CN113512393A - Soaking-resistant flame-retardant single-component silane modified polyether sealant and preparation method thereof - Google Patents
Soaking-resistant flame-retardant single-component silane modified polyether sealant and preparation method thereof Download PDFInfo
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- CN113512393A CN113512393A CN202110862880.3A CN202110862880A CN113512393A CN 113512393 A CN113512393 A CN 113512393A CN 202110862880 A CN202110862880 A CN 202110862880A CN 113512393 A CN113512393 A CN 113512393A
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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
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention discloses a water-immersion-resistant flame-retardant single-component silane modified polyether sealant which comprises the following components in parts by weight: 100 parts of silane-terminated modified polyether; 8-15 parts of a plasticizer; 18-40 parts of pigment and filler; 12-36 parts of a flame retardant; 1-6 parts of a thixotropic agent; 0.02-1 part of ultraviolet absorbent; 0.02-1 part of ultraviolet stabilizer; 2-6 parts of a crosslinking agent; 0.2-2 parts of a water removing agent; 1-4 parts of a self-made tackifier; 0.1-0.8 part of catalyst; the self-made tackifier is organosilicon modified epoxy resin synthesized by reacting organosilicon oligomer with at least two hydrolyzable alkoxy silanes at one end with epoxy resin, wherein alkoxy is methoxy, ethoxy or propyl; the invention also discloses a preparation method of the sealant. The invention improves the soaking resistance, flame retardance and bonding performance of the single-component modified silane polyether sealant so as to simultaneously meet the dual requirements of buildings on the waterproof performance and the flame retardance of the sealant.
Description
Technical Field
The invention relates to the field of sealants, in particular to a water-immersion-resistant flame-retardant single-component silane modified polyether sealant and a preparation method thereof.
Background
The assembly type building is one of the main directions of future building development, along with the development of prefabrication, large-scale, high-rise, underground, diversification and long service life of the modern assembly type building, the performance and the quality of the sealant for the building are higher and higher, and particularly, the requirement of the building industry on the waterproof and fireproof levels is higher and higher, so that the requirements on the waterproof performance and the flame retardant performance of the used building sealant are higher and higher; currently, polysulfide sealant, silicone sealant and polyurethane sealant widely applied to the building industry have some defects, such as low curing speed, easy aging and hardening, lack of durability, strong pungent odor during curing, environmental pollution and health hazard; the polyurethane building sealant is low in price, excellent in adhesion and excellent in deformation adaptability, but the structure of the polyurethane building sealant contains a large number of urethane bonds, so that the polyurethane building sealant is seriously insufficient in ultraviolet resistance and the like; silicone adhesive is excellent in acid and alkali resistance and weather resistance, but easily contaminates adjacent parts, and has poor surface decoration properties. However, the traditional modified silane polyether sealant has poor water resistance and low strength compared with epoxy adhesives, polyurethane adhesives, acrylic adhesives and the like, and the application field of the traditional modified silane polyether sealant is greatly limited, so that the research on the sealant with excellent water immersion resistance, flame resistance and excellent performance has very important significance.
Disclosure of Invention
The invention aims to overcome at least one defect (deficiency) of the prior art and provides the soaking-resistant flame-retardant single-component silane modified polyether sealant and the preparation method thereof, so that the soaking resistance, the flame resistance and the bonding performance of the single-component modified silane polyether sealant are improved, and the dual requirements of buildings on the waterproof performance and the flame retardant performance of the sealant are met.
