CN108164680A - A kind of middle high-modulus silane modified polyether resin material and preparation method thereof - Google Patents
A kind of middle high-modulus silane modified polyether resin material and preparation method thereof Download PDFInfo
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- CN108164680A CN108164680A CN201711440120.3A CN201711440120A CN108164680A CN 108164680 A CN108164680 A CN 108164680A CN 201711440120 A CN201711440120 A CN 201711440120A CN 108164680 A CN108164680 A CN 108164680A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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Abstract
This application involves a kind of middle high-modulus silane modified polyether resin materials.The application also provides a kind of method for preparing middle high-modulus silane modified polyether resin material.In the above-mentioned methods, specific polyether polyol is made to be reacted with organic multiple isocyanate first, obtains the base polyurethane prepolymer for use as with specific isocyanate base content；Then the base polyurethane prepolymer for use as is made to be reacted with silane end-cappers, obtains the middle high-modulus silane modified polyether resin material.The advantageous effect of the application is that the middle high-modulus silane modified polyether resin material of the application has preferable mobility at normal temperatures, it is colourless to weak yellow liquid, the silane-modified fluid sealant of high-modulus in can further preparing can form preferable adhesive property with numerous base materials.
Description
Technical field
This application involves fluid sealant technical fields.Specifically, this application involves a kind of middle high-modulus silane modified polyethers
Resin material and preparation method thereof.
Background technology
Authoritative institution's survey report shows that the silane-modified fluid sealant market share of Japan is 45% at present, and Europe is 30%,
The U.S. is 23%, but Chinese market only accounts for 2%.Why silane-modified fluid sealant can be accounted in the market share of developed country
It is so big and the market share is so low at home, inventor think this still need our compatriots to continue the work done it
One.
Silane-modified fluid sealant, steam mainly through the air are reacted with the silane group in fluid sealant,
Small molecule alcohol substance is sloughed, so as to form cross-linked structure, the effect of adhering and sealing is carried out to bond.It is this silane-modified close
Sealing, core starting materials rely primarily on silane modified polyether resin and play a role.Silane modified polyether resin is mainly using containing
The silane coupling agent of active group blocks polyurethane resin, has polyurethane again so as to form a kind of existing silane structure
The silane modified polyether resin of structure.
The sealing structure of component is seam commonly used glue kind of the fluid sealant in processing component.This fluid sealant needs to have
The standby extensive cementability with base material has certain modulus, intensity and resilience.Meanwhile as people’s lives level is got over
Come higher, the performances such as safety and environmental protection are also increasingly paid attention to, rather than just pursuing bum cheap products.Exactly cope with
The fluid sealant development trend in domestic and international market future, silane modified polyether seal glue product come into being.
Main raw material(s) in silane modified polyether seal glue product is silane modified polyether resin.Growing sealing
Glue market causes the research and development of silane modified polyether resin more and more to seem important.Carrying out middle high-modulus silane modified polyether resin will
It may consequently contribute to the entire market expansion of silane-modified fluid sealant and occupying for share.
For this purpose, there is an urgent need in the art to develop a kind of middle high-modulus silane modified polyether resin material and preparation method thereof.
Invention content
The application's is designed to provide a kind of middle high-modulus silane modified polyether resin material, above-mentioned existing so as to solve
The technical issues of in technology.The purpose of the application, which also resides in provide, a kind of prepares middle high-modulus silane modified polyether resin material
Method.In the preparation of the application in the method for high-modulus silane modified polyether resin material, make specific polyether polyols first
Alcohol is reacted with organic multiple isocyanate, obtains the base polyurethane prepolymer for use as with specific isocyanate base content；Then make described poly-
Urethane performed polymer is reacted with silane end-cappers, obtains the middle high-modulus silane modified polyether resin material.
The middle high-modulus silane modified polyether resin material of the application is a technology based on silicane-modified polyurethane.Production
Product it is main with safety and environmental protection, curing is pollution-free, without there is the performances such as discharge of poisonous waste.The middle high-modulus fluid sealant pair realized
A variety of base materials have good adhesive property.
To achieve these goals, the application provides following technical proposals.
In the first aspect, the application provides a kind of method for preparing middle high-modulus silane modified polyether resin material, institute
The method of stating may include following step：
S1：At a temperature of 65-95 DEG C, polyether polyol is made to react for the first predetermined time with organic multiple isocyanate, is obtained
To base polyurethane prepolymer for use as；And
S2：At a temperature of 65-90 DEG C and in an inert atmosphere, the base polyurethane prepolymer for use as is made to be reacted with silane end-cappers
Second predetermined time obtained the middle high-modulus silane modified polyether resin material；
Wherein described polyether polyol degree of functionality is 2-3, number-average molecular weight 4000-8000.
In a kind of embodiment of first aspect, first predetermined time can be 2-5 hours.
In a kind of embodiment of first aspect, second predetermined time can be 2-5 hours.
In a kind of embodiment of first aspect, the method is additionally included in before step S1 to the polyether polyol
Carry out dehydration degassing process.
In a kind of embodiment of first aspect, dehydration degassing process is carried out to the polyether polyol and is included in vacuum
Under the conditions of and at a temperature of 110-120 DEG C, by the polyether polyols dehydration of alcohols degassing process third predetermined time.
