CN113527629B - Modified polyether resin for high-weather-resistance high-performance building outer wall and sealant - Google Patents
Modified polyether resin for high-weather-resistance high-performance building outer wall and sealant Download PDFInfo
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- CN113527629B CN113527629B CN202110661099.XA CN202110661099A CN113527629B CN 113527629 B CN113527629 B CN 113527629B CN 202110661099 A CN202110661099 A CN 202110661099A CN 113527629 B CN113527629 B CN 113527629B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
Abstract
The invention discloses a modified polyether resin for a high weather-resistant high-performance building outer wall, which is prepared by the following preparation method: uniformly mixing polyether polyol and organic polyisocyanate under the condition of completely no water vapor, and reacting under the action of a catalyst to obtain a polyurethane prepolymer; adding a polyol chain extender into the polyurethane prepolymer in an inert atmosphere to react to obtain a chain-extended polyurethane prepolymer; and adding an isocyanate silane blocking agent into the chain-extended polyurethane prepolymer for reaction, and obtaining the polyurethane after the reaction is completed. The modified polyether resin disclosed by the invention is organically combined by utilizing the advantages of various materials and matching with proper reaction conditions through improvement on a preparation method, so that the performances of the materials, such as tensile strength, elongation at break, adhesiveness after water ultraviolet aging and the like, are improved, and the requirements of long-term effective outer wall waterproofing can be met.
Description
Technical Field
The invention relates to the technical field of silane modified polyether, in particular to modified polyether resin for a high-weather-resistance high-performance building outer wall, and especially relates to sealant containing the modified polyether resin.
Background
Sealant is an indispensable material in the fields of construction, transportation and equipment assembly, and high-performance sealant is attracting more and more attention, and although the usage amount and cost of the sealant are small in proportion to the total amount of the application field, the sealant often plays a decisive role in product performance.
The silane modified polyether sealant (MS sealant for short) has the advantages of polyurethane sealant and silicone sealant, overcomes the defects of the polyurethane sealant and the silicone sealant, has excellent mechanical strength, finishing property and stain resistance, has no isocyanate and organic solvent in the product, and is a main development direction of novel sealants at home and abroad. For MS sealant used in the building industry, the MS sealant is exposed outdoors for a long time and needs to be subjected to comprehensive damage caused by factors such as illumination, cold and hot, wind and rain, bacteria and the like, and has high requirements on weather resistance and ultraviolet resistance, and only the sealant with good weather resistance and ultraviolet resistance can keep excellent sealing or bonding effect for a long time.
In the prior art, patent CN106589286a discloses a silane modified polyurethane resin and a method for preparing the same, which first reacts polyether glycol with isocyanate to generate NCO-terminated prepolymer, and then adds active H-functional mercaptopropyl trimethoxysilane for end capping. In the above-described method, the properties of the resulting polymer vary greatly due to the time and conditions of addition of the silane blocking agent, and thus the production process is not easily controlled. Patent CN102112571B discloses a pressure sensitive adhesive composition which reacts polyester polyol with isocyanate to form end-capped prepolymer to prepare solvent resistant adhesive, but cannot resist water outdoor for a long period of time and weather aging, and thus cannot meet the requirement of outdoor building water resistance. The MS resins sold in the market at present comprise typical products such as Brillouin S303H, wake E35 and the like, the physical properties of the products are common, degradation and hardening are easy to occur under outdoor climate conditions, and in China and the like, the exterior wall of a building is regulated to be re-glued for 10-15 years. Therefore, the conventional single-component silane modified polyether sealant in the prior art and the market has insufficient weather resistance, and cannot meet the long-term effective waterproof requirement of the outer wall.
Disclosure of Invention
In order to overcome the defects of the prior art, one of the purposes of the invention is to provide a modified polyether resin for a high-weather-resistance high-performance building outer wall, which has the performances of tensile strength, elongation at break, adhesiveness after water ultraviolet aging and the like superior to those of the conventional silane modified resin in the current market, has the advantages of high strength, high elongation, high weather resistance and the like, and can meet the requirement of effective outer wall water resistance for a long time.
