WO2019127239A1 - 一种低模量高粘附装配式建筑用硅烷改性聚醚胶及其制备方法 - Google Patents

一种低模量高粘附装配式建筑用硅烷改性聚醚胶及其制备方法 Download PDF

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WO2019127239A1
WO2019127239A1 PCT/CN2017/119482 CN2017119482W WO2019127239A1 WO 2019127239 A1 WO2019127239 A1 WO 2019127239A1 CN 2017119482 W CN2017119482 W CN 2017119482W WO 2019127239 A1 WO2019127239 A1 WO 2019127239A1
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Prior art keywords
polyether
vacuum
modified polyether
silane
low modulus
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PCT/CN2017/119482
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English (en)
French (fr)
Inventor
陈建军
付子恩
黄恒超
陈洋庆
龙飞
杨苏邯
刘光华
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广州市白云化工实业有限公司
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Priority to PCT/CN2017/119482 priority Critical patent/WO2019127239A1/zh
Priority to US16/770,864 priority patent/US11802229B2/en
Publication of WO2019127239A1 publication Critical patent/WO2019127239A1/zh

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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/022—Polycondensates containing more than one epoxy group per molecule characterised by the preparation process or apparatus used
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5026—Amines cycloaliphatic
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/72—Complexes of boron halides
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K3/40—Glass
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives

Definitions

  • the invention belongs to the field of building materials and manufacturing thereof, and particularly relates to a silane-modified polyether glue for low modulus and high adhesion assembly type building and a preparation method thereof.
  • the prefabricated building is built like a building block.
  • the main components of the house, especially the precast concrete PC components, are produced at the factory and assembled on site.
  • This production method has high construction efficiency, low resource and energy consumption, less environmental pollution, and on-site.
  • There are many advantages such as fewer construction workers and high capital equipment turnover. It has been well developed in countries such as Europe, America, and Japan. At present, China is also strongly supporting the development of fabricated buildings.
  • Premier Li Keqiang proposed in the two national conferences that the proportion of prefabricated buildings in new buildings in the next 10 years should reach 30%. Future assembled buildings will have better market prospects.
  • the sealant is the first line of defense for waterproof sealing, and its performance will directly affect the waterproof sealing effect. Because the joints of the prefabricated building will change displacement under the action of thermal expansion and contraction, wind pressure and foundation settlement of the prefabricated components, it is necessary to select a sealant product with low modulus and high displacement capability.
  • the silane-modified polyether adhesive can be adjusted by formula to make the product have the characteristics of low modulus, high displacement resistance, good elasticity and good adhesion to the substrate, which is very suitable for the joint sealing of the assembled building.
  • silane-modified polyether glue for prefabricated building on the market has two types of products, single and double components.
  • the one-component low modulus silane modified polyether adhesive has the advantages of low modulus, good flexibility, good adhesion to fabricated building materials (such as cement concrete, steel, etc.), simple operation during construction, and the like, but single component
  • the silane-modified polyether adhesive needs high temperature dehydration during the production process, and the production process is complicated.
  • the one-component silane-modified polyether adhesive mainly relies on moisture curing, and there is a disadvantage of slow curing in the surface and inside when curing. If the joint of the fabricated building changes when the glue is not completely cured, there is a risk of degumming. .
  • the two-component low modulus silane modified polyether adhesive has the advantages of low modulus, good flexibility, simple production process, no need for high temperature dehydration, fast deep layer curing, small curing rate with external environment, and the like, two component low modulus.
  • the silane-modified polyether adhesive utilizes its own moisture during curing, and the outer and inner layers of the adhesive layer are simultaneously cured, which overcomes the shortcoming of slow curing of the one-component silane-modified polyether adhesive, and is suitable for the joint of the assembled building plate with large displacement variation. seal.
  • the existing two-component low modulus silane-modified polyether adhesive has substantially no adhesion to the substrate, and its adhesion to the substrate is completed depending on the primer.
  • the present invention provides a low modulus high adhesion assembly type silane-modified polyether adhesive for building.
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • the plasticizer is 0 when the weight fraction of the terminal hydroxyl branching polyether is different.
  • the branched polyether epoxy resin is one or both of a branched polyether epoxy resin TBEPO and a branched polyether epoxy resin FBEPO, and the branched polyether ring
  • the oxygen resin TBEPO structure is:
  • the branched polyether epoxy resin FBEPO structure is:
  • the silane-modified polyether polymer has the following structural features:
  • the silane-modified polyether has a viscosity in the range of 6-82 Pa.s at 25 °C.
  • the branched polyether epoxy resin is a mixture of the branched polyether epoxy resin TBEPO and the branched polyether epoxy resin FBEPO in a ratio of 3:(1.8-2.2).
  • the silane-modified polyether is a silane-modified polyether having a viscosity of 8 Pa.s and a silane-modified polyether having a viscosity of 40 Pa.s is mixed at a ratio of 22:(7-9).
  • the plasticizer is dioctyl phthalate, diisononyl phthalate, diisononyl phthalate, dibutyl phthalate, adipic acid.
  • the terminal hydroxyl branched polyether is one or both of a polyether triol, a pentaerythrine tetraol.
  • the thixotropic agent is one or more of a polyamide wax, hydrogenated castor oil, and organic bentonite.
  • the reinforcing filler A is one or more of heavy calcium carbonate, nano-active calcium carbonate, silicon micropowder, and kaolin.
  • the reinforcing filler B is one or more of heavy calcium carbonate, nano-active calcium carbonate, silicon micropowder, and kaolin.
  • the toner is titanium dioxide and/or carbon black.
  • the light stabilizer is one or more of a hindered amine light stabilizer and a benzotriazole light stabilizer.
  • the hindered amine light stabilizer is bis(2,2,6,6-tetramethyl-4piperidinyl) sebacate.