The invention adopts the technical scheme that a water-immersion-resistant flame-retardant single-component silane modified polyether sealant is provided, which comprises the following components in parts by weight:
the self-made tackifier is organosilicon modified epoxy resin synthesized by reacting organosilicon oligomer with at least two hydrolyzable alkoxy silanes at one end with epoxy resin, wherein the alkoxy is methoxy, ethoxy or propyl;
the self-made tackifier is prepared by the following method:
s1, mixing the organic silicon oligomer and a solvent according to a ratio, heating the mixture to 45-55 ℃ while stirring, preserving heat, dropwise adding hydrochloric acid according to a ratio to react, after the reaction is carried out for 2-3 hours, sequentially carrying out atmospheric distillation and reduced pressure distillation on the mixture, and cooling to room temperature to obtain the incompletely hydrolyzed organic silicon oligomer;
s2, mixing the epoxy resin and the solvent according to the proportion, heating to 60-80 ℃ while stirring, and then preserving heat to completely dissolve the epoxy resin;
s3, mixing the incompletely hydrolyzed organic silicon oligomer prepared in the step S1 with the completely dissolved epoxy resin prepared in the step S2, adding a modified catalyst into the mixture according to the proportion, heating to 130-160 ℃ while stirring to separate the solvent, then carrying out heat preservation reaction for 1-2 hours, and cooling to below 40-60 ℃ after the reaction is finished, thus obtaining the self-made tackifier.
Preferably, the hydrochloric acid is a hydrochloric acid solution with the mass portion of 36-38%.
In the technical scheme, organosilicon modified epoxy resin is prepared by reacting organosilicon oligomer containing a plurality of unhydrolyzed alkoxy groups with epoxy resin and is used as a silane coupling agent for tackifying the sealant, a certain amount of active alkoxy groups, epoxy groups and hydroxyl groups are reserved on the molecular structure of the prepared organosilicon modified epoxy resin, so that the organosilicon modified epoxy resin has the excellent adhesive property of the epoxy resin while the characteristic of hydrolyzable active alkoxy groups is reserved, and the reaction mechanism of the organosilicon oligomer containing the unhydrolyzed alkoxy groups and the epoxy resin is as shown in formula 1; the active alkoxy of the self-made tackifier gives full play to the bridging coupling effect of the alkoxy, the hydrolyzed epoxy can be subjected to condensation reaction with hydroxyl on a cement base surface, and can be condensed with terminal hydroxyl formed by hydrolyzing the silyl-terminated modified polyether to form a cross-linked network elastomer, meanwhile, epoxy groups and incompletely reacted hydroxyl of the self-made tackifier have excellent bonding performance on the cement base material, and a bonding part has better water resistance, the bonding performance cannot be reduced after water is soaked, and the bonding failure conditions such as stripping, falling and the like are not easy to occur, so that the problems of weak bonding and poor water resistance of the traditional single-component silane modified polyether sealant to the cement base material are solved, and the construction step that a primer needs to be applied in advance to increase the adhesive force of the sealant when the traditional single-component silane modified polyether sealant is adopted is also omitted; the addition of the flame retardant can endow the sealant with heat resistance, so that the sealant has high-efficiency flame retardant effect and can simultaneously meet the dual requirements of high-rise buildings on water resistance and flame retardance; the ultraviolet absorber and the ultraviolet stabilizer are matched to improve the ultraviolet resistance of the sealant and improve the weather resistance of the sealant; the cross-linking agent can be hydrolyzed with the silyl-terminated modified polyether to form hydroxyl-terminated groups for condensation reaction to form a three-dimensional reticular elastomer, and the cross-linking reaction density or the properties such as tensile modulus, elongation at break and the like of the system are further adjusted to improve the physical properties of the sealant.
Formula 1:
in the formula, R is
Further, the epoxy resin is one or a mixture of two of E51 epoxy resin and E20 epoxy resin, and/or the modification catalyst is tetrabutyl orthotitanate, and/or the solvent is xylene.
Furthermore, the weight ratio of the organic silicon oligomer, the epoxy resin, the solvent and the modified catalyst is (30-40): 60-70): 75-85): 0.01-1.
Preferably, the weight ratio of the silicone oligomer, the epoxy resin, the solvent and the modification catalyst is 35:65:80: 0.02.