The second object of the invention is to provide a sealant containing the modified polyether resin for the building outer wall with high weather resistance and high performance, which has the characteristics of small performance change after water ultraviolet aging, excellent weather resistance effect and the like.
One of the purposes of the invention is realized by adopting the following technical scheme:
the modified polyether resin for the high weather-resistant high-performance building outer wall is prepared by the following preparation method, and the preparation method comprises the following preparation steps:
s1: uniformly mixing polyether polyol and organic polyisocyanate under the condition of completely no water vapor, and reacting under the action of a catalyst to obtain a polyurethane prepolymer;
s2: adding a polyol chain extender into the polyurethane prepolymer in an inert atmosphere to react to obtain a chain-extended polyurethane prepolymer;
s3: and adding an isocyanate silane end-capping agent into the chain-extended polyurethane prepolymer for reaction, and obtaining the modified polyether resin for the building outer wall with high weather resistance and high performance after the reaction is finished.
Wherein in step S1, the molar ratio of polyether polyol to organic polyisocyanate is 1 (2.05-2.2), preferably the molar ratio of polyether polyol to organic polyisocyanate is 1:2.05. in step S2, the molar ratio of the polyol chain extender to the polyurethane prepolymer is (2-2.2): 1, preferably, the molar ratio of polyol chain extender to polyurethane prepolymer is 2:1. in step S3, the molar ratio of isocyanate silane blocking agent to chain-extended polyurethane prepolymer is 1: (0.95-1.2), preferably, the molar ratio of isocyanate silane blocking agent to chain extended polyurethane prepolymer is 1: (1-1.1).
Further, the modified polyether resin for the high weather-resistant high-performance building outer wall is prepared by a preparation method, which comprises the following preparation steps:
s1: uniformly mixing polyether polyol with a molar ratio of 1 (2.05-2.2) with organic polyisocyanate under the condition of completely no water vapor and at the temperature of 50-100 ℃, and reacting for 3-5 h under the action of a catalyst at the temperature of 60-130 ℃ to obtain polyurethane prepolymer;
s2: adding a polyol chain extender into the polyurethane prepolymer in an inert atmosphere at the temperature of 100-120 ℃ to react for 3-5 hours to obtain a chain-extended polyurethane prepolymer; wherein the molar ratio of the polyol chain extender to the polyurethane prepolymer is (2-2.2): 1, a step of;
s3: adding an isocyanate silane blocking agent into the chain-extended polyurethane prepolymer at the temperature of 65-90 ℃ to react for 2-3 hours, thus obtaining the modified polyether resin for the building outer wall with high weather resistance and high performance; wherein, the mol ratio of isocyanate silane end capping agent to chain-extended polyurethane prepolymer is 1: (0.95-1.2).
Preferably, in step S1, the mixing temperature of the polyether polyol and the organic polyisocyanate is 60 ℃ to 90 ℃ and the reaction temperature is 100 ℃ to 120 ℃; more preferably, the polyether polyol is mixed with the organic polyisocyanate at a temperature of 75 ℃ to 85 ℃ and the reaction temperature is 110 ℃ to 115 ℃. In step S2, the addition temperature of the polyol chain extender is 110-115 ℃. In step S3, the isocyanate silane blocking agent is added at a temperature of 70-85 ℃, preferably 78-82 ℃.
Further, the polyether polyol has a functionality of 2 to 3 and a number average molecular weight of 2000 to 30000. Since the hydroxyl value of the polyether polyol is a key parameter for predicting the viscosity of the prepolymer, determining the soft segment content and obtaining a resin finished product with stable performance, the hydroxyl value can be obtained by calculation through parameters such as functionality, number average molecular weight and the like. Preferably, the polyether polyol has a number average molecular weight of 12000-20000.