  • the benzotriazole light stabilizer is 2-(5-chloro(2H)-benzotriazol-2-yl)-4-(methyl)-6- (uncle Butyl) phenol.
  • the organotin catalyst is one of tin diethylhexanoate, dibutyltin dilaurate, dioctyltin diacetate, stannous octoate, diorganotin bis( ⁇ -diketonate). Or a variety.
  • the amine curing agent is one or more of 1,3-cyclohexyldimethylamine, isophoronediamine, and polyetheramine D-230.
  • the invention also provides a preparation method of the above-mentioned low modulus high adhesion assembly type silane modified polyether glue for building.
  • the preparation method of the above-mentioned low modulus high adhesion assembly type silane modified polyether glue comprises the following steps:
  • a component adding the silane-modified polyether, a plasticizer, a hydroxyl terminated branched polyether, a branched polyether epoxy resin, a thixotropic agent, white carbon black, and a toner to the planet In the machine cylinder, stirring; b, adding the incremental filler A, dispersing and stirring under vacuum; c, unloading the vacuum, adding the hollow glass microspheres to the planetary machine cylinder, and stirring under vacuum; d, After cooling and vacuuming, the coupling agent is added, and after being stirred under vacuum, the vacuum is discharged and discharged, that is, obtained;
  • component B a, adding the plasticizer, hydroxyl terminated polyether, light stabilizer, incremental filler B to another planetary machine cylinder, stirring; b, vacuum removal, adding The organotin catalyst and the amine curing agent are stirred under vacuum conditions; c, the vacuum discharge is obtained, that is, it is obtained.
  • the above preparation method comprises the following steps:
  • a component a, adding the silane-modified polyether, a plasticizer, a hydroxyl terminated branched polyether, a branched polyether epoxy resin, a thixotropic agent, white carbon black, and a toner to the planet
  • b add the incremental filler A, and disperse and stir for 30-50 min under the condition of vacuum degree 0.08-0.1 MPa
  • c vacuum off, add the hollow glass microspheres to
  • the mixture is stirred for 15 to 20 minutes under a vacuum degree of 0.08-0.1 MPa
  • d the planetary machine material cylinder is cooled by the cooling water, and the material temperature is reduced to below 50 ° C, the vacuum is removed, and the coupling agent is added.
  • the vacuum discharge is discharged, that is, obtained;
  • Component B a. Add the plasticizer, hydroxyl terminated polyether, light stabilizer, and incremental filler B to another planetary machine cylinder, and stir at a vacuum of 0.08 to 0.1 MPa. 30 ⁇ 50min; b, vacuum off, add the organotin catalyst, amine curing agent, stirring at a vacuum of 0.08 ⁇ 0.1MPa for 10 ⁇ 20min; c, unloading vacuum discharge, that is.
  • the method for preparing the branched polyether epoxy resin is as follows:
  • the method for preparing the branched polyether epoxy resin is as follows:
  • the boron trifluoride-diethyl ether complex is used as a catalyst in a nitrogen atmosphere at 55-65 ° C for 5-10 h after reacting with epichlorohydrin. Removing the unreacted small molecule; the boron trifluoride-diethyl ether complex accounts for 0.3-1.0% of the total mass of the polyether polyol and the epichlorohydrin;
  • the present invention has the following beneficial effects:
  • the low modulus high adhesion assembly type silane modified polyether glue of the invention is a two component silane modified polyether glue, and the two components A and B are mixed, and the water can be utilized by itself. Simultaneous curing of the outer and inner layers of the rubber layer can overcome the shortcoming of slow curing of the one-component silane-modified polyether adhesive, and has the advantages of deep deep curing.
  • the component A is used as a bonding accelerator with a branched polyether epoxy resin as a bonding accelerator, so that the compatibility of the two-component polyether adhesive system is good, and the double is greatly improved.
  • the adhesion of the component silane-modified polyether adhesive to the prefabricated component materials used in the prefabricated building can achieve good bonding and waterproofing effect without using the primer, and can also avoid the misuse of the existing primer construction. The risk of water leakage.
  • the present invention also preferably optimizes various components in the silane-modified polyether adhesive by both the branched polyether epoxy resin TBEPO and the branched polyether epoxy resin FBEPO at 3: (1.8-2.2) Mixing in proportion and compounding with the silane-modified polyether and hydroxyl terminated branched polyether of suitable viscosity to make the sealant prepared by the two-component polyether adhesive system have better bonding effect.
  • the low modulus high adhesion assembly type silane modified polyether adhesive of the invention does not require high temperature dehydration, simple process, easy operation, low production cost, and is advantageous for industrial production and use.
  • the invention provides a low modulus high adhesion assembly type silane modified polyether glue for building and a preparation method thereof.
  • the present invention will be more fully described below with reference to the embodiments, the following A preferred embodiment of the invention.
  • the invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that the understanding of the present disclosure will be more fully understood.
  • the embodiment provides a branched polyether epoxy resin and a preparation method thereof, comprising the following steps:
  • Epoxy resin FBEPO having an epoxy value of 0.63 and a viscosity of 560 mPa.s.
  • the embodiment provides a branched polyether epoxy resin and a preparation method thereof, comprising the following steps:
  • the organic phase was poured into a beaker, placed in a blast oven at 120 ° C for 12 h, and then desolventized in a vacuum oven at 120 ° C for 1 h to obtain a low viscosity liquid branched polyether with good fluidity.
  • the epoxy resin TBEPO was found to have an epoxy value of 0.12 and a viscosity of 2800 mPa.s.
  • the silane-modified polyether adhesive for low modulus and high adhesion assembly type building according to the embodiment, in parts by weight, comprises:
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • the silane-modified polyether has a viscosity of 40 Pa.s and has the following structural features:
  • the planetary machine feed cylinder is cooled by the cooling water. After the temperature of the material drops to below 50 °C, the vacuum is removed, and isocyanate propyltrimethoxysilane is added. After the vacuum is 0.08-0.1 MPa, the vacuum is discharged for 15 minutes. Got it.