Further, the end silane modified polyether is one or two mixtures of ethoxy silane end-capped polypropylene oxide ether or methoxy silane end-capped polypropylene oxide ether; the ethoxysilane or methoxysilane contained in the polyoxypropylene ether is hydrolyzable siloxy, forms terminal hydroxyl after hydrolysis, and can be condensed with active alkoxy of a self-made tackifier to form a cross-linked network elastomer so as to improve the physical properties of the sealant, such as elasticity, adhesiveness and the like.
Further, the plasticizer is one or more of diisooctyl phthalate, diisononyl phthalate, alkyl sulfonate or low molecular weight polyether, and/or the pigment and filler is one or more of nano calcium carbonate, talcum powder, fumed silica, carbon black and titanium dioxide.
Further, the flame retardant is one or a mixture of two of organic montmorillonite and ammonium polyphosphate.
In the technical scheme, the organic montmorillonite has good compatibility with the sealant system, can avoid the problem that the performance of the sealant is reduced due to the instability of the system caused by excessive addition of the flame retardant, and has a thickening effect, so that the effect of the thixotropic agent can be exerted, and the anti-sagging or anti-deformation effect is improved; the ammonium polyphosphate with small polymerization degree has larger hygroscopicity, so that the ammonium polyphosphate can absorb moisture in the air after construction to accelerate the water vapor to enter the colloid, thereby improving the deep curing speed of the sealant.
Furthermore, the flame retardant is a compound of organic montmorillonite and ammonium polyphosphate, and the weight ratio of the organic montmorillonite to the ammonium polyphosphate is 1 (2-7).
Preferably, the organo montmorillonite is a nanoscale organo montmorillonite.
In the technical scheme, the flame retardant with higher-efficiency flame-retardant effect is obtained by compounding the organic montmorillonite and the ammonium polyphosphate, and the ammonium polyphosphate is gradually decomposed into phosphoric acid (H) by heating at high temperature in the flame-retardant process3PO4) Metaphosphoric acid (HPO)3) Strong acids such as polymetaphosphoric acid, etc. which can promote the dehydration and charring of polymer, and the water produced during the dehydration can lower the temperature of condensed phase and the concentration of combustible in diluted gas phase, so as to obtain excellent fire retarding effectThe montmorillonite compounded ammonium polyphosphate can play a synergistic role, promotes the thermal degradation reaction of the ammonium polyphosphate, advances the reaction, and enables the polymer to be dehydrated more quickly, so that the thermal degradation of the protected material is effectively delayed, and the flame retardant property of the product is effectively improved.
Further, the thixotropic agent is one or more of modified hydrogenated castor oil, fumed silica and polyamide wax, and/or the ultraviolet absorbent is one or more of UV-531, UV-327, HTP and UV-P, and/or the ultraviolet stabilizer is Tinuvin 770.
Further, the cross-linking agent is one or more of methyl trimethoxy silane, butyl trimethoxy silane or phenyl trimethoxy silane, and/or the water removing agent is vinyl trimethoxy silane, and/or the catalyst is one or a composition of more than any two of dibutyltin dilaurate, dimethyltin dilaurate, dibutyltin diacetate or stannous octoate-laurylamine.