Further, the organic polyisocyanate is one or more of isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), 4' -dicyclohexylmethane diisocyanate (HMDI), and tetramethylxylylene diisocyanate (TMXDI). Preferably, the organic polyisocyanate is tetramethyl xylylene diisocyanate. Since tetramethyl xylylene diisocyanate is an aliphatic isocyanate, and its NCO is not bonded to an aromatic ring, it has excellent light stability and outdoor durability, and compared with other aliphatic isocyanates, it does not substantially undergo side reaction with a polyol, and it can greatly reduce the viscosity of a prepolymer, and at the same time, it does not substantially react with moisture, and the produced prepolymer has excellent flexibility and adhesion.
Further, the catalyst is one or two of tertiary amine catalyst and metal catalyst.
Preferably, the tertiary amine catalyst is one or more than two of N-methylmorpholine, N-ethylmorpholine and triethylamine; the metal catalyst is one or more of bismuth carboxylate, dibutyl tin dilaurate, dioctyl tin dicarboxylate, stannous octoate and stannous acetate.
Further, the polyol chain extender is an alkoxylated cyclohexanediol with reactive hydroxyl groups.
Further, the alkoxylated cyclohexanediol is an alkoxylated ortho-cyclohexanediol of structural formula (i):
wherein n is an integer of 1 to 5, and m is an integer of 1 to 5. That is, n is one of 1, 2, 3, 4 and 5, and m is one of 1, 2, 3, 4 and 5, and the values of n and m may be the same or different.
Further, n=1, m=1 in the alkoxylated ortho-cyclohexanediols of the formula (i). When n=1, m=1, the structural formula is the following formula (ii):
further, in step S1, before the polyether polyol is added, it is necessary to subject the polyether polyol to dehydration and degassing treatment at a temperature of 110 to 115 ℃ and under vacuum. Since polyisocyanates are extremely sensitive to water, trace amounts of water consume more isocyanate and also affect prepolymer viscosity and product physical properties, it is extremely important to control the moisture content of polyether polyols. Wherein the treatment time of dehydration and degassing is 3-4 h, and the moisture content is less than 300ppm after the dehydration and degassing treatment by a moisture meter. The preparation method of the specific polyurethane prepolymer comprises the following steps: and (3) under the condition of stirring, the temperature of 110-115 ℃ and vacuumizing, pumping polyether polyol to carry out dehydration and degassing treatment for 3-4 h, cooling to 75-85 ℃, adding organic polyisocyanate, stirring and mixing for 30min, heating to 110-115 ℃ and reacting for 3-5 h to obtain the polyurethane prepolymer.
Further, the isocyanate silane blocking agent is 3-isocyanatopropyl trimethoxysilane.
The second purpose of the invention is realized by adopting the following technical scheme:
the sealant comprises the modified polyether resin for the high-weather-resistance high-performance building outer wall.
Further, the addition amount of the modified polyether resin for the high weather-resistant high-performance building outer wall is 20% -40% of the total weight of the sealant.
Compared with the prior art, the invention has the beneficial effects that:
according to the modified polyether resin for the high weather-resistant and high-performance building outer wall, through improvement on a preparation method, polyether polyol and organic polyisocyanate are firstly adopted to react, under proper reaction conditions, polyurethane prepolymer with good outdoor flexibility and adhesiveness is obtained through reaction, then a polyol chain extender is added to conduct chain extension, so that heat resistance, hardness and elasticity of a product are further improved, and finally an isocyanate silane blocking agent is used for blocking, so that the high-strength, high-elongation and high weather-resistant silane modified polyether resin material is obtained.
The sealant has the characteristics of small performance change after water ultraviolet aging, excellent weather-proof effect and the like by adding the modified polyether resin.
Detailed Description
The present invention will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
The following are specific examples of the present invention, in which raw materials, equipment, etc. used are available in a purchase manner except for specific limitations.
In the following examples:
polyether polyol PREMINOL S4013F, available from Asahi Kabushiki Kaisha, has a functionality of 2 and a number average molecular weight of 12000;
polyether polyol PREMINOL S4318F, available from Asahi Kabushiki Kaisha, has a functionality of 2 and a number average molecular weight of 18000;
isophorone diisocyanate (IPDI), a popular product;
hexamethylene Diisocyanate (HDI), a popular product;
tetramethyl xylylene diisocyanate (TMXDI) has a molecular weight of 244.3 and is newly produced by ALLNEX in the United states.