  • the A and B components are mixed at a mass ratio of 10:1, and the mixture is uniformly mixed with a special two-component mixture, and the rubber is extracted by a special two-component glue gun.
  • the silane-modified polyether adhesive for low modulus and high adhesion assembly type building according to the embodiment, in parts by weight, comprises:
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • the silane-modified polyether has a viscosity of 40 Pa.s and has the following structural features:
  • the A and B components are mixed at a mass ratio of 10:1, and the mixture is uniformly mixed with a special two-component mixture, and the rubber is extracted by a special two-component glue gun.
  • the silane-modified polyether adhesive for low modulus and high adhesion assembly type building according to the embodiment, in parts by weight, comprises:
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • silane-modified polyethers 40 Pa.s and 13 Pa.s were respectively used in the above components, and the above silane-modified polyethers have the following structural features:
  • silane-modified polyether dioctyl phthalate, polyether triol N330, pentaerythrine tetraol PP150, branched polyether epoxy resin FBEPO, organic bentonite, white carbon black, Titanium dioxide is added to the planetary machine cylinder and stirred for 10 minutes;
  • the A and B components are mixed at a mass ratio of 10:1, and the mixture is uniformly mixed with a special two-component mixture, and the rubber is extracted by a special two-component glue gun.
  • the silane-modified polyether adhesive for low modulus and high adhesion assembly type building according to the embodiment, in parts by weight, comprises:
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • silane-modified polyethers 40 Pa.s and 8 Pa.s were used in the above components, and the silane-modified polyether has the following structural features in a ratio of 22:8:
  • silane modified polyether polypropylene glycol, pentaerythrine tetraol PP150, branched polyether epoxy resin TBEPO, branched polyether epoxy resin FBEPO, polyamide wax, organic bentonite, white carbon black Titanium dioxide is added to the planetary machine cylinder and stirred for 5 minutes;
  • the silane-modified polyether adhesive for low modulus and high adhesion assembly type building according to the embodiment, in parts by weight, comprises:
  • Component A is a compound having Component A:
  • Component B is a compound having Component B:
  • silane-modified polyethers of 40Pa.s, 13Pa.s and 8Pa.s are respectively used in the above components, and the above silane-modified polyether has the following structural features:
  • terminal polyether triol N330 bis(2,2,6,6-tetramethyl-4piperidinyl) sebacate, 2-(5-chloro(2H)-benzotriene Zin-2-yl)-4-(methyl)-6-(tert-butyl)phenol, nano-active calcium carbonate is added to the planetary machine cylinder, and stirred under a vacuum of 0.08-0.1 MPa for 40 min;
  • the A and B components are mixed at a mass ratio of 10:1, and the mixture is uniformly mixed with a special two-component mixture, and the rubber is extracted by a special two-component glue gun.
  • the present comparative example differs from Example 6 in that no branched polyether epoxy resin was added to the A component of the present comparative example, and the remaining components and preparation methods were the same as in Example 6.
  • the low modulus high adhesion assembly type silane modified polyether adhesive of the invention can meet the requirements of various indexes of ISO 11600-F-25LM, and can meet the assembly joint of the building. Sealing requirements. Comparative Example 1 has no adhesion to the substrate when it is not used with the primer, and cannot meet the requirements for use.

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Abstract

一种低模量高粘附装配式建筑用硅烷改性聚醚胶，分为A组分与B组分，其中A组分包括：硅烷改性聚醚、增塑剂、端羟基支化聚醚、支化聚醚环氧树脂、偶联剂、触变剂、白炭黑、增强填料A、中空玻璃微球和色粉，B组分包括增塑剂、端羟基支化聚醚、光稳定剂、增强填料B、有机锡催化剂和胺类固化剂。本申请所述双组份聚醚胶体系的相容性好，极大地提高了所述双组份聚醚胶的粘接性，应用于装配式建筑使用的预制构件材料拼缝连接，无需配合底涂使用也可达到很好的粘接及防水效果，同时还可避免现有底涂施工误操作带来的漏水风险。

Description

一种低模量高粘附装配式建筑用硅烷改性聚醚胶及其制备方法 技术领域
本发明属于建筑材料及其制造领域，特别涉及一种低模量高粘附装配式建筑用硅烷改性聚醚胶及其制备方法。
背景技术
装配式建筑就像搭积木一样建房子，房屋的主要构件，尤其是预制混凝土PC构件，在工厂生产，在现场组装，这种生产方式具有建造效率高、资源能源消耗小、环境污染少、现场施工人员少、资金设备周转率高等许多优点。在欧美日本等国家得到了很好的发展，目前中国也在大力支持装配式建筑的发展。2016年李克强总理在全国两会中提出未来10年装配式建筑占新建建筑的比例要达到30％。未来装配式建筑将有比较好的市场前景。
装配式建筑在拼装过程中存在大量接缝需要进行防水密封处理，尤其是外墙接缝，密封胶是防水密封的第一道防线，其性能好坏将直接影响到防水密封效果。由于装配式建筑接缝在预制构件热胀冷缩、风压、地基沉降等作用下会产生位移变化，因此需要选用低模量高位移能力的密封胶产品。硅烷改性聚醚胶通过配方调整可使产品具有模量低、抗位移能力高、弹性好、对基材粘接性好等特点，非常适合装配式建筑接缝密封。目前市面上的装配式建筑用硅烷改性聚醚胶(MS胶)有单、双组份两种类型的产品。单组份低模量硅烷改性聚醚胶具有模量低、柔韧性好、对装配式建筑材料(如水泥混凝土、钢材等)粘接性好、施工过程操作简单等优点，然而单组份硅烷改性聚醚胶生产过程中需进行高温脱水，生产过程比较复杂。此外单组份硅烷改性聚醚胶主要依靠湿气固化，固化时由表及里，存在深层固化慢的缺点，假如装配式建筑接缝在胶未完全固化时发生位移变化，则存在脱胶风险。双组份低模量硅烷改性聚醚胶具有模量低、柔韧性好、生产工艺简单、不需要高温脱水、深层固化快、固化速率随外界环境变化小等优点，双组份低模量硅烷改性聚醚胶固化时利用自身的水分，胶层外部和内部同时固化，克服了单组份硅烷改性聚醚胶深层固化慢的缺陷，比较适合位移变化大的装配式建筑板块接缝密封。然而现有双组份低模量硅烷改性聚醚胶对基材基本没有粘接性，其对基材的粘接性完成依赖性于底涂。 如果施工过程中操作不当，某部位底涂没刷好，将带来严重的漏水风险。此外，使用底涂增加了一道工序，操作比较复杂，并且底涂中含有的溶剂对人体和环境都有一定的危害。
因此有必要开发一种具有良好粘接性的双组份低模量硅烷改性聚醚胶。
发明内容
基于此，针对上述问题，本发明提供了一种低模量高粘附装配式建筑用硅烷改性聚醚胶。
具体技术方案如下：
一种低模量高粘附装配式建筑用硅烷改性聚醚胶，按重量份数计，包括：
A组分：
Figure PCTCN2017119482-appb-000001
B组分：
Figure PCTCN2017119482-appb-000002
其中，所述增塑剂与所述端羟基支化聚醚所占的重量份数不同时为0。
在其中一些实施例中，所述支化聚醚环氧树脂为：支化聚醚环氧树脂TBEPO和支化聚醚环氧树脂FBEPO中的一种或两种，所述支化聚醚环氧树脂TBEPO结构为：
Figure PCTCN2017119482-appb-000003
其中，1≤a≤25，1≤b≤25，1≤c≤25，3≤a+b+c≤70；
所述支化聚醚环氧树脂FBEPO结构为：
Figure PCTCN2017119482-appb-000004
其中，1≤o≤15，1≤p≤15，1≤q≤15，1≤r≤15，4≤o+p+q+r≤40。
在其中一些实施例中，所述硅烷改性聚醚聚合物具有如下结构特征：
Figure PCTCN2017119482-appb-000005
所述硅烷改性聚醚在25℃下粘度范围为6-82Pa.s。