The invention also provides a preparation method of the soaking-resistant flame-retardant single-component silane modified polyether sealant, which comprises the following steps:
a1, mixing the silane-terminated modified polyether, the plasticizer and the pigment and filler according to the proportion, and stirring for 15-25 min;
a2, adding an ultraviolet absorbent, an ultraviolet stabilizer and a thixotropic agent into the mixture obtained in the step A1 according to a ratio, mixing and stirring for 15-25 min, heating to 100-110 ℃ while stirring, preserving heat, dehydrating for 3-4 h under the environment that the relative vacuum degree is-0.08-0.1 MPa, and reducing the temperature to below 50 ℃ to obtain a dehydrated product;
a3, adding organic montmorillonite and ammonium polyphosphate into the dehydration product prepared in the step A2 according to the proportion, stirring for 5-15 min, and then vacuumizing and stirring for 10-20 min;
a4, adding a cross-linking agent, a water removing agent and a self-made tackifier into the mixture obtained in the step A3 according to the proportion, and vacuumizing and stirring for 5-15 min;
and A5, adding a catalyst into the mixture obtained in the step A4 according to a ratio, vacuumizing, stirring for 15-25 min, and then filling nitrogen for protection to obtain the water-immersion-resistant flame-retardant single-component silane-modified polyether sealant.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the self-made tackifier containing active alkoxy, epoxy group and hydroxyl is prepared by reacting the organic silicon oligomer containing unhydrolyzed alkoxy with the epoxy resin, so that the water resistance and the bonding performance of the single-component silane modified polyether sealant are improved, a primer is not required to be applied in advance before construction, a larger bonding strength can be obtained, the bonding part can still keep better water soaking bonding performance after long-term water soaking, and the bonding failure conditions such as stripping, falling and the like are not easy to occur;
(2) the flame retardant is prepared by compounding organic montmorillonite with ammonium polyphosphate, which has good system compatibility, so that a more efficient flame retardant effect can be obtained, the thermal degradation of a protected material is effectively delayed, the flame retardant level of the sealant is improved, the organic montmorillonite and the ammonium polyphosphate can also respectively play roles of a thixotropic agent and promoting deep curing, the addition of other additives can be reduced, the sealant system is stable, and the performance of the sealant is prevented from being reduced due to excessive additives;
(3) the sealant has excellent physical properties such as elasticity, adhesiveness and the like through a plurality of component distribution ratios, has good weather resistance, and is more suitable for adhesion of building assembly materials.
Detailed Description
The endpoints of the ranges and any values disclosed herein are limited to the precise range or value. For ranges of values, one or more new ranges of values may be obtained by combining the endpoints of each range, the endpoints of each range and the individual values, and the individual values with each other, and these ranges of values are considered to be specifically disclosed herein.
The preparation methods used in the following examples are all conventional methods unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Wherein the silyl-terminated modified polyether is silyl-terminated modified polyether S303H available from Japan and is terminated with dimethoxysilyl groups, and has a viscosity of 13 Pa.S;
the plasticizer was an alkyl sulfonate ester available from nissan Mesamoll, germany;
the pigment and filler are nano calcium carbonate purchased from Guangxi Huana new material science and technology limited company;
the thixotropic agent is polyamide wax from Huanyu chemical industry;
the ultraviolet absorber was UV-327 available from sublimation Co., Ltd, of Dongguan city;
the UV stabilizer was Tinuvin770 available from sublimation Co., Ltd, of Dongguan;
the cross-linking agent is methyl trimethoxy silane purchased from New Material Ltd of New blue sky in Hubei;
the water removing agent is vinyl trimethoxy silane purchased from New Material Ltd of New blue sky in Hubei;
the catalyst is dibutyltin dilaurate purchased from Jiangsu Haolong chemical Co., Ltd;
the fire retardant is organic montmorillonite OMMT purchased from Hubei Furrida chemical technology Co., Ltd and ammonium polyphosphate purchased from Mingkai Fine chemical Co., Ltd.
Example 1
The embodiment provides a water-immersion-resistant flame-retardant single-component silane modified polyether sealant which comprises the following components in parts by weight:
the organic silicon modified epoxy resin is synthesized by reacting an organic silicon oligomer of the self-made monomethyl triethoxysilane with epoxy resin E51, the modified catalyst is tetrabutyl orthotitanate, and the solvent is xylene; 35:65:80:0.02.