Specific examples are as follows:
example 1:
the modified polyether resin for the high weather-resistant high-performance building outer wall is prepared by the following preparation method, and the preparation method comprises the following preparation steps:
s1: 1000g of polyether polyol PREMINOL S4318F is put into a reaction kettle, heated to 110 ℃, stirred, vacuumized, dehydrated and degassed for 3 hours, cooled to 85 ℃, then tetramethyl xylylene diisocyanate (TMXDI) is added, then 2g of bismuth carboxylate is added, stirred and mixed for 30 minutes at the reaction temperature of 85 ℃, then heated to 112 ℃ and reacted for 4 hours to obtain polyurethane prepolymer; wherein the molar ratio of the polyether polyol PREMINOL S4318F to the tetramethyl xylylene diisocyanate is 1:2.05;
s2: adding the alkoxylated o-cyclohexanediol into the polyurethane prepolymer under stirring, and stirring and mixing the mixture at 115 ℃ for reaction for 4 hours to obtain the chain-extended polyurethane prepolymer; wherein, the mole ratio of the alkoxylated o-cyclohexanediol to the polyurethane prepolymer is 2:1, a step of;
s3: cooling the obtained polyurethane prepolymer after chain extension to 82 ℃ under stirring, stirring and mixing with 3-isocyanatopropyl trimethoxy silane serving as an isocyanatosilane end-capping agent for reaction for 2 hours, cooling, and discharging under the protection of nitrogen to obtain silane modified polyether resin, wherein the molar ratio of the isocyanatosilane end-capping agent to the polyurethane prepolymer after chain extension is 1:1.
example 2:
the modified polyether resin for the high weather-resistant high-performance building outer wall is prepared by the following preparation method, and the preparation method comprises the following preparation steps:
s1: 1000g of polyether polyol PREMINOL S4318F is put into a reaction kettle, heated to 110 ℃, stirred, vacuumized, dehydrated and degassed for 3 hours, cooled to 85 ℃, then added with tetramethyl xylylene diisocyanate (TMXDI), stirred and mixed for 30 minutes at the reaction temperature of 85 ℃, then added with 3g of bismuth carboxylate, heated to 112 ℃ and reacted for 4 hours to obtain polyurethane prepolymer; wherein the molar ratio of the polyether polyol PREMINOL S4318F to the tetramethyl xylylene diisocyanate is 1:2.1;
s2: adding the alkoxylated o-cyclohexanediol into the polyurethane prepolymer under stirring, and stirring and mixing the mixture at 110 ℃ for reaction for 4 hours to obtain the chain-extended polyurethane prepolymer; wherein, the mole ratio of the alkoxylated o-cyclohexanediol to the polyurethane prepolymer is 2:1, a step of;
s3: cooling the obtained polyurethane prepolymer after chain extension to 82 ℃ under stirring, stirring and mixing with 3-isocyanatopropyl methyl dimethoxy silane serving as an isocyanatosilane end-capping agent, reacting for 2 hours, cooling, and discharging under the protection of nitrogen to obtain silane modified polyether resin, wherein the molar ratio of the isocyanatosilane end-capping agent to the polyurethane prepolymer after chain extension is 1:1.