In a kind of embodiment of first aspect, the third predetermined time can be 2-3 hours.
In a kind of embodiment of first aspect, the organic multiple isocyanate include isophorone diisocyanate,
One or more of hexamethylene diisocyanate, toluene di-isocyanate(TDI) or methyl diphenylene diisocyanate.
In a kind of embodiment of first aspect, in step sl, the isocyanate group of the base polyurethane prepolymer for use as (-
NCO) content is 0.4%-0.7%, and the percentage accounts for the percentage of base polyurethane prepolymer for use as gross mass for the quality of isocyanate group
Than.
In a kind of embodiment of first aspect, the step S1 is included under stirring, in 110-115 DEG C of temperature
Under degree, after polyether polyol is vacuumized dehydration degassing process 2-3 hours, then it is cooled to 30-45 DEG C and adds in organic polyisocyanate
Cyanate esters, and base polyurethane prepolymer for use as is obtained by the reaction at a temperature of 65-95 DEG C.
In a kind of embodiment of first aspect, in step s 2, the silane end-cappers is contain amino or imido
The silane end-cappers of base.
It in a kind of embodiment of first aspect, in step s 2, is counted on the basis of quality, the addition of silane end-cappers
Equivalent is the 90%-110% of isocyanate group.
In second aspect, the application provides a kind of silane-modified poly- by high-modulus in preparation as described in relation to the first aspect
Middle high-modulus silane modified polyether resin material prepared by the method for ether resin material.
In a kind of embodiment of second aspect, the middle high-modulus silane modified polyether resin material and catalyst two
The modulus that dibutyl tin laurate mixes and moisture solidification conserves gel after a week in air is 1.37-1.8mPa.
Compared with prior art, the advantageous effect of the application is the middle high-modulus silane modified polyether resinous wood of the application
Material has preferable mobility, colourless to weak yellow liquid, the silane-modified sealing of high-modulus in can further preparing at normal temperatures
Glue can form preferable adhesive property with numerous base materials.
Specific embodiment
Unless otherwise indicated, from context cues or belong to the convention of the prior art, otherwise number all in the application
Weight is all based on, and test used and characterizing method are all synchronous with the submission date of the application with percentage.It is being applicable in
In the case of, any patent, patent application or disclosure involved in the application are fully incorporated in this as reference, and its
Patent families of equal value are also introduced into as reference, disclosed by these special documents about in this field synthetic technology, product
With the definition of fabrication design, polymer, comonomer, initiator or catalyst etc..If the specific art disclosed in the prior art
Defining for language is inconsistent with any definition provided herein, then term provided herein of being subject to defines.
Digital scope in the application is approximation, therefore unless otherwise stated, it may include the number other than range
Value.Numberical range include with the increased all numerical value from lower limiting value to upper limit value of 1 unit, condition be any lower value with
There are the intervals of at least two unit between arbitrary high value.If for example, compositional, physics or other property (such as molecules
Amount, melt index (MI) etc.) it is 100 to 1000, it is meant that clearly list all single numbers, such as 100,101,102 etc., with
And all subranges, such as 100 to 166,155 to 170,198 to 200 etc..For comprising the numerical value less than 1 or comprising big
In the range of 1 score (such as 1.1,1.5 etc.), then suitably regard 1 unit as 0.0001,0.001,0.01 or 0.1.
For including the range of the units less than 10 (such as 1 to 5), usually regarding 1 unit as 0.1., these are only intended to table
The specific example of the content reached, and all possible combination of the numerical value between cited minimum and peak is all recognized
For clear record in this application.Numberical range in the application particularly provides various comonomers in acrylate copolymer
In content, content of the various components in photoetching compositions, temperature and these components during acrylic ester synthesizing it is each
Kind feature and property.
About chemical compound in use, unless explicitly stated otherwise, otherwise odd number includes all isomeric forms, otherwise also
So (for example, " hexane " either individually or collectively includes whole isomers of hexane).In addition, it unless explicitly stated otherwise, otherwise uses
"one", the noun that " one kind " or "the" are described also includes its plural form.
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise all in the application to use term "comprising"s, the composition of " comprising " or " having ", which can include, appoints
What additional additive, auxiliary material or compound.On the contrary, out to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process that do not specifically describe or list.Unless expressly stated, otherwise term "or" refers to
The separate member listed or any combination thereof.
In the first aspect, the application provides a kind of method for preparing middle high-modulus silane modified polyether resin material, institute
The method of stating may include following step：
S1：At a temperature of 65-95 DEG C, polyether polyol is made to react for the first predetermined time with organic multiple isocyanate, is obtained
To base polyurethane prepolymer for use as；And
S2：At a temperature of 65-90 DEG C and in an inert atmosphere, the base polyurethane prepolymer for use as is made to be reacted with silane end-cappers
Second predetermined time obtained the middle high-modulus silane modified polyether resin material；
Wherein described polyether polyol degree of functionality is 2-3, number-average molecular weight 4000-8000.
In second aspect, the application provides a kind of silane-modified poly- by high-modulus in preparation as described in relation to the first aspect
Middle high-modulus silane modified polyether resin material prepared by the method for