The self-made tackifier is prepared by the following method:
s1, mixing the organic silicon oligomer and a solvent according to a ratio, heating the mixture to 50 ℃ while stirring, preserving heat, dropwise adding hydrochloric acid with the mass fraction of 38% according to the ratio for reaction, after the reaction is carried out for 2.5 hours, sequentially carrying out normal pressure distillation and reduced pressure distillation on the mixture, distilling off ethanol and part of water generated by the reaction, and then cooling to room temperature to obtain the organic silicon oligomer which is not completely hydrolyzed;
s2, mixing the epoxy resin and the solvent according to the proportion, heating to 70 ℃ while stirring, and then preserving heat to completely melt the epoxy resin;
s3, mixing the incompletely hydrolyzed organic silicon oligomer prepared in the step S1 with the completely melted epoxy resin prepared in the step S2, adding a modified catalyst into the mixture according to the proportion, heating to 150 ℃ while stirring to separate the solvent, then carrying out heat preservation reaction for 1.5h, and cooling to below 50 ℃ after the reaction is finished, thus obtaining the self-made tackifier.
The preparation method of the soaking-resistant flame-retardant single-component silane modified polyether sealant comprises the following steps:
a1 adding silane-terminated modified polyether, plasticizer and pigment and filler into a reaction kettle with a high-speed dispersion disc and a heating jacket, mixing, and stirring for 20 min;
a2, adding an ultraviolet absorbent, an ultraviolet stabilizer and a thixotropic agent into the mixture obtained in the step A1 according to a ratio, mixing and stirring for 20min, heating to 100-110 ℃ while stirring, preserving heat, dehydrating for 3-4 h under the environment that the relative vacuum degree is-0.08-0.1 MPa, and reducing the temperature to below 50 ℃ to obtain a dehydrated product;
a3, adding organic montmorillonite and ammonium polyphosphate into the dehydration product prepared in the step A2 according to the proportion, stirring for 10min, and then vacuumizing and stirring for 15 min;
a4 adding a cross-linking agent, a water removing agent and a self-made tackifier into the mixture obtained in the step A3 according to the proportion, and vacuumizing and stirring for 10 min;
and A5, adding a catalyst into the mixture obtained in the step A4 according to a ratio, vacuumizing, stirring for 20min, and then filling nitrogen for protection to obtain the water-immersion-resistant flame-retardant single-component silane modified polyether sealant.
Example 2
The embodiment provides a water-immersion-resistant flame-retardant single-component silane-modified polyether sealant, wherein a preparation method of a self-made tackifier and a preparation method of the water-immersion-resistant flame-retardant single-component silane-modified polyether sealant are basically the same as those in embodiment 1, and the embodiment is different from embodiment 1 in that the water-immersion-resistant flame-retardant single-component silane-modified polyether sealant comprises the following components in parts by weight:
the self-made tackifier is organosilicon modified epoxy resin synthesized by reacting organosilicon oligomer of monomethyl triethoxysilane with epoxy resin E51, the modified catalyst is tetrabutyl orthotitanate, and the solvent is xylene; the weight ratio of the organic silicon oligomer, the epoxy resin, the solvent and the modified catalyst is 35:65:80: 0.02.
Example 3
The embodiment provides a water-immersion-resistant flame-retardant single-component silane-modified polyether sealant, wherein a preparation method of a self-made tackifier and a preparation method of the water-immersion-resistant flame-retardant single-component silane-modified polyether sealant are basically the same as those in embodiment 1, and the embodiment is different from embodiment 1 in that the water-immersion-resistant flame-retardant single-component silane-modified polyether sealant comprises the following components in parts by weight:
the self-made tackifier is organosilicon modified epoxy resin synthesized by reacting organosilicon oligomer of monomethyl triethoxysilane with epoxy resin E51, the modified catalyst is tetrabutyl orthotitanate, and the solvent is xylene; the weight ratio of the organic silicon oligomer, the epoxy resin, the solvent and the modified catalyst is 35:65:80: 0.02.
