WO2017118374A1 - 硅烷改性的聚醚密封胶组合物和硅烷改性的聚醚密封胶及其制备方法 - Google Patents

硅烷改性的聚醚密封胶组合物和硅烷改性的聚醚密封胶及其制备方法 Download PDF

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WO2017118374A1
WO2017118374A1 PCT/CN2017/070123 CN2017070123W WO2017118374A1 WO 2017118374 A1 WO2017118374 A1 WO 2017118374A1 CN 2017070123 W CN2017070123 W CN 2017070123W WO 2017118374 A1 WO2017118374 A1 WO 2017118374A1
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weight
parts
tackifier
amount
silane
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French (fr)
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徐斌
张玲玲
林信平
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BYD Co Ltd
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BYD Co Ltd
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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
    • 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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • C08K3/36—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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • 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
    • 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
    • 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
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • 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

Definitions

  • the invention relates to the field of sealants, in particular to a silane-modified polyether sealant composition and a silane-modified polyether sealant and a preparation method thereof.
  • the silane-modified polyether sealant currently on the market is based on alkoxy-terminated polyether as a raw material, and an appropriate amount of reinforcing filler (calcium carbonate, silica, organic montmorillonite, etc.), plasticizer (o-benzene) Di-decyl dicarboxylate, benzoate, phenyl pentadecane sulfonate, polyether polyol, etc.), water remover (calcium oxide, strong hydrolyzable silane coupling agent, etc.), tackifier (aminosilane) , an epoxysilane, an acrylic modified silane, etc.), an organotin catalyst (dibutyltin dilaurate, stannous oxalate, etc.).
  • reinforcing filler calcium carbonate, silica, organic montmorillonite, etc.
  • plasticizer o-benzene Di-decyl dicarboxylate, benzoate, phenyl pentade
  • Such silane-terminated polyether sealant products mainly have the following disadvantages: (1) the mechanical properties of the sealant are not very good, the elasticity of the product with high tensile strength is not very good, and the strength of the product with good elasticity is not very high; The storage stability is not good, it may become thicker and clear with time, even the gel, the storage period is not very long.
  • the object of the present invention is to provide a good elasticity and strength and a storage stability compared with the defects that the existing silane-modified polyether sealant is not well matched in elasticity and strength and has poor storage stability.
  • the present invention provides a silane-modified polyether sealant composition.
  • the composition contains: an alkoxy-terminated polyether, calcium carbonate, white carbon, an organic chelate tin catalyst, a plasticizer, a water scavenger, and a tackifier, wherein
  • the alkoxy-terminated polyether has an apparent viscosity of 7000-16000 mPa ⁇ s
  • the tackifier is one of a bisaminosilane tackifier, a monoaminosilane tackifier, and an alkoxysilane tackifier or A variety.
  • the present invention also provides a process for preparing a silane-modified polyether sealant, which comprises mixing the components contained in the above composition.
  • the invention also provides a silane-modified polyether sealant produced by the process.
  • the silane-modified polyether sealant prepared by using the silane-modified polyether sealant composition of the present invention can have better elasticity and strength, and has better storage stability.
  • the invention provides a silane-modified polyether sealant composition.
  • the composition contains: an alkoxy-terminated polyether, calcium carbonate, white carbon, an organic chelate tin catalyst, a plasticizer, a water scavenger, and a tackifier, wherein the alkane
  • the oxygen-terminated polyether has an apparent viscosity of 7000 to 16000 mPa ⁇ s
  • the tackifier is one or more of a bisaminosilane tackifier, a monoaminosilane tackifier, and an alkoxysilane tackifier.
  • a silane-modified polyether sealant which is excellent in elasticity and strength and has better storage stability, preferably, relative to 100 parts by weight of the alkoxy-terminated polyether
  • the calcium carbonate is used in an amount of 80 to 150 parts by weight (preferably 80 to 130 parts by weight)
  • the white carbon black is used in an amount of 5 to 20 parts by weight
  • the organic chelate tin catalyst is used in an amount of 0.1 to 1 part by weight.
  • the plasticizer is used in an amount of 10 to 50 parts by weight (preferably 10 to 45 parts by weight)
  • the water-removing agent is used in an amount of 1 to 5 parts by weight
  • the tackifier is used in an amount of 1 to 5 parts by weight. Share.
  • the calcium carbonate is used in an amount of 80 to 130 parts by weight
  • the white carbon black is used in an amount of 10 to 15 parts by weight, based on 100 parts by weight of the alkoxy-terminated polyether
  • the organic chelate is used in an amount of 0.2 to 1 part by weight
  • the plasticizer is used in an amount of 10 to 45 parts by weight
  • the water-removing agent is used in an amount of 1 to 3 parts by weight
  • the tackifier is used in an amount of 1 to 3 parts by weight. Parts by weight.
  • the calcium carbonate is used in an amount of 90 to 120 parts by weight
  • the white carbon black is used in an amount of 10 to 15 parts by weight, based on 100 parts by weight of the alkoxy-terminated polyether
  • the organic chelating agent The amount of the tin catalyst is 0.2-1 part by weight
  • the plasticizer is used in an amount of 25-40 parts by weight
  • the water removing agent is used in an amount of 1-3 parts by weight
  • the tackifier is used in an amount of 1- 3 parts by weight.
  • the calcium carbonate is used in an amount of 100 to 120 parts by weight, and the white carbon black is used in an amount of 10 to 15 parts by weight, based on 100 parts by weight of the alkoxy-terminated polyether, the organic chelating agent
  • the tin catalyst is used in an amount of 0.2-0.5 parts by weight
  • the plasticizer is used in an amount of 30-40 parts by weight
  • the water-removing agent is used in an amount of 1-2 parts by weight
  • the tackifier is used in an amount of 1- 2 parts by weight.