example 3:
the modified polyether resin for the high weather-resistant high-performance building outer wall is prepared by the following preparation method, and the preparation method comprises the following preparation steps:
s1: 1000g of polyether polyol PREMINOL S4318F is put into a reaction kettle, heated to 110 ℃, stirred, vacuumized, dehydrated and degassed for 3 hours, cooled to 85 ℃, then isophorone diisocyanate (IPDI) is added, 3g of dibutyl tin dilaurate is added, stirred and mixed for 30 minutes at the reaction temperature of 85 ℃, then heated to 112 ℃ and reacted for 4 hours to obtain polyurethane prepolymer; wherein the molar ratio of the polyether polyol PREMINOL S4318F to the tetramethyl xylylene diisocyanate is 1:2.2;
s2: adding the alkoxylated o-cyclohexanediol into the polyurethane prepolymer under the stirring state, and stirring and mixing the mixture for reaction for 4 hours at 110 ℃ to obtain the chain-extended polyurethane prepolymer; wherein, the molar ratio of the alkoxylated o-cyclohexanediol to the polyurethane prepolymer is 2.2:1, a step of;
s3: cooling the obtained polyurethane prepolymer after chain extension to 82 ℃ under stirring, stirring and mixing with 3-isocyanatopropyl trimethoxy silane serving as an isocyanatosilane end-capping agent for reaction for 2 hours, cooling, and discharging under the protection of nitrogen to obtain silane modified polyether resin, wherein the molar ratio of the isocyanatosilane end-capping agent to the polyurethane prepolymer after chain extension is 1:1.1.
in the above embodiments, each material is not limited to the above-described components, each material may also be formed of other single components or multiple components described in the present invention, and the component content of each material is not limited to the above-described content, and the component content of each material may also be a combination of other component contents described in the present invention, which is not described herein.
Comparative example 1:
the modified polyether resin for the high weather-resistant high-performance building outer wall is prepared by the following preparation method, and the preparation method comprises the following preparation steps:
s1: 1000g of polyether polyol PREMINOL S4318F is put into a reaction kettle, heated to 110 ℃, stirred, vacuumized, dehydrated and degassed for 3 hours, cooled to 85 ℃, then added with tetramethyl xylylene diisocyanate (TMXDI), added with 2g of dibutyl tin dilaurate, stirred and mixed for 30 minutes at the reaction temperature of 85 ℃, then heated to 112 ℃ and reacted for 4 hours to obtain polyurethane prepolymer; wherein the molar ratio of the polyether polyol PREMINOL S4318F to the tetramethyl xylylene diisocyanate is 1:2.05;
s2: cooling the polyurethane prepolymer to 82 ℃ under stirring, stirring and mixing with 3-isocyanatopropyl trimethoxy silane serving as an isocyanatosilane end-capping agent for reaction for 2 hours, cooling, and discharging under the protection of nitrogen to obtain the required silane modified polyether resin, wherein the molar ratio of the isocyanatosilane end-capping agent to the chain-extended polyurethane prepolymer is 1:1.
comparative example 2:
in contrast to example 1, comparative example 2 uses 1,4 butanediol instead of the alkoxylated ortho-cyclohexanediol of example 1 as a chain extender, and the other components and preparation method are the same as in example 1.
Comparative example 3:
unlike example 1, comparative example 3 has a chain extension temperature of 130 ℃ in step S2, namely:
s2: adding the alkoxylated o-cyclohexanediol into the polyurethane prepolymer under stirring, and stirring and mixing the mixture at 130 ℃ for reaction for 4 hours to obtain the chain-extended polyurethane prepolymer; wherein, the mole ratio of the alkoxylated o-cyclohexanediol to the polyurethane prepolymer is 2:1.
other components and preparation methods were the same as in example 1.
Comparative example 4:
unlike example 1, the molar ratio of polyether polyol PREMINOL S4318F to tetramethyl xylylene diisocyanate in S1 of comparative example 4 was 1:3; the molar ratio of the alkoxylated o-cyclohexanediol to the polyurethane prepolymer in S2 is 3:1, other components and preparation methods were the same as in example 1.
Performance test:
1) Preparation of sealant
The silane-modified polyether resins obtained in examples 1 to 3 and comparative example 1 were added to a sealant material to prepare a sealant, and the sealant was prepared as follows:
s1: 200g of DIDP (diisodecyl phthalate) is put into a vacuum kneader, 300g of 200A nano calcium carbonate and 200g of LM2200 heavy calcium carbonate are added, and vacuum dehydration is carried out for 3 hours at 120 ℃ to prepare base rubber;
s2: 700g of the base adhesive is added into a high-speed dispersing machine, then 300 silane modified polyether resin and 10 vinyl trimethoxysilane are added, stirring is carried out for 30min, after uniform mixing, 10g of basf stabilizer B75, 10g of N- (beta-aminoethyl) -gamma-aminopropyl trimethyl (ethoxysilane), 10g of 1146 silane coupling agent and 2g of dibutyl tin dilaurate are added, and pumping and stirring are carried out for 30min, thus preparing the modified polyether sealant.
