3-3:1.

35. The method according to claim 34, wherein the mass ratio of the water to the double bond modified polyether-polycarbonate raw product is 0.5 to 1.5:1.

36. The method of claim 1, wherein the hydrogen-containing silane of step (3) comprises any one or a combination of at least two of trimethoxysilane, triethoxysilane, methyldimethoxysilane, and methyldiethoxysilane.

37. The method of claim 36, wherein the hydrogen-containing silane comprises methyldimethoxysilane and/or trimethoxysilane.

38. The process of claim 1, wherein the reaction of step (3) is carried out in the presence of a hydrosilylation catalyst.

39. The method of claim 38, wherein the hydrosilylation catalyst is a platinum metal catalyst.

40. The method according to claim 38, wherein the mass of the hydrosilylation catalyst is 0.1% -1% of the mass of the double bond modified polyether-polycarbonate.

41. The preparation method according to claim 1, wherein the reaction temperature in the step (3) is 60-130 ℃, and the reaction time is 2-7 hours.

42. A reactive sealant resin prepared by the method of any one of claims 1-41.

43. A reactive sealant comprising the reactive sealant resin of claim 42.