Example 4
The embodiment provides a water-immersion-resistant flame-retardant single-component silane-modified polyether sealant, wherein a preparation method of a self-made tackifier and a preparation method of the water-immersion-resistant flame-retardant single-component silane-modified polyether sealant are basically the same as those in embodiment 1, and the embodiment is different from embodiment 1 in that the water-immersion-resistant flame-retardant single-component silane-modified polyether sealant comprises the following components in parts by weight:
the self-made tackifier is organosilicon modified epoxy resin synthesized by reacting organosilicon oligomer of monomethyl triethoxysilane with epoxy resin E51, the modified catalyst is tetrabutyl orthotitanate, and the solvent is xylene; the weight ratio of the organic silicon oligomer, the epoxy resin, the solvent and the modified catalyst is 35:65:80: 0.02.
Comparative example 1
The comparative example provides a single-component silane modified polyether sealant, the composition and the preparation method of which are basically the same as those of the example 1, and the difference between the single-component silane modified polyether sealant and the example 1 is that ammonium polyphosphate is adopted to replace the organic montmorillonite in an equivalent manner in the comparative example.
Comparative example 2
The comparative example provides a single-component silane modified polyether sealant, the composition and the preparation method of which are basically the same as those of the example 1, and the difference between the single-component silane modified polyether sealant and the example 1 is that the ammonium polyphosphate is replaced by the organic montmorillonite in an equivalent manner.
Comparative example 3
The comparative example provides a single-component silane modified polyether sealant, the composition and the preparation method of which are basically the same as those of the example 1, and the difference between the single-component silane modified polyether sealant and the example 1 is that aluminum hydroxide is adopted to replace ammonium polyphosphate and organic montmorillonite in an equivalent manner.
Comparative example 4
The comparative example provides a single-component silane modified polyether sealant, the composition and the preparation method of which are basically the same as those of the example 1, and the difference is that the comparative example does not contain organic montmorillonite or ammonium polyphosphate.
Comparative example 5
The comparative example provides a single-component silane-modified polyether sealant, the composition and the preparation method of which are basically the same as those of example 1, and the difference is that the self-made tackifier prepared in example 1 is not contained in the comparative example.
Comparative example 6
The comparative example provides a single-component silane modified polyether sealant, the composition and the preparation method of which are basically the same as those of the example 1, and the difference is that the conventional silane coupling agent gamma-aminopropyl triethoxysilane is adopted in the comparative example to replace the self-made adhesive in the example 1.
Comparative example 7
The comparative example provides a single-component silane modified polyether sealant, the composition and the preparation method of which are basically the same as those of the example 1, and the difference is that the conventional silane coupling agent gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane is adopted to replace the self-made adhesive in the example 1.
The single-component silane modified polyether sealants prepared in examples 1 to 4 and comparative examples 1 to 5 were subjected to performance tests, and the tensile strength, elongation at break and elastic recovery rate of the sealant were evaluated according to GB/T5281998 determination of tensile stress strain performance of vulcanized rubber and thermoplastic rubber, weather resistance of the sealant was evaluated according to GB/T52816585 and 1996 test method of vulcanization artificial weathering (fluorescent ultraviolet rays), and flame retardancy of the sealant was evaluated according to UL-94 standard. The test performance is shown in table 1.
Table 1:
as can be seen from the comparison of the table above, the sealant products of examples 1 to 4 have excellent physical properties, good weather resistance, no cracking after being irradiated by ultraviolet rays for 3000h, and excellent water resistance and flame retardant property, which are superior to those of comparative examples 1 to 4.