在其中一些实施例中，所述支化聚醚环氧树脂为所述支化聚醚环氧树脂TBEPO与所述支化聚醚环氧树脂FBEPO以3:(1.8-2.2)的比例混合。
在其中一些实施例中，所述硅烷改性聚醚为粘度为8Pa.s的硅烷改性聚醚和粘度为40Pa.s的硅烷改性聚醚以22:(7-9)的比例混合。
在其中一些实施例中，所述增塑剂为邻苯二甲酸二辛酯、邻苯二甲酸二异癸酯、邻苯二甲酸二异壬酯、邻苯二甲酸二丁酯、己二酸二辛酯、已二酸二异癸酯、癸二酸二辛酯、癸二酸二异辛酯、磷酸二苯一辛酯、磷酸甲苯二苯酯、 聚丙二醇中的一种或多种。
在其中一些实施例中，所述端羟基支化聚醚为聚醚三元醇、季戊聚醚四元醇的一种或两种。
在其中一些实施例中，所述触变剂为聚酰胺蜡、氢化蓖麻油、有机膨润土中的一种或多种。
在其中一些实施例中，所述增强填料A为重质碳酸钙、纳米活性碳酸钙、硅微粉、高岭土中的一种或多种。
在其中一些实施例中，所述增强填料B为重质碳酸钙、纳米活性碳酸钙、硅微粉、高岭土中的一种或多种。
在其中一些实施例中，所述色粉是钛白粉和/或炭黑。
在其中一些实施例中，所述光稳定剂为受阻胺类光稳定剂和苯并三唑类光稳定剂中的一种或多种。
在其中一些实施例中，所述受阻胺类光稳定剂为双(2,2,6,6-四甲基-4哌啶基)癸二酸酯。
在其中一些实施例中，所述苯并三唑类光稳定剂为2-(5-氯代(2H)-苯并三唑-2-基)-4-(甲基)-6-(叔丁基)酚。
在其中一些实施例中，所述有机锡催化剂为二乙基己酸锡、二月桂酸二丁基锡、二醋酸二辛基锡、辛酸亚锡、二有机锡双(β-二酮酯)中的一种或多种。
在其中一些实施例中，所述胺类固化剂为1，3-环己二甲胺、异佛尔酮二胺、聚醚胺D-230一种或多种。
本发明还提供了一种上述低模量高粘附装配式建筑用硅烷改性聚醚胶的制备方法。
具体技术方案如下：
上述低模量高粘附装配式建筑用硅烷改性聚醚胶的制备方法，包括以下步骤：
(1)A组分：a、将所述硅烷改性聚醚、增塑剂、端羟基支化聚醚、支化聚醚环氧树脂、触变剂、白炭黑、色粉添加到行星机料缸中，搅拌；b、添加所述增量填料A，真空条件下分散搅拌；c、卸真空，将所述中空玻璃微球添加到上述行星机料缸中，真空条件搅拌；d、降温、卸真空后，添加所述偶联剂，真空条件下搅拌后，卸真空、出料，即得；
(2)B组分：a、将所述增塑剂、端羟基支化聚醚、光稳定剂、增量填料B添加到另一行星机料缸中，搅拌；b、卸真空，添加所述有机锡催化剂、胺类固化剂，真空条件下搅拌；c、卸真空出料，即得。
在其中一些实施例中，上述制备方法，包括以下步骤：
(1)A组分：a、将所述硅烷改性聚醚、增塑剂、端羟基支化聚醚、支化聚醚环氧树脂、触变剂、白炭黑、色粉添加到行星机料缸中，搅拌5-10min；b、添加所述增量填料A，在真空度0.08～0.1MPa的条件下分散搅拌30-50min；c、卸真空，将所述中空玻璃微球添加到上述行星机料缸中，在真空度0.08-0.1MPa下搅拌15～20min；d、所述行星机料缸通冷却水降温，物料温度降至50℃以下后卸真空、添加所述偶联剂，在真空度0.08～0.1MPa下搅拌15～20min后卸真空出料，即得；
(2)B组分：a、将所述增塑剂、端羟基支化聚醚、光稳定剂、增量填料B添加到另一行星机料缸中，在真空度0.08～0.1MPa下搅拌30～50min；b、卸真空，添加所述有机锡催化剂、胺类固化剂，在真空度0.08～0.1MPa下搅拌10～20min；c、卸真空出料，即得。
在其中一些实施例中，上述支化聚醚环氧树脂的制备方法如下：
(1)将聚醚多元醇加热并真空脱水，以三氟化硼-乙醚络合物作为催化剂，与环氯丙烷反应后，脱除未反应小分子；
(2)加入适量甲苯稀释后，加入过量固体氢氧化钠，提取有机相、除去溶剂并干燥后即得。
在其中一些实施例中，上述支化聚醚环氧树脂的制备方法如下：
(1)将聚醚多元醇在100-150℃真空脱水后，在55-65℃氮气氛围中，以三氟化硼-乙醚络合物作为催化剂，与环氧氯丙烷反应5-10h后，脱除未反应小分子；所述三氟化硼-乙醚络合物占聚醚多元醇与环氧氯丙烷总质量的0.3-1.0％；
(2)降温至25-50℃，并加入适量甲苯稀释，加入过量固体氢氧化钠，保温4-6h，提取有机相溶液，除去溶剂并干燥后即得。
基于上述技术方案，本发明具有以下有益效果：
本发明所述的低模量高粘附装配式建筑用硅烷改性聚醚胶是一种双组分硅烷改性聚醚胶，其A、B两个组分混合后，利用自身的水分可使胶层外部和内部同时固化，可克服单组份硅烷改性聚醚胶固化慢的缺陷，具有深层固化快的优 点。其中，A组分中以支化聚醚环氧树脂作为粘接促进剂配合端羟基支化聚醚使用，使得双组份聚醚胶体系的相容性好，且极大地提高了所述双组份硅烷改性聚醚胶对装配式建筑使用的预制构件材料的粘接性，无需配合底涂使用也可达到很好的粘接及防水效果，同时还可避免现有底涂施工误操作带来的漏水风险。
并且，本发明还对该硅烷改性聚醚胶中的各种成分进行了优选，通过支化聚醚环氧树脂TBEPO与支化聚醚环氧树脂FBEPO两者以3:(1.8-2.2)按比例混合，并与合适粘度的硅烷改性聚醚、端羟基支化聚醚实现组分之间的复配，使得双组份聚醚胶体系制备得到的密封胶的粘结效果更好。
本发明所述的低模量高粘附装配式建筑用硅烷改性聚醚胶制备时不需要高温脱水、工艺简单、步骤易于操作，生产成本低，利于工业化生产与使用。
具体实施方式
本发明提供了一种低模量高粘附装配式建筑用硅烷改性聚醚胶及其制备方法，为了便于理解本发明，下面将参照实施例对本发明进行更全面的描述，以下给出了本发明的较佳实施例。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
以下所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对以下实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
实施例1
本实施例提供一种支化聚醚环氧树脂及其制备方法，包括以下步骤：
(1)称取768g的季戊聚醚四元醇PP150，加热至120℃真空脱水气20min，然后通干燥氮气冷却至室温，加入5.62g的三氟化硼-乙醚络合物作为催化剂， 用磁力搅拌器搅拌均匀；
(2)升温至60±2℃，均匀搅拌用恒压漏斗在2h内缓慢滴加356g环氧氯丙烷，然后保温6h，然后真空除去未反应环氧氯丙烷；
(3)降温至45±2℃加入适量甲苯稀释后，2h内分多次加入过量112.4g的固体氢氧化钠，保温6h；
(4)将产物抽滤，用分液漏斗收集滤液用甲苯萃取有机相，用蒸馏水洗涤至中性；