Test product 1
The silane modified polyether resin obtained in the embodiment 1 is adopted as the silane modified polyether resin in the sealant, the dosage is 300g, and the preparation method of the sealant is prepared by adopting the sealant preparation step.
Test product 2
A sealant, wherein the silane-modified polyether resin obtained in example 1 and example 2 is used as the silane-modified polyether resin, the silane-modified polyether resin used in example 1 is 150g, the silane-modified polyether resin used in example 2 is 150g, and the sealant is prepared by the sealant preparation method through the above steps.
Test product 3
The silane modified polyether resin obtained in the embodiment 3 is adopted as the silane modified polyether resin in the sealant, the dosage is 300g, and the preparation method of the sealant is prepared by adopting the sealant preparation step.
Test product 4
The silane modified polyether resin in the sealant is prepared by adopting the silane modified polyether resin obtained in the comparative example 1 with the dosage of 300g, and the preparation method of the sealant is prepared by adopting the preparation steps of the sealant.
Test product 5
The silane modified polyether resin in the sealant is prepared by adopting the silane modified polyether resin obtained in the comparative example 2 with the dosage of 300g, and the preparation method of the sealant is prepared by adopting the preparation steps of the sealant.
Test product 6
The silane modified polyether resin in the sealant is prepared by adopting the silane modified polyether resin obtained in the comparative example 3 with the dosage of 300g, and the preparation method of the sealant is prepared by adopting the preparation steps of the sealant.
Test product 7
The silane modified polyether resin in the sealant is prepared by adopting the silane modified polyether resin obtained in the comparative example 4 with the dosage of 300g, and the preparation method of the sealant is prepared by adopting the preparation steps of the sealant.
Test product 8
A sealant was prepared using 300g of a commercially available silane-modified polyether resin sample I as a silane-modified polyether resin, and the sealant was prepared by the above-described sealant preparation step.
The preparation method of the commercial silane modified polyether resin sample I is as follows:
1000g of bis (allyl polyether) polyol 8000 molecular weight, controlling the temperature of the material at 39-42 ℃, adding 2g of platinum catalyst, stirring for 0.5 hours, then continuing to add trimethoxysilane (hydrogen-containing silane), and keeping the temperature at 40 ℃ for 3 hours to obtain trimethoxysilyl terminated polyether resin.
Test product 9
A sealant was prepared using 300g of a commercially available silane-modified polyether resin sample II as a silane-modified polyether resin by the method described above.
The preparation method of the commercial silane modified polyether resin sample II is as follows:
1000g of 20000 polyether polyol with molecular weight is added into a kettle, the temperature of the material is controlled to be more than 85 ℃, and the mixture is stirred and dehydrated for 2 hours; 2g of dibutyl tin dilaurate is added, the temperature of the mixture is controlled at 80 ℃, then ALink35 is added, and the mixture is stirred and reacted for 3 hours to obtain the silane modified trimethoxy terminated polyether resin.
2) Performance detection
The detection was carried out according to JC/T881-2017 Standard of construction sealant for concrete joints, and the specific results are shown in Table 1 below.
TABLE 1 Performance test results
As can be seen from the above Table 1, the sealants of the test products 1 to 3 all achieved relatively excellent physical properties, including tensile strength, elongation, adhesion after water ultraviolet aging, and the like, which were superior to those of the conventional silane modified resins in the market, and the test products 1 to 3 were small in change in properties after water ultraviolet aging and excellent in weather resistance.