Comparative example 1 does not contain the organic montmorillonite of example 1, so the flame retardance of the prepared sealant is reduced, and the flame retardant grade is V-1; comparative example 2 does not contain the ammonium polyphosphate of example 1, the flame retardance of the prepared sealant is further reduced, and the flame retardant grade of the product is changed into V-2, because the ammonium polyphosphate has higher temperature required by thermal decomposition, when the ammonium polyphosphate is used alone, the ammonium polyphosphate is decomposed when the material gradually starts thermal degradation, and the polymer dehydrates slowly, so that the material cannot be comprehensively protected; comparative example 3 in the comparative example, aluminum hydroxide is used for replacing ammonium polyphosphate and organic montmorillonite in equal amount, the flame retardance of the prepared sealant is reduced to V-1, and the use of the aluminum hydroxide has certain influence on the physical performance and the performance is reduced to some extent; comparative example 4, the organic montmorillonite and the ammonium polyphosphate in the example 1 are removed at the same time, so that the flame retardant property is not achieved, and the combustion phenomenon occurs; compared with the comparative examples 1, 2 and 4, the organic montmorillonite and the ammonium polyphosphate are compounded, so that the organic montmorillonite and the ammonium polyphosphate play a synergistic role in promoting the thermal degradation reaction of the ammonium polyphosphate, advancing the decomposition reaction of the ammonium polyphosphate and enabling the polymer to dehydrate more quickly, thereby effectively delaying the thermal degradation of the protected material, and the flame retardant grade of the organic montmorillonite and ammonium polyphosphate compounded sealant product can be improved to V-0.
Comparative example 5 contains no self-made tackifier in example 1, the water-soaking adhesion is seriously reduced, a test piece tensile test shows a partial interface failure form after soaking in water for 7 days, and test surfaces show 100% interface failure after soaking in water for 15 days and above; comparative examples 6 and 7 use conventional silane coupling agents gamma-aminopropyltriethoxysilane and gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane to replace the self-made tackifier in example 1, the water resistance of the sealant is improved compared with that of comparative example 5, but the water-soaking adhesion is not ideal, a test piece tensile test is in a partial interface failure form after soaking for 15 days, a test piece tensile test is in an interface failure form after soaking for 30 days, and products of examples 1 to 5 are still in a cohesive failure form after soaking for 30 days, so that the sealant has more excellent water resistance and adhesion performance, can still maintain better water-soaking adhesion performance after soaking in water at the adhesion part, and is not easy to peel off, fall off and other adhesion failures, and the defects of poor water resistance and low strength of the conventional modified silane polyether sealant are overcome, can simultaneously meet the double requirements of high-rise buildings on water resistance and flame retardance.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the technical solutions of the present invention, and are not intended to limit the specific embodiments of the present invention. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention claims should be included in the protection scope of the present invention claims.
Claims (10)
1. The soaking-resistant flame-retardant single-component silane modified polyether sealant is characterized by comprising the following components in parts by weight:
the self-made tackifier is organosilicon modified epoxy resin synthesized by reacting organosilicon oligomer with at least two hydrolyzable alkoxysilanes with epoxy resin;
the self-made tackifier is prepared by the following method:
s1, mixing the organic silicon oligomer and a solvent according to a ratio, heating the mixture to 45-55 ℃ while stirring, preserving heat, dropwise adding hydrochloric acid according to a ratio to react, after the reaction is carried out for 2-3 hours, sequentially carrying out atmospheric distillation and reduced pressure distillation on the mixture, and cooling to room temperature to obtain the incompletely hydrolyzed organic silicon oligomer;
s2, mixing the epoxy resin and the solvent according to the proportion, heating to 60-80 ℃ while stirring, and then preserving heat to completely melt the epoxy resin;
s3, mixing the incompletely hydrolyzed organic silicon oligomer prepared in the step S1 with the completely melted epoxy resin prepared in the step S2, adding a modified catalyst into the mixture according to the proportion, heating to 130-160 ℃ while stirring to separate the solvent, then carrying out heat preservation reaction for 1-2 hours, and cooling to below 50 ℃ after the reaction is finished, thus obtaining the self-made tackifier.
2. The single-component silane-modified polyether sealant with water immersion resistance and flame retardance as claimed in claim 1, wherein the epoxy resin is one or a mixture of E51 epoxy resin and E20 epoxy resin; and/or the modified catalyst is tetrabutyl orthotitanate; and/or, the solvent is xylene; and/or the alkoxy is methoxy, ethoxy or propyl.