(5)将有机相倒入烧杯中，置于120℃鼓风干燥箱中去溶剂12h，然后在120℃真空干燥箱中真空脱溶剂1h，得到流动性较好的低粘度液体支化聚醚环氧树脂FBEPO，测得环氧值为0.63，粘度560mPa.s。
上述步骤中涉及的化学反应如下：
Figure PCTCN2017119482-appb-000006
其中，1≤o≤15，1≤p≤15，1≤q≤15，1≤r≤15，4≤o+p+q+r≤40。
实施例2
本实施例提供一种支化聚醚环氧树脂及其制备方法，包括以下步骤：
(1)称取1450g的聚醚三元醇N330，加热至120℃真空脱水气30min，然 后通干燥氮气冷却至室温，加入7.96g的三氟化硼-乙醚络合物作为催化剂，用磁力搅拌器搅拌均匀；
(2)升温至60±0.5℃，均匀搅拌用恒压漏斗在2h内缓慢滴加142g环氧氯丙烷，然后保温8h，然后真空除去未反应环氧氯丙烷；
(3)降温至45±0.5℃加入适量甲苯稀释后，2h内分多次加入159.2g的固体氢氧化钠，保温4h；
(4)将产物抽滤，用分液漏斗收集滤液用甲苯萃取有机相，用蒸馏水洗涤至中性；
(5)将有机相倒入烧杯中，置于120℃鼓风干燥箱中去溶剂12h，然后在120℃真空干燥箱中真空脱溶剂1h，得到流动性较好的低粘度液体支化聚醚环氧树脂TBEPO，测得环氧值为0.12，粘度2800mPa.s。
上述步骤中涉及的化学反应如下：
Figure PCTCN2017119482-appb-000007
其中，1≤a≤25，1≤b≤25，1≤c≤25，3≤a+b+c≤70。
实施例3
本实施例所述低模量高粘附装配式建筑用硅烷改性聚醚胶，按重量份数计，包括：
A组分：
Figure PCTCN2017119482-appb-000008
B组分：
Figure PCTCN2017119482-appb-000009
其中，上述硅烷改性聚醚的粘度为40Pa.s，并具有如下结构特征：
Figure PCTCN2017119482-appb-000010
本实施例所述低模量高粘附装配式建筑用硅烷改性聚醚胶的制备方法，包括以下步骤：
1、制备得到A组分：
(1)将上述硅烷改性聚醚、季戊聚醚四元醇PP150、实施例1制备得到的支化聚醚环氧树脂FBEPO、聚酰胺蜡、白炭黑、钛白粉添加到行星机料缸中，搅拌8min；
(2)向其中添加纳米活性碳酸钙，在真空度0.08～0.1MPa的条件下分散搅拌50min；
(3)卸真空，将中空玻璃微球添加到上述行星机料缸中，在真空度0.08～0.1MPa下搅拌15min；
(4)行星机料缸通冷却水降温，物料温度降至50℃以下后卸真空、添加异 氰酸酯基丙基三甲氧基硅烷，在真空度0.08～0.1MPa下搅拌15min后卸真空出料，即得。
2、制备得到B组分：
(1)将季戊聚醚四元醇PP150、双(2,2,6,6-四甲基-4哌啶基)癸二酸酯、重质碳酸钙添加到行星机料缸中，在真空度0.08～0.1MPa下搅拌30min；
(2)卸真空，添加所述二月桂酸二丁基锡、1,3-环己二甲胺、聚醚胺D-230，在真空度0.08～0.1MPa下搅拌15min；
(3)卸真空出料，即得。
3、使用时A、B组分以10：1的质量比混合，使用专用双组份搅拌混合均匀，用专用的双组份胶枪抽取胶料后进行施胶。
实施例4
本实施例所述低模量高粘附装配式建筑用硅烷改性聚醚胶，按重量份数计，包括：
A组分：
Figure PCTCN2017119482-appb-000011
B组分：
Figure PCTCN2017119482-appb-000012
Figure PCTCN2017119482-appb-000013
上述硅烷改性聚醚的粘度为40Pa.s，并具有如下结构特征：
Figure PCTCN2017119482-appb-000014
本实施例所述低模量高粘附装配式建筑用硅烷改性聚醚胶的制备方法，包括以下步骤：
1、制备得到A组分：
(1)将硅烷改性聚醚、邻苯二甲酸二辛酯、聚醚三元醇N330、支化聚醚环氧树脂TBEPO、氢化蓖麻油、白炭黑、炭黑添加到行星机料缸中，搅拌10min；
(2)添加纳米活性碳酸钙、硅微粉，在真空度0.08～0.1MPa的条件下分散搅拌40min；
(3)卸真空，将中空玻璃微球添加到上述行星机料缸中，在真空度0.08～0.1MPa下搅拌15min；
(4)向行星机料缸通冷却水降温，物料温度降至50℃以下后卸真空、添加异氰酸酯基丙基三甲氧基硅烷，在真空度0.08～0.1MPa下搅拌18min后卸真空出料，即得；
2、制备得到B组分：
(1)将邻苯二甲酸二丁酯、聚醚三元醇N330、双(2,2,6,6-四甲基-4哌啶基)癸二酸酯、纳米活性碳酸钙添加到行星机料缸中，在真空度0.08～0.1MPa下搅拌50min；
(2)卸真空，添加二乙基己酸锡、1,3-环己二甲胺、聚醚胺D-230，在真空度0.08～0.1MPa下搅拌15min；
(3)卸真空出料，即得。
3、使用时A、B组分以10：1的质量比混合，使用专用双组份搅拌混合均匀，用专用的双组份胶枪抽取胶料后进行施胶。
实施例5
本实施例所述低模量高粘附装配式建筑用硅烷改性聚醚胶，按重量份数计，包括：
A组分：
Figure PCTCN2017119482-appb-000015
B组分：
Figure PCTCN2017119482-appb-000016
上述组分中采用了两种粘度的硅烷改性聚醚，分别为40Pa.s和13Pa.s，以18:5的比例混合，上述硅烷改性聚醚具有如下结构特征：
Figure PCTCN2017119482-appb-000017
本实施例所述低模量高粘附装配式建筑用硅烷改性聚醚胶的制备方法，包括以下步骤：
1、制备得到A组分：
(1)将硅烷改性聚醚、邻苯二甲酸二辛酯、聚醚三元醇N330、季戊聚醚四元醇PP150、支化聚醚环氧树脂FBEPO、有机膨润土、白炭黑、钛白粉添加到行星机料缸中，搅拌10min；
(2)添加纳米活性碳酸钙、重质碳酸钙，在真空度0.08～0.1MPa的条件下分散搅拌45min；
(3)卸真空，将中空玻璃微球添加到上述行星机料缸中，在真空度0.08～0.1MPa下搅拌20min；
(4)向行星机料缸通冷却水降温，物料温度降至50℃以下后卸真空、添加γ-甲基丙烯酰氧丙基三甲氧基硅烷，在真空度0.08～0.1MPa下搅拌20min后卸真空出料，即得；
2、制备得到B组分：
(1)将磷酸甲苯二苯酯、季戊聚醚四元醇PP150、2-(5-氯代(2H)-苯并三唑-2-基)-4-(甲基)-6-(叔丁基)酚、纳米活性碳酸钙添加到行星机料缸中，在真空度0.08～0.1MPa下搅拌45min；