  • the alkoxy-terminated polyether may be a polyether prepared by a silane-modified polyether sealant conventionally employed in the art.
  • Specific examples of the alkoxy-terminated polyether may be, for example, one or more of a dimethoxy-terminated polyether, a triethoxy-terminated polyether, and a trimethoxy-terminated polyether.
  • the alkoxy-terminated polyether having an apparent viscosity of 7000-16000 mPa ⁇ s is a high tensile modulus alkoxy-terminated polyether having a high crosslink density during curing. Conducive to increase the tensile strength.
  • the present invention employs an alkoxy-terminated polyether having an apparent viscosity of from 7,000 to 16,000 mPa ⁇ s, it can be blended with other components of the composition to obtain a silane-modified polyether sealant required by the present invention, in order to obtain A silane-modified polyether sealant having a more excellent property, preferably, the alkoxy-terminated polyether has an apparent viscosity of from 8,000 to 15,000 mPa ⁇ s, more preferably 8000-12000mPa ⁇ s.
  • the calcium carbonate is preferably nano-calcium carbonate, more preferably nano-calcium carbonate having a particle size of 50-200 nm, preferably 100-150 nm. It is particularly preferable to use nano calcium carbonate after surface treatment with stearic acid.
  • the white carbon black is preferably fumed silica, and it is particularly preferable to use fumed silica which is surface-treated with dimethyldichlorosilane as the white carbon black of the present invention.
  • the combination of the calcium carbonate and the white carbon black can be reinforced with each other to maximize the interaction between the organic substance and the inorganic powder, and improve the mechanical properties of the obtained polyether sealant, in particular
  • the combination of the above-mentioned surface treated nano-calcium carbonate and the surface-treated fumed silica can better improve the compatibility of the inorganic powder and the organic component, and the dispersion effect can be improved. Therefore, the present invention employs the combination of the calcium carbonate and white carbon black as a reinforcing inorganic powder combination, which can better blend the other components of the composition, so that the obtained polyether sealant can obtain better elasticity and Strength and better storage stability.
  • the weight ratio of the calcium carbonate to the white carbon is from 100:5 to 20, preferably from 100:8 to 15.
  • the organic chelate tin catalyst has high catalytic activity, and is capable of blending with other components in the composition to obtain a silane-modified polyether having good elasticity and strength and good storage stability.
  • the sealant, preferably, the organic chelate tin catalyst is dibutyltin bis(acetylacetonate).
  • the plasticizer has a function of diluting the entire composition and increasing the elastoplasticity of the sealant, which is capable of blending with other components in the composition to obtain good elasticity and strength and good storage stability.
  • the plasticizer described in the present invention is preferably a small molecule plasticizer. When a small molecular substance which is inert in reaction is used as a plasticizer dispersed in a sealant, the interaction force of the organic molecular segment can be maintained. When stretched, it can make a certain relative sliding and increase the elongation.
  • the plasticizer is one or more of polypropylene glycol having a number average molecular weight of from 2,000 to 3,000, dinonyl phthalate, benzoate and phenyl pentadecyl sulfonate.
  • the water scavenger removes moisture by reacting with moisture in the composition system, and is capable of obtaining silane modification with good elasticity and strength and good storage stability in combination with other components in the composition.
  • the polyether sealant preferably, the water scavenger is one or more of vinyltrimethoxysilane, anhydrous calcium chloride and calcium oxide, more preferably vinyltrimethoxysilane.
  • the tackifier has an effect of increasing adhesive properties and assisting in curing cross-linking, and is capable of blending with other components in the composition to obtain a silane which has good elasticity and strength and good storage stability.
  • sexual polyether sealant is one or more of a bisaminosilane tackifier, a monoaminosilane tackifier, and an alkoxysilane tackifier.
  • a specific example of the bisaminosilane tackifier may be: N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane.
  • a specific example of the monoaminosilane tackifier may be: ⁇ -aminopropyltrimethoxysilane.
  • alkoxysilane tackifier may be: ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane.
  • the tackifier is N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, and ⁇ -(2,3-epoxypropane
  • One or more of oxy)propyltrimethoxysilane is particularly preferably N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane.
  • the composition may further contain a colorant, and the colorant may be, for example, one or more of carbon black, titanium white powder, and iron oxide.
  • the colorant is used in an amount of from 1 to 10 parts by weight relative to 100 parts by weight of the alkoxy-terminated polyether.
  • the composition does not contain a crosslinking agent, and the composition of the present invention can obtain elasticity and even without using a crosslinking agent.
  • the present invention also provides a process for preparing a silane-modified polyether sealant, which comprises mixing the components contained in the above composition.
  • the method of the present invention may comprise a method of mixing the components contained in the above composition in any form, for example, a method of mixing the components contained in the above composition at a time, or a method of mixing in a certain order may be employed, wherein In the case of a one-time mixing process, the method comprises: an alkoxy-terminated polyether, a plasticizer, a water scavenger, calcium carbonate, white carbon, an optional colorant, a tackifier, and an organic chelate. The tin catalyst is mixed.
  • the mixing conditions may include, for example, first mixing at a temperature of 50-100 ° C, 500-1000 rpm for 100-180 min, and then mixing at a temperature of 15-40 ° C, at a speed of 500-1000 rpm for 20-40 min. .
  • the method further comprises vacuum defoaming the mixed product, and the vacuum degassing conditions may include, for example, a vacuum of -0.1 MPa to -0.05 MPa, a temperature of 15 to 40 ° C, and a rotation speed of 500 to 1000 rpm. Defoaming for 10-30 min.
  • the method for preparing the silane-modified polyether sealant of the present invention will mix the components contained in the above composition in a certain order, that is, preferably, the method comprises:
  • the types and amounts of the alkoxy-terminated polyether, calcium carbonate, white carbon, organic chelate tin catalyst, plasticizer, water scavenger and tackifier are as above The description is not repeated here.