In addition, the test product 1 can be used as a high-modulus high-strength sealant, and is suitable for waterproof sealing of an outer wall; the tensile modulus of the test product 2 is lower than 0.4Mpa, and the test product can be used as a low-modulus high-strength product and is suitable for waterproof sealing of an outer wall. Compared with the test products 4-9, the test product 3 only has a small bonding failure area, and the performance of the test product for waterproof sealing of the outer wall is not affected.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention is not limited thereto, but any insubstantial changes and substitutions made by those skilled in the art on the basis of the present invention are intended to be within the scope of the present invention as claimed.
Claims (7)
1. The modified polyether resin for the building outer wall with high weather resistance and high performance is characterized by being prepared by a preparation method, wherein the preparation method comprises the following preparation steps of:
s1: under the condition of completely no water vapor, uniformly mixing polyether polyol with the molar ratio of 1 (2.05-2.2) with organic polyisocyanate, and reacting under the action of a catalyst to obtain polyurethane prepolymer; the organic polyisocyanate is tetramethyl xylylene diisocyanate;
s2: adding a polyol chain extender into the polyurethane prepolymer in an inert atmosphere at the temperature of 100-120 ℃ to react to obtain a chain-extended polyurethane prepolymer; the polyol chain extender is alkoxylated cyclohexanediol; wherein the molar ratio of the polyol chain extender to the polyurethane prepolymer is (2-2.2): 1, a step of;
s3: adding an isocyanate silane blocking agent into the chain-extended polyurethane prepolymer for reaction, and obtaining the modified polyether resin for the high weather-resistant high-performance building outer wall after the reaction is finished;
the alkoxylated cyclohexanediol is an alkoxylated ortho-cyclohexanediol of the structural formula (I), and the structural formula is:
（Ⅰ）
wherein n is an integer of 1 to 5, and m is an integer of 1 to 5.
2. The modified polyether resin for the exterior wall of the building with high weather resistance and high performance according to claim 1, wherein the modified polyether resin is prepared by a preparation method comprising the following preparation steps:
s1: uniformly mixing polyether polyol with a molar ratio of 1 (2.05-2.2) with organic polyisocyanate under the condition of completely no water vapor and at the temperature of 50-100 ℃, and reacting for 3-5 h under the action of a catalyst at the temperature of 60-130 ℃ to obtain polyurethane prepolymer;
s2: adding a polyol chain extender into the polyurethane prepolymer in an inert atmosphere at the temperature of 100-120 ℃ to react for 3-5 hours to obtain a chain-extended polyurethane prepolymer; wherein the molar ratio of the polyol chain extender to the polyurethane prepolymer is (2-2.2): 1, a step of;
s3: adding an isocyanate silane blocking agent into the chain-extended polyurethane prepolymer at the temperature of 65-90 ℃ to react for 2-3 hours, thus obtaining the modified polyether resin for the building outer wall with high weather resistance and high performance; wherein, the mol ratio of isocyanate silane end capping agent to chain-extended polyurethane prepolymer is 1: (0.95-1.2).
3. The modified polyether resin for external walls of buildings having high weather resistance and high performance according to claim 1, wherein the polyether polyol has a functionality of 2 to 3 and a number average molecular weight of 2000 to 30000.
4. The modified polyether resin for the exterior wall of the building with high weather resistance and high performance according to claim 1, wherein the catalyst is one or two of a tertiary amine catalyst and a metal catalyst.
5. The modified polyether resin for external walls of buildings having high weather resistance and high performance according to claim 1, wherein n=1 and m=1 in said alkoxylated o-cyclohexanediol of the formula (i).
6. The modified polyether resin for external walls of buildings having high weather resistance and high performance according to claim 1, wherein the polyether polyol is dehydrated and degassed at a temperature of 110 ℃ to 115 ℃ under vacuum condition before being added in step S1.
7. A sealant comprising the modified polyether resin for a high weather-resistant high-performance building exterior wall according to any one of claims 1 to 6.
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| CN116355377B (en) * | 2023-04-04 | 2023-11-03 | 中铁建华南建设(广州)高科技产业有限公司 | Silane modified polyether resin material, preparation method thereof and grouting material |
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