(2)卸真空，添加二醋酸二辛基锡、1，3-环己二甲胺、异佛尔酮二胺，在真空度0.08～0.1MPa下搅拌15min；
(3)卸真空出料，即得。
3、使用时A、B组分以10：1的质量比混合，使用专用双组份搅拌混合均匀，用专用的双组份胶枪抽取胶料后进行施胶。
实施例6
本实施例所述低模量高粘附装配式建筑用硅烷改性聚醚胶，按重量份数计，包括：
A组分：
Figure PCTCN2017119482-appb-000018
Figure PCTCN2017119482-appb-000019
B组分：
Figure PCTCN2017119482-appb-000020
上述组分中采用了两种粘度的硅烷改性聚醚，分别为40Pa.s和8Pa.s，按照22:8的比例混合，硅烷改性聚醚具有如下结构特征：
Figure PCTCN2017119482-appb-000021
本实施例所述低模量高粘附装配式建筑用硅烷改性聚醚胶的制备方法，包括以下步骤：
1、制备得到A组分：
(1)将硅烷改性聚醚、聚丙二醇、季戊聚醚四元醇PP150、支化聚醚环氧树脂TBEPO、支化聚醚环氧树脂FBEPO、聚酰胺蜡、有机膨润土、白炭黑、钛白粉添加到行星机料缸中，搅拌5min；
(2)添加纳米活性碳酸钙、重质碳酸钙，在真空度0.08～0.1MPa的条件下 分散搅拌50min；
(3)卸真空，将中空玻璃微球添加到上述行星机料缸中，在真空度0.08～0.1MPa下搅拌20min；
(4)行星机料缸通冷却水降温，物料温度降至50℃以下后卸真空、添加γ-甲基丙烯酰氧丙基三甲氧基硅烷，在真空度0.08～0.1MPa下搅拌15min后卸真空出料，即得。
2、制备得到B组分：
(1)将聚醚三元醇N330、2-(5-氯代(2H)-苯并三唑-2-基)-4-(甲基)-6-(叔丁基)酚、高岭土添加到另一行星机料缸中，在真空度0.08～0.1MPa下搅拌30min；
(2)卸真空，添加所述二有机锡双(β-二酮酯)、1，3-环己二甲胺、聚醚胺D-230，在真空度0.08～0.1MPa下搅拌20min；
(3)卸真空出料，即得。
实施例7
本实施例所述低模量高粘附装配式建筑用硅烷改性聚醚胶，按重量份数计，包括：
A组分：
Figure PCTCN2017119482-appb-000022
Figure PCTCN2017119482-appb-000023
B组分：
Figure PCTCN2017119482-appb-000024
上述组分中采用了三种粘度的硅烷改性聚醚，分别为40Pa.s、13Pa.s和8Pa.s，按一定比例混合，上述硅烷改性聚醚具有如下结构特征：
Figure PCTCN2017119482-appb-000025
本实施例所述低模量高粘附装配式建筑用硅烷改性聚醚胶的制备方法，包括以下步骤：
1、制备得到A组分：
(1)将硅烷改性聚醚、聚醚三元醇N330、季戊聚醚四元醇PP150、支化聚醚环氧树脂TBEPO、聚酰胺蜡、氢化蓖麻油、白炭黑、钛白粉添加到行星机料缸中，搅拌7min；
(2)接着添加纳米活性碳酸钙，在真空度0.08～0.1MPa的条件下分散搅拌45min；
(3)卸真空，将中空玻璃微球添加到行星机料缸中，在真空度0.08～0.1MPa下搅拌16min；
(4)向行星机料缸通冷却水降温，物料温度降至50℃以下后卸真空、添加异氰酸酯基丙基三甲氧基硅烷，在真空度0.08～0.1MPa下搅拌20min后卸真空出料，即得。
2、制备得到B组分：
(1)将端聚醚三元醇N330、双(2，2，6，6-四甲基-4哌啶基)癸二酸酯、2-(5-氯代(2H)-苯并三唑-2-基)-4-(甲基)-6-(叔丁基)酚、纳米活性碳酸 钙添加到行星机料缸中，在真空度0.08～0.1MPa下搅拌40min；
(2)卸真空，添加辛酸亚锡、1，3-环己二甲胺、聚醚胺D-230，在真空度0.08～0.1MPa下搅拌20min；
(3)卸真空出料，即得。
3、使用时A、B组分以10：1的质量比混合，使用专用双组份搅拌混合均匀，用专用的双组份胶枪抽取胶料后进行施胶。
对比例1
本对比例与实施例6的区别在于，本对比例的A组分中未添加支化聚醚环氧树脂，其余组分及制备方法与实施例6相同。
将实施例3-7及对比例1制备的低模量高粘附装配式建筑用硅烷改性聚醚胶进行性能测试，具体测试标准和测试数据如表1所示。
表1 性能测试结果
Figure PCTCN2017119482-appb-000026
从表1的实验结果可以看出，本发明的低模量高粘附装配式建筑用硅烷改性聚醚胶能符合ISO 11600-F-25LM的各项指标要求，可满足装配式建筑接缝密 封需求。而对比例1在不配合底涂使用时对基材没有粘接性，不能满足使用要求。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对本发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (22)

  1. 一种低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，按重量份数计，包括：
    A组分：
    Figure PCTCN2017119482-appb-100001
    B组分：
    Figure PCTCN2017119482-appb-100002
    其中，所述增塑剂与所述端羟基支化聚醚所占的重量份不同时为0。
  2. 根据权利要求1所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述支化聚醚环氧树脂为：支化聚醚环氧树脂TBEPO和支化聚醚环氧树脂FBEPO中的一种或两种，所述支化聚醚环氧树脂TBEPO结构为：
    Figure PCTCN2017119482-appb-100003
    其中，1≤a≤25，1≤b≤25，1≤c≤25，3≤a+b+c≤70；
    所述支化聚醚环氧树脂FBEPO结构为：
    Figure PCTCN2017119482-appb-100004
    其中，1≤o≤15，1≤p≤15，1≤q≤15，1≤r≤15，4≤o+p+q+r≤40。
  3. 根据权利要求1所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述硅烷改性聚醚具有如下结构特征：
    Figure PCTCN2017119482-appb-100005
    所述硅烷改性聚醚在25℃下粘度为6-82Pa.s。