  • a coloring agent may be added in the step (1), and the kind and amount of the coloring agent are as described above, and are not described herein again.
  • the method for preparing the silane-modified polyether sealant of the present invention may mix the components contained in the above composition in a certain order, the method comprising:
  • the types of the alkoxy-terminated polyether, calcium carbonate, white carbon, organic chelate tin catalyst, plasticizer, water scavenger, tackifier, and colorant are The amount used is as described above and will not be described herein.
  • the white carbon black is preferably dried at a high temperature before mixing, for example, at 100 to 150 ° C for 12 to 30 hours.
  • the mixing conditions of step (1) include a temperature of 70-90 ° C (preferably 80-90 ° C) and a time of 60-180 min (preferably 120-150 min).
  • the mixing rate of the mixing may be, for example, 600 to 1500 rpm, preferably 900 to 1100 rpm.
  • the mixing of this step can achieve the purpose of water removal, which can be carried out by various means conventional in the art, such as mixing in a power mixer.
  • the mixing conditions of the step (2) include a temperature of 15 to 40 ° C (preferably 25 to 40 ° C) and a time of 10 to 60 min (preferably 20 to 40 min).
  • the mixing rate of the mixing may be, for example, 200 to 900 rpm, preferably 300 to 500 rpm.
  • This step mixing is preferably carried out in an inert gas atmosphere, for example, in an atmosphere of one or more inert gases such as nitrogen, helium and neon.
  • the mixing conditions of the step (3) include a temperature of 15 to 40 ° C (preferably 25 to 40 ° C) and a time of 10 to 60 min (preferably 20 to 40 min).
  • the mixing rate of the mixing may be, for example, 200 to 900 rpm, preferably 300 to 500 rpm.
  • the method comprises subjecting the product obtained by mixing to a vacuum defoaming treatment after performing the mixing of the step (3).
  • the product obtained by the mixing in the step (3) may be sent to a vacuum defoaming machine for defoaming, and the conditions of the vacuum defoaming treatment include: a degree of vacuum of -0.1 MPa to -0.05 MPa, and a temperature of 15 to 40 ° C (preferably 25-40 ° C), time is 10-60 min (preferably 20-30 min).
  • This vacuum defoaming treatment can be carried out under stirring, for example, under stirring at a rotation speed of 200 to 900 rpm, preferably 300 to 500 rpm.
  • the method comprises: adding the water removal agent in two steps, In step (1), 40-60% by weight of the water-removing agent is added to the total amount of the water-removing agent, and the remaining water-removing agent is added in the step (3) and is carried out with the product obtained in the step (2) and the organic chelate tin catalyst. mixing.
  • the silane-modified polyether sealant of the present invention does not exclude other additive components as long as such additive components do not affect the properties of the silane-modified polyether sealant obtained by the present invention.
  • an additive for example, organic montmorillonite or the like can be used. These additives may be added in any of the above steps as long as such addition does not affect the properties of the silane-modified polyether sealant obtained by the present invention.
  • the invention also provides a silane-modified polyether sealant prepared by the above process.
  • the resulting silane-modified polyether sealant can have both good elasticity and strength and good storage stability. It has a fast curing speed, high bonding strength and long-term preservation. It is an excellent silane-modified polyether sealant.
  • silane-modified polyether sealant composition of the present invention and the silane-modified polyether sealant and a method for preparing the same are further illustrated by the following examples. However, the invention is not limited to the embodiments listed below.
  • step (2) The product obtained in the step (1) is cooled to below 40 ° C, and 10 g of N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane is added under a nitrogen atmosphere at 25 ° C. Stirring at 300 rpm for 20 min;
  • step (3) To the product obtained in the step (2), 2 g of dibutyltin bis(acetylacetonate) and 10 g of vinyltrimethoxysilane were added, and stirred at 300 ° C for 30 min at 25 ° C, and then the product was sent. The mixture was placed in a vacuum defoaming machine and defoamed at a vacuum of -0.06 MPa at 25 ° C for 30 min at 300 rpm to obtain a sealant A1.
  • sealant A2 According to the method described in Example 1, except that 300 g of polypropylene glycol, 1000 g of nano calcium carbonate, 15 g of N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane were used, and Carbon black to obtain sealant A2.
  • Example 1 The procedure of Example 1 was followed except that 130 g of fumed silica, 15 g of N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, and 5 g of bis(acetylacetonate) were used. Dibutyltin to obtain sealant A3.
  • Example 1 The procedure of Example 1 was followed except that a triethoxy-terminated polyether (available from Ruiyang Litai 15000E grade, an apparent viscosity of 16000 mPa ⁇ s) was used instead of the dimethoxy-terminated polyether.
  • the sealant A4 was obtained by using didecyl phthalate instead of polypropylene glycol.
  • Example 1 The procedure of Example 1 was carried out except that all the components used in Example 1 were stirred at 80 ° C for 15 min at 900 rpm, and then stirred at 1000 ° C for 30 min at 30 ° C for a vacuum degree of - The mixture was degassed at 0.06 MPa and at 30 ° C for 15 min at 1000 rpm to obtain a sealant A5.
  • Example 1 The procedure of Example 1 was carried out except that ⁇ -aminopropyltrimethoxysilane was used instead of N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane to prepare a sealant A6.
  • Example 1 The procedure of Example 1 was carried out except that n-butyl dilaurate was used instead of bis(acetylacetonate) dibutyltin, and a silane coupling agent ⁇ -aminopropyltrimethoxysilane was used instead of N-( ⁇ - Aminoethyl)- ⁇ -aminopropyltrimethoxysilane to prepare a sealant D1.