3. The soaking-resistant flame-retardant one-component silane-modified polyether sealant as claimed in claim 1 or 2, wherein the weight ratio of the silicone oligomer, the epoxy resin, the solvent and the modified catalyst is (30-40): (60-70): (75-85): 0.01-1.
4. The water-immersion-resistant flame-retardant single-component silane-modified polyether sealant as claimed in claim 1, wherein the silicone oligomer is at least one of monomethyltriethoxysilane, dimethyldiethoxysilane, and monophenyltriethoxysilane; and/or the end silane modified polyether is one or two mixture of ethoxy silane end-capped polypropylene oxide ether or methoxy silane end-capped polypropylene oxide ether.
5. The water-immersion-resistant flame-retardant one-component silane-modified polyether sealant as claimed in claim 1, wherein the plasticizer is one or more of diisooctyl phthalate, diisononyl phthalate, alkyl sulfonate or low molecular weight polyether, and/or the pigment and filler is one or more of nano calcium carbonate, talcum powder, fumed silica, carbon black and titanium dioxide.
6. The water-immersion-resistant flame-retardant single-component silane-modified polyether sealant as claimed in claim 1, wherein the flame retardant is one or a mixture of two of organic montmorillonite and ammonium polyphosphate.
7. The soaking-resistant flame-retardant single-component silane-modified polyether sealant as claimed in claim 6, wherein the flame retardant is a compound of organic montmorillonite and ammonium polyphosphate, and the weight ratio of the organic montmorillonite to the ammonium polyphosphate is 1 (2-7).
8. The single component silane modified polyether sealant with water immersion resistance and flame retardance as claimed in claim 1, wherein the thixotropic agent is one or more of modified hydrogenated castor oil, fumed silica and polyamide wax, and/or the ultraviolet absorber is one or more of UV-531, UV-327, HTP and UV-P, and/or the ultraviolet stabilizer is Tinuvin 770.
9. The one-component silane modified polyether sealant with water immersion resistance and flame retardance as claimed in claim 1, wherein the cross-linking agent is one or more of methyl trimethoxy silane, butyl trimethoxy silane or phenyl trimethoxy silane, and/or the water removing agent is vinyl trimethoxy silane, and/or the catalyst is one or a combination of any two of dibutyltin dilaurate, dimethyltin dilaurate, dibutyltin diacetate and stannous octoate-laurylamine.
10. The preparation method of the soaking-resistant flame-retardant one-component silane-modified polyether sealant as claimed in any one of claims 1 to 9, which is characterized by comprising the following steps:
a1, mixing the silane-terminated modified polyether, the plasticizer and the pigment and filler according to the proportion, and stirring for 15-25 min;
a2, adding an ultraviolet absorbent, an ultraviolet stabilizer and a thixotropic agent into the mixture obtained in the step A1 according to a ratio, mixing and stirring for 15-25 min, heating to 100-110 ℃ while stirring, preserving heat, dehydrating for 3-4 h under the environment that the relative vacuum degree is-0.08-0.1 MPa, and reducing the temperature to below 50 ℃ to obtain a dehydrated product;
a3, adding organic montmorillonite and ammonium polyphosphate into the dehydration product prepared in the step A2 according to the proportion, stirring for 5-15 min, and then vacuumizing and stirring for 10-20 min;
a4, adding a cross-linking agent, a water removing agent and a self-made tackifier into the mixture obtained in the step A3 according to the proportion, and vacuumizing and stirring for 5-15 min;
and A5, adding a catalyst into the mixture obtained in the step A4 according to a ratio, vacuumizing, stirring for 15-25 min, and then filling nitrogen for protection to obtain the water-immersion-resistant flame-retardant single-component silane-modified polyether sealant.
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