  4. 根据权利要求2所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述支化聚醚环氧树脂为所述支化聚醚环氧树脂TBEPO与所述支化聚醚环氧树脂FBEPO以3:(1.8-2.2)的比例混合。
  5. 根据权利要求2所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述硅烷改性聚醚为粘度为8Pa.s的硅烷改性聚醚和粘度为40Pa.s的硅烷改性聚醚以22:(7-9)的比例混合。
  6. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述增塑剂为邻苯二甲酸二辛酯、邻苯二甲酸二异癸酯、 邻苯二甲酸二异壬酯、邻苯二甲酸二丁酯、己二酸二辛酯、已二酸二异癸酯、癸二酸二辛酯、癸二酸二异辛酯、磷酸二苯一辛酯、磷酸甲苯二苯酯、聚丙二醇中的一种或多种。
  7. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述端羟基支化聚醚为聚醚三元醇、季戊聚醚四元醇的一种或两种。
  8. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述偶联剂为γ-甲基丙烯酰氧丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、异氰酸酯基丙基三甲氧基硅烷中的一种或一种以上的混合物。
  9. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述触变剂为聚酰胺蜡、氢化蓖麻油、有机膨润土中的一种或多种。
  10. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述增强填料A为重质碳酸钙、纳米活性碳酸钙、硅微粉、高岭土中的一种或多种。
  11. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述增强填料B为重质碳酸钙、纳米活性碳酸钙、硅微粉、高岭土中的一种或多种。
  12. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述色粉是钛白粉和/或炭黑。
  13. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述光稳定剂为受阻胺类光稳定剂和苯并三唑类光稳定剂中的一种或多种。
  14. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述有机锡催化剂为二乙基己酸锡、二月桂酸二丁基锡、二醋酸二辛基锡、辛酸亚锡、二有机锡双(β-二酮酯)中的一种或多种。
  15. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述胺类固化剂为1，3-环己二甲胺、异佛尔酮二胺、聚醚胺D-230一种或多种。
  16. 根据权利要求13所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述受阻胺类光稳定剂为双(2,2,6,6-四甲基-4哌啶基)癸二酸酯。
  17. 根据权利要求13所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，所述苯并三唑类光稳定剂为2-(5-氯代(2H)-苯并三唑-2-基)-4-(甲基)-6-(叔丁基)酚。
  18. 根据权利要求1-5任一项所述的低模量高粘附装配式建筑用硅烷改性聚醚胶，其特征在于，按重量份数计，包括：
    A组分：
    Figure PCTCN2017119482-appb-100006
    B组分：
    Figure PCTCN2017119482-appb-100007
  19. 如权利要求1-18任一项所述低模量高粘附装配式建筑用硅烷改性聚醚 胶的制备方法，其特征在于，包括以下步骤：
    (1)A组分：a、将所述硅烷改性聚醚、增塑剂、端羟基支化聚醚、支化聚醚环氧树脂、触变剂、白炭黑、色粉添加到行星机料缸中，搅拌；b、添加所述增量填料A，真空条件下分散搅拌；c、卸真空，将所述中空玻璃微球添加到上述行星机料缸中，真空条件搅拌；d、降温、卸真空后，添加所述偶联剂，真空条件下搅拌后，卸真空、出料，即得；
    (2)B组分：a、将所述增塑剂、端羟基支化聚醚、光稳定剂、增量填料B添加到另一行星机料缸中，搅拌；b、卸真空，添加所述有机锡催化剂、胺类固化剂，真空条件下搅拌；c、卸真空出料，即得。
  20. 根据权利要求19所述的制备方法，其特征在于，包括以下步骤：
    (1)A组分：a、将所述硅烷改性聚醚、增塑剂、端羟基支化聚醚、支化聚醚环氧树脂、触变剂、白炭黑、色粉添加到行星机料缸中，搅拌5-10min；b、添加所述增量填料A，在真空度0.08～0.1MPa的条件下分散搅拌30-50min；c、卸真空，将所述中空玻璃微球添加到上述行星机料缸中，在真空度0.08-0.1MPa下搅拌15～20min；d、所述行星机料缸通冷却水降温，物料温度降至50℃以下后卸真空、添加所述偶联剂，在真空度0.08～0.1MPa下搅拌15～20min后卸真空出料，即得；
    (2)B组分：a、将所述增塑剂、端羟基支化聚醚、光稳定剂、增量填料B添加到另一行星机料缸中，在真空度0.08～0.1MPa下搅拌30～50min；b、卸真空，添加所述有机锡催化剂、胺类固化剂，在真空度0.08～0.1MPa下搅拌10～20min；c、卸真空出料，即得。
  21. 根据权利要求19或20所述的制备方法，其特征在于，所述支化聚醚环氧树脂的制备方法如下：
    (1)将聚醚多元醇加热并真空脱水，以三氟化硼-乙醚络合物作为催化剂，与环氯丙烷反应后，脱除未反应小分子；
    (2)加入适量甲苯稀释后，加入过量固体氢氧化钠，提取有机相、除去溶剂并干燥后即得。
  22. 根据权利要求21所述的制备方法，其特征在于，所述支化聚醚环氧树脂的制备方法如下：
    (1)将聚醚多元醇在100-150℃真空脱水后，在55-65℃氮气氛围中，以三 氟化硼-乙醚络合物作为催化剂，与环氧氯丙烷反应5-10h后，脱除未反应小分子；所述三氟化硼-乙醚络合物占聚醚多元醇与环氧氯丙烷总质量的0.3-1.0％；
    (2)降温至25-50℃，并加入适量甲苯稀释，加入过量固体氢氧化钠，保温4-6h，提取有机相溶液，除去溶剂并干燥后即得。
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