  • Example 1 The procedure of Example 1 was followed except that a dimethoxy-terminated polyether (available from Wacker Chemie AG GENIOSIL XT grade) having an apparent viscosity of 6000 mPa ⁇ s was used instead of the apparent viscosity in Example 1. A dimethoxy-terminated polyether of 8000 mPa ⁇ s to prepare a sealant D2.
  • a dimethoxy-terminated polyether available from Wacker Chemie AG GENIOSIL XT grade
  • Example 2 According to the method described in Example 1, except that a dimethoxy-terminated polyether (purchased from Ruiyang Litai 12000DS brand) having an apparent viscosity of 20,000 mPa ⁇ s was used instead of the apparent viscosity in Example 1. It is a dimethoxy-terminated polyether of 8000 mPa ⁇ s, thereby producing a sealant D3.
  • a dimethoxy-terminated polyether purchased from Ruiyang Litai 12000DS brand
  • the method for measuring the dry time includes: applying an appropriate amount of sealant on a clean Teflon plate at (25 ⁇ 5) ° C, (55 ⁇ 5)% RH, the thickness is about 2 mm, and is used every 1 min. The finger touches the rubber surface, and the time until the hand is not sticky is the dry time;
  • the method of measuring the curing speed includes: using a polytetrafluoroethylene chute having a length of about 300 mm and a depth of 0-10 mm. Squeeze a proper amount of sealant into the chute, scrape it with a spatula, do not allow air bubbles in the glue layer, and lift it from the thinnest part after being placed for 24 hours at (25 ⁇ 2) °C, (55 ⁇ 5)% RH. The film, up to the uncured adhesion, is measured for the depth of the groove, expressed in mm/24h.
  • the tensile strength and elongation at break are measured according to the method described in GB/T528-1998;
  • the Al-Al bond strength is measured according to the method described in GB/T7124-2008;
  • Thixotropy (characterized as sag) is measured according to the method of GB/T13477.6-2002;
  • the hardness is measured according to the method described in GB/T531-1999;
  • the storage period is measured by placing a sealed tube containing a clear dealcoholized sealant into a dark, dry ring at 25 ° C. Preserved in the environment, sampling regularly (about 1 month), extruding and observing the appearance of the sealant, and testing its mechanical properties (ie, tensile strength and elongation at break) (according to the above test), appearance and performance
  • the critical time of change is small and its normal storage period.
  • silane-modified polyether sealant when the silane-modified polyether sealant is prepared by using the components of the silane-modified polyether sealant composition of the present invention, both the elasticity and the strength can be obtained, and A silane-modified polyether sealant having good storage stability, for example, a surface dry time of 30 minutes or less, preferably 10 minutes or less; a curing speed of 4.5 mm/24 h or more, preferably 5-7 mm/24 h; and a tensile strength of 3 MPa.
  • elongation at break is about 180-240%; Al-Al bond strength is 2.4 MPa or higher, preferably 2.8-4 MPa; thixotropy-sag is 0.4 mm or less, preferably 0.2 or less; The hardness Shore A is 45-55; the storage period is 4 months or longer, preferably 6 months or longer.

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Abstract

提供了硅烷改性的聚醚密封胶组合物和硅烷改性的聚醚密封胶及其制备方法，所述硅烷改性的聚醚密封胶组合物含有：烷氧基封端的聚醚、碳酸钙、白炭黑、有机螯合锡催化剂、增塑剂、除水剂和增粘剂，其中，所述烷氧基封端的聚醚的表观粘度为7000-16000mPa·s，所述增粘剂为双氨基硅烷增粘剂、单氨基硅烷增粘剂和烷氧基硅烷增粘剂中的一种或多种。

Description

硅烷改性的聚醚密封胶组合物和硅烷改性的聚醚密封胶及其制备方法 技术领域
本发明涉及密封胶领域，具体涉及硅烷改性的聚醚密封胶组合物和硅烷改性的聚醚密封胶及其制备方法。
背景技术
目前市场上的硅烷改性的聚醚密封胶是以烷氧基封端的聚醚为原料，加以适量补强填料(碳酸钙、二氧化硅、有机蒙脱土等)，增塑剂(邻苯二甲酸二癸酯、苯甲酸酯、十五烷基磺酸苯酯、聚醚多元醇等)，除水剂(氧化钙、强水解性硅烷偶联剂等)，增粘剂(氨基硅烷、环氧基硅烷、丙烯酸改性硅烷等)，以有机锡催化剂(正二月桂酸二丁基锡、草酸亚锡等)。这样的硅烷封端的聚醚密封胶产品主要存在以下几个缺点：(1)密封胶力学性能不是很好，高拉伸强度的产品弹性不是很好，弹性好的产品强度不是很高；(2)贮存稳定性不好，可能随着时间的推移会变稠明显，甚至凝胶，贮存期不是很长。
发明内容
本发明的目的在于针对现有的硅烷改性的聚醚密封胶弹性和强度不能很好匹配且贮存稳定性不好的缺陷，提供一种兼具较好的弹性和强度、且贮存稳定性较好的硅烷改性的聚醚密封胶组合物和硅烷改性的聚醚密封胶及其制备方法。
为了实现上述目的，在本发明的一个方面，本发明提供一种硅烷改性的聚醚密封胶组合物。根据本发明的实施例，所述组合物含有：烷氧基封端的聚醚、碳酸钙、白炭黑、有机螯合锡催化剂、增塑剂、除水剂和增粘剂，其中，所述烷氧基封端的聚醚的表观粘度为7000-16000mPa·s，所述增粘剂为双氨基硅烷增粘剂、单氨基硅烷增粘剂和烷氧基硅烷增粘剂中的一种或多种。
在本发明的再一个方面，本发明还提供了一种硅烷改性的聚醚密封胶的制备方法，该方法包括将上述组合物含有的成分进行混合。
在本发明的又一个方面，本发明还提供了该方法制得的硅烷改性的聚醚密封胶。
通过采用本发明的硅烷改性的聚醚密封胶组合物制得的硅烷改性的聚醚密封胶，能够兼具较好的弹性和强度、且贮存稳定性较好。
本发明的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本发明的实践了解到。
发明详细描述
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
在本发明的一个方面，本发明提供一种硅烷改性的聚醚密封胶组合物。根据本发明的实施例，该组合物含有：烷氧基封端的聚醚、碳酸钙、白炭黑、有机螯合锡催化剂、增塑剂、除水剂和增粘剂，其中，所述烷氧基封端的聚醚的表观粘度为7000-16000mPa·s，所述增粘剂为双氨基硅烷增粘剂、单氨基硅烷增粘剂和烷氧基硅烷增粘剂中的一种或多种。
根据本发明的实施例，为了能够得到弹性和强度都好且贮存稳定性更好的硅烷改性的聚醚密封胶，优选情况下，相对于100重量份的烷氧基封端的聚醚，所述碳酸钙的用量为80-150重量份(优选为80-130重量份)，所述白炭黑的用量为5-20重量份，所述有机螯合锡催化剂的用量为0.1-1重量份，所述增塑剂的用量为10-50重量份(优选为10-45重量份)，所述除水剂的用量为1-5重量份，所述增粘剂的用量为1-5重量份。
更优选地，相对于100重量份的烷氧基封端的聚醚，所述碳酸钙的用量为80-130重量份，所述白炭黑的用量为10-15重量份，所述有机螯合锡催化剂的用量为0.2-1重量份，所述增塑剂的用量为10-45重量份，所述除水剂的用量为1-3重量份，所述增粘剂的用量为1-3重量份。
更进一步优选地，相对于100重量份的烷氧基封端的聚醚，所述碳酸钙的用量为90-120重量份，所述白炭黑的用量为10-15重量份，所述有机螯合锡催化剂的用量为0.2-1重量份，所述增塑剂的用量为25-40重量份，所述除水剂的用量为1-3重量份，所述增粘剂的用量为1-3重量份。
更进一步优选地，相对于100重量份的烷氧基封端的聚醚，所述碳酸钙的用量为100-120重量份，所述白炭黑的用量为10-15重量份，所述有机螯合锡催化剂的用量为0.2-0.5重量份，所述增塑剂的用量为30-40重量份，所述除水剂的用量为1-2重量份，所述增粘剂的用量为1-2重量份。
根据本发明的实施例，所述烷氧基封端的聚醚可以采用本领域常规采用的制备硅烷改性的聚醚密封胶的聚醚。作为所述烷氧基封端的聚醚的具体实例例如可以为：二甲氧基封端的聚醚、三乙氧基封端的聚醚和三甲氧基封端的聚醚中的一种或多种。
本发明采用表观粘度为7000-16000mPa·s的烷氧基封端的聚醚是一种高拉伸模量的烷氧基封端的聚醚，其在固化过程中具有较高的交联密度，有利于提高拉伸强度。尽管本发明采用表观粘度为7000-16000mPa·s的烷氧基封端的聚醚即可与所述组合物的其他成分配合得到本发明所需的硅烷改性的聚醚密封胶，为了能够获得性质更为优良的硅烷改性的聚醚密封胶，优选地，所述烷氧基封端的聚醚的表观粘度为8000-15000mPa·s，更优选为 8000-12000mPa·s。
根据本发明的实施例，所述碳酸钙优选为纳米碳酸钙，更优选采用颗粒大小为50-200nm(优选为100-150nm)的纳米碳酸钙。特别优选采用硬脂酸表面处理后的纳米碳酸钙。
根据本发明的实施例，所述白炭黑优选为气相法白炭黑，特别优选采用二甲基二氯硅烷表面处理后的气相法白炭黑作为本发明所述的白炭黑。
在本发明中，所述碳酸钙和白炭黑的组合能够相互配合地补强，以最大限度地提升有机物与无机粉体的相互作用力，提高所得的聚醚密封胶的力学性能，特别是采用经过表面处理后的上述纳米碳酸钙和表面处理后的气相法白炭黑的组合，能够更好地提高无机粉体和有机组分的相容性，分散效果会得到提高。因此，本发明采用所述碳酸钙和白炭黑的组合作为增强作用无机粉体组合，能够较好地配合所述组合物的其他成分，使得所得的聚醚密封胶能够获得较好的弹性和强度以及较好的贮存稳定性。优选地，所述碳酸钙和白炭黑的重量比为100：5-20，优选为100：8-15。
根据本发明的实施例，所述有机螯合锡催化剂具有较高的催化活性，其能够配合所述组合物中的其他成分获得弹性和强度都好且贮存稳定性好的硅烷改性的聚醚密封胶，优选地，所述有机螯合锡催化剂为双(乙酰丙酮酸)二丁基锡。
根据本发明的实施例，所述增塑剂具有稀释整个组合物的体系以及增加密封胶弹塑性的作用，其能够配合所述组合物中的其他成分获得弹性和强度都好且贮存稳定性好的硅烷改性的聚醚密封胶。本发明中所述的增塑剂优选为小分子增塑剂，当采用反应惰性的小分子物质作为增塑剂分散在密封胶中能在维持着有机分子链段相互作用力的前提下，在拉伸时使其能发生一定的相对滑动，提高伸长率。
更优选地，所述增塑剂为数均分子量为2000-3000的聚丙二醇、邻苯二甲酸二癸酯、苯甲酸酯和十五烷基磺酸苯酯中的一种或多种。
根据本发明的实施例，所述除水剂通过与组合物体系中的水分反应来除去水分，能够配合所述组合物中的其他成分获得弹性和强度都好且贮存稳定性好的硅烷改性的聚醚密封胶，优选地，所述除水剂为乙烯基三甲氧基硅烷、无水氯化钙和氧化钙中的一种或多种，更优选为乙烯基三甲氧基硅烷。
根据本发明的实施例，所述增粘剂具有增加粘接性能且助于固化交联的作用，能够配合所述组合物中的其他成分获得弹性和强度都好且贮存稳定性好的硅烷改性的聚醚密封胶。本发明中所述增粘剂为双氨基硅烷增粘剂、单氨基硅烷增粘剂和烷氧基硅烷增粘剂中的一种或多种。
其中，所述双氨基硅烷增粘剂的具体实例可以为：N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷。
所述单氨基硅烷增粘剂的具体实例可以为：γ-氨丙基三甲氧基硅烷。
所述烷氧基硅烷增粘剂的具体实例可以为：γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷。
优选情况下，所述增粘剂为N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、γ-氨丙基三甲氧基硅烷和γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷中的一种或多种，特别优选为N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷。
根据本发明的实施例，所述组合物还可以含有着色剂，所述着色剂例如可以为炭黑、钛白粉和氧化铁中的一种或多种。优选地，相对于100重量份的烷氧基封端的聚醚，所述着色剂的用量为1-10重量份。
根据本发明的实施例，在本发明的一种优选的实施方式中，所述组合物不含有交联剂，即便在不采用交联剂的情况下，本发明的组合物也可以获得弹性和强度都好且贮存稳定性好的硅烷改性的聚醚密封胶。
在本发明的再一个方面，本发明还提供了一种硅烷改性的聚醚密封胶的制备方法，该方法包括将上述组合物含有的成分进行混合。
尽管本发明的方法可以包括将上述组合物含有的成分按照任何形式混合的方法，例如可以采用将上述组合物含有的成分进行一次性混合的方法，或者按照一定的顺序混合的方法，其中，对于一次性混合的方法来说，该方法包括：将将烷氧基封端的聚醚、增塑剂、除水剂、碳酸钙、白炭黑、任选的着色剂、增粘剂和有机螯合锡催化剂进行混合。
该混合的条件例如可以包括：先在50-100℃的温度下、500-1000rpm的转速下混合100-180min，然后再在15-40℃的温度下、500-1000rpm的转速下混合20-40min。该方法还包括将混合后的产物进行真空脱泡，所述真空脱泡的条件例如可以包括：真空度为-0.1MPa至-0.05MPa、在15-40℃的温度下、500-1000rpm的转速下脱泡10-30min。
优选地，本发明的硅烷改性的聚醚密封胶的制备方法将按照一定的顺序将上述组合物含有的成分进行混合，即，优选地，该方法包括：
(1)将烷氧基封端的聚醚、增塑剂、除水剂、碳酸钙和白炭黑进行混合；
(2)将步骤(1)所得的产物与增粘剂进行混合；
(3)将步骤(2)所得的产物和有机螯合锡催化剂进行混合。
根据本发明实施例，该方法中，所述烷氧基封端的聚醚、碳酸钙、白炭黑、有机螯合锡催化剂、增塑剂、除水剂和增粘剂的种类和用量如上文中所描述的，在此不再赘述。
根据本发明的实施例，优选的，可以在步骤(1)中加入着色剂，该着色剂的种类和用量如上文中所描述的，在此不再赘述。
根据本发明的实施例，优选的，本发明的硅烷改性的聚醚密封胶的制备方法可以按照一定的顺序将上述组合物含有的成分进行混合，该方法包括：
(1)将烷氧基封端的聚醚、增塑剂、除水剂、碳酸钙、白炭黑和任选的着色剂进行混合；
(2)将步骤(1)所得的产物与增粘剂进行混合；
(3)将步骤(2)所得的产物和有机螯合锡催化剂进行混合。
根据本发明实施例，该方法中，所述烷氧基封端的聚醚、碳酸钙、白炭黑、有机螯合锡催化剂、增塑剂、除水剂、增粘剂和着色剂的种类和用量如上文中所描述的，在此不再赘述。
根据本发明的实施例，步骤(1)中，白炭黑在混合前优选经过高温烘干，例如在100-150℃下烘干12-30h。优选情况下，步骤(1)的混合条件包括：温度为70-90℃(优选为80-90℃)，时间为60-180min(优选为120-150min)。该混合的搅拌速率例如可以为600-1500rpm，优选为900-1100rpm)。该步骤的混合可以达到除水的目的，该混合过程可以通过本领域常规的各种方式进行，例如在动力混合机中进行混合。
根据本发明的实施例，优选地，步骤(2)的混合条件包括：温度为15-40℃(优选为25-40℃)，时间为10-60min(优选为20-40min)。该混合的搅拌速率例如可以为200-900rpm，优选为300-500rpm。该步骤混合优选在非活泼性气体气氛中进行，例如可以在氮气、氦气和氖气中的一种或多种非活泼性气体的气氛中进行。通过在非活泼性气体气氛中的分散处理，可以有利于缩短以下的真空脱泡处理的时间。
根据本发明，优选地，步骤(3)的混合条件包括：温度为15-40℃(优选为25-40℃)，时间为10-60min(优选为20-40min)。该混合的搅拌速率例如可以为200-900rpm，优选为300-500rpm。更优选地，该方法包括：在进行步骤(3)的混合后，对混合所得产物进行真空脱泡处理。可以将步骤(3)混合所得产物送入至真空脱泡机中进行脱泡，该真空脱泡处理的条件包括：真空度为-0.1MPa至-0.05MPa，温度为15-40℃(优选为25-40℃)，时间为10-60min(优选为20-30min)。该真空脱泡处理可以在搅拌下进行，例如可以在转速为200-900rpm、优选为300-500rpm的搅拌下进行。
根据本发明的实施例，为了能够获得更好的除水效果，以便获得贮存稳定性好的硅烷改性的聚醚密封胶，优选地，该方法包括：将除水剂分两步加入，在步骤(1)中加入除水剂总用量的40-60重量％的除水剂，剩余的除水剂在步骤(3)中加入并与步骤(2)所得的产物和有机螯合锡催化剂进行混合。
当然，本发明的硅烷改性的聚醚密封胶并不排除其他的添加剂成分，只要这样的添加剂成分并不影响本发明所得的硅烷改性的聚醚密封胶的性能即可。作为这样的添加剂例如可以为有机蒙脱土等。这些添加剂可以在上述任意步骤中加入混合，只要这样的添加不会影响本发明所得的硅烷改性的聚醚密封胶的性能即可。
在本发明的又一个方面，本发明还提供了由上述方法制得的硅烷改性的聚醚密封胶。所得的硅烷改性的聚醚密封胶能够兼具较好的弹性和强度的且贮存稳定性较好。其固化速度快，粘结强度高，能够长期保存，是一种优良的硅烷改性的聚醚密封胶。
下面通过列举实施例，对本发明的硅烷改性的聚醚密封胶组合物和硅烷改性的聚醚密封胶及其制备方法进行进一步说明。但本发明并限定于以下所列举的实施例。
实施例1
(1)将1000g的二甲氧基封端的聚醚(购自Kaneka公司S303H牌号，表观粘度为8000mPa·s)、400g的聚丙二醇(购自上海高桥石化公司，数均分子量为3000)、10g的乙烯基三甲氧基硅烷、1200g的纳米碳酸钙(购自美国特种矿物公司，颗粒大小约为100nm，预先在120℃下干燥24h)、100g的气相法白炭黑(购自德固赛公司R974牌号，预先在120℃下干燥24h)和15g的炭黑加入到动力混合机中，在80℃下、以1000rpm的转速搅拌150min，以混合除水；
(2)将步骤(1)所得的产物降温至40℃以下，并在氮气气氛下加入10g的N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷，并在25℃下、以300rpm的转速搅拌20min；
(3)向步骤(2)所得的产物中加入2g的双(乙酰丙酮酸)二丁基锡和10g的乙烯基三甲氧基硅烷，并在25℃下、以300rpm的转速搅拌30min，随后将产物送入至真空脱泡机中，于真空度为-0.06MPa下、25℃下、以300rpm的转速搅拌脱泡15min出料，得到密封胶A1。
实施例2
根据实施例1所述的方法，不同的是，采用300g的聚丙二醇，1000g的纳米碳酸钙，15g的N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷，并且不加入炭黑，从而得到密封胶A2。
实施例3
按照实施例1的方法进行，不同的是，采用130g的气相法白炭黑，15g的N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷，5g的双(乙酰丙酮酸)二丁基锡，从而得到密封胶A3。
实施例4
按照实施例1的方法进行，不同的是，采用三乙氧基封端的聚醚(购自瑞阳立泰公司15000E牌号，表观粘度为16000mPa·s)代替二甲氧基封端的聚醚，采用邻苯二甲酸二癸酯代替聚丙二醇，从而得到密封胶A4。
实施例5
按照实施例1的方法进行，不同的是，将实施例1采用的全部成分一起在80℃下、以900rpm的转速搅拌150min，再在30℃下以1000rpm的转速搅拌30min，于真空度为-0.06MPa下、30℃下、以1000rpm的转速搅拌脱泡15min出料，得到密封胶A5。
实施例6
按照实施例1的方法进行，不同的是，采用γ-氨丙基三甲氧基硅烷代替N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷，从而制得密封胶A6。
对比例1
按照实施例1的方法进行，不同的是，采用正丁基二月桂酸锡代替双(乙酰丙酮酸)二丁基锡，采用硅烷偶联剂γ-氨丙基三甲氧基硅烷代替N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷，从而制得密封胶D1。
对比例2
按照实施例1的方法进行，不同的是，采用表观粘度为6000mPa·s的二甲氧基封端的聚醚(购自瓦克化学公司GENIOSIL XT牌号)代替实施例1中的表观粘度为8000mPa·s的二甲氧基封端的聚醚，从而制得密封胶D2。
对比例3
根据实施例1所述的方法，不同的是，采用表观粘度为20000mPa·s的二甲氧基封端的聚醚(购自瑞阳立泰公司12000DS牌号)代替实施例1中的表观粘度为8000mPa·s的二甲氧基封端的聚醚，从而制得密封胶D3。
测试例
对上述所得密封胶A1-A6和D1-D3的表干时间、固化速度、拉伸强度、断裂伸长率、Al-Al粘结强度、触变性、硬度和贮存期进行测量，结果如表1所示，其中：
表干时间的测量方法包括：在(25±5)℃、(55±5)％RH条件下，在干净的聚四氟乙烯板上涂上适量的密封胶，厚度约2mm，每隔1min用手指轻触胶面，至不粘手的时间即为表干时间；
固化速度的测量方法包括：用一个长约300mm，深度为0-10mm渐深的聚四氟乙烯斜槽。向斜槽中挤出适量的密封胶，用刮刀刮平，勿使胶层内有气泡，在(25±2)℃、(55±5)％RH条件下放置24h后从最薄处揭起胶膜，直至未固化的粘连处，测该处槽的深度，以mm/24h表示。
伸强度及断裂伸长率按照GB/T528-1998中记载的方法进行测量；
Al-Al粘结强度是按照GB/T7124-2008中记载的方法进行测量；
触变性(表征为下垂度)是按照GB/T13477.6-2002样的方法进行测量的；
硬度按照GB/T531-1999中记载的方法进行测量；
贮存期的测量方法包括：将装有透明脱醇型密封胶的密封管放入到25℃阴暗干燥的环 境中保存，定期(约1个月)取样，挤出观察密封胶的外观状态，并对其力学性能(即伸强度及断裂伸长率)进行测试(按照上述检测实验)，外观状态及性能变化不大的临界时间及为其正常贮存期。
表1实施例1-6和对比例1-3所得密封胶A1-A6和D1-D3
Figure PCTCN2017070123-appb-000001
通过表1的数据可以看出，通过采用本发明的硅烷改性的聚醚密封胶组合物的成分来制备硅烷改性的聚醚密封胶时，能够获得兼具较好的弹性和强度、且贮存稳定性较好的硅烷改性的聚醚密封胶，例如表干时间在30min以下，优选在10min以下；固化速度在4.5mm/24h以上，优选在5-7mm/24h；拉伸强度在3MPa以上，优选在4MPa以上；断裂伸长率在180-240％左右；Al-Al粘结强度在2.4MPa以上，优选在2.8-4MPa；触变性-下垂度在0.4mm以下，优选在0.2以下；硬度邵氏A在45-55；贮存期在4个月以上，优选在6个月以上。
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和 组合。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (23)

  1. 一种硅烷改性的聚醚密封胶组合物，其特征在于，所述组合物含有：烷氧基封端的聚醚、碳酸钙、白炭黑、有机螯合锡催化剂、增塑剂、除水剂和增粘剂，其中，所述烷氧基封端的聚醚的表观粘度为7000-16000mPa·s，所述增粘剂为双氨基硅烷增粘剂、单氨基硅烷增粘剂和烷氧基硅烷增粘剂中的一种或多种。
  2. 根据权利要求1所述的组合物，其特征在于，相对于100重量份的所述烷氧基封端的聚醚，所述碳酸钙的用量为80-150重量份，所述白炭黑的用量为5-20重量份，所述有机螯合锡催化剂的用量为0.1-1重量份，所述增塑剂的用量为10-50重量份，所述除水剂的用量为1-5重量份，所述增粘剂的用量为1-5重量份。
  3. 根据权利要求1或2所述的组合物，其特征在于，相对于100重量份的所述烷氧基封端的聚醚，所述碳酸钙的用量为80-130重量份，所述白炭黑的用量为10-15重量份，所述有机螯合锡催化剂的用量为0.2-1重量份，所述增塑剂的用量为10-45重量份，所述除水剂的用量为1-3重量份，所述增粘剂的用量为1-3重量份。
  4. 根据权利要求1-3中任一项所述的组合物，其特征在于，所述碳酸钙为颗粒大小为50-200nm的纳米碳酸钙。
  5. 根据权利要求1-4中任一项所述的组合物，其特征在于，所述碳酸钙和白炭黑的重量比为100：5-20。
  6. 根据权利要求1-5中任一项所述的组合物，其特征在于，所述烷氧基封端的聚醚为二甲氧基封端的聚醚、三乙氧基封端的聚醚和三甲氧基封端的聚醚中的一种或多种。
  7. 根据权利要求1-6中任一项所述的组合物，其特征在于，所述有机螯合锡催化剂为双(乙酰丙酮酸)二丁基锡。
  8. 根据权利要求1-7中任一项所述的组合物，其特征在于，所述增塑剂为数均分子量2000-3000的聚丙二醇、邻苯二甲酸二癸酯、苯甲酸酯和十五烷基磺酸苯酯中的一种或多种。
  9. 根据权利要求1-8中任一项所述的组合物，其特征在于，所述除水剂为乙烯基三甲氧基硅烷、无水氯化钙和氧化钙中的一种或多种。
  10. 根据权利要求1-9中任一项所述的组合物，其特征在于，所述除水剂为乙烯基三甲氧基硅烷。
  11. 根据权利要求1-10中任一项所述的组合物，其特征在于，所述增粘剂为N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、γ-氨丙基三甲氧基硅烷和γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷中的一种或多种，更优选为N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷。
  12. 根据权利要求1-11中任一项所述的组合物，其特征在于，所述组合物还含有着色 剂。
  13. 根据权利要求1-12中任一项所述的组合物，其特征在于，所述着色剂为炭黑、钛白粉和氧化铁中的一种或多种。
  14. 根据权利要求1-13中任一项所述的组合物，其特征在于，相对于100重量份的所述烷氧基封端的聚醚，所述着色剂的用量为1-10重量份。
  15. 一种硅烷改性的聚醚密封胶的制备方法，其特征在于，所述方法包括将权利要求1-14中任一项所述的组合物含有的成分进行混合。
  16. 根据权利要求15所述的方法，其特征在于，包括：
    (1)将烷氧基封端的聚醚、增塑剂、除水剂、碳酸钙和白炭黑进行混合；
    (2)将步骤(1)所得的产物与增粘剂进行混合；
    (3)将步骤(2)所得的产物和有机螯合锡催化剂进行混合。
  17. 根据权利要求16所述的方法，其特征在于，进一步包括：在步骤(1)中，加入着色剂。
  18. 根据权利要求16或17所述的方法，其特征在于，步骤(1)的混合条件包括：温度为70-90℃，时间为60-180min。
  19. 根据权利要求16-18中任一项所述的方法，其特征在于，步骤(2)的混合条件包括：温度为15-40℃，时间为10-60min。
  20. 根据权利要求16-19中任一项所述的方法，其特征在于，步骤(3)的混合条件包括：温度为15-40℃，时间为10-60min。
  21. 根据权利要求16-20中任一项所述的方法，其特征在于，所述方法包括：将所述除水剂分两步加入，在步骤(1)中加入除水剂总用量的40-60重量％的除水剂，剩余的除水剂在步骤(3)中加入并与步骤(2)所得的产物和所述有机螯合锡催化剂进行混合。
  22. 根据权利要求16-21中任一项所述的方法，其特征在于，进一步包括：在进行步骤(3)的混合后，对混合所得产物进行真空脱泡处理。
  23. 根据权利要求15-22中任一项所述的方法制得的硅烷改性的聚醚密封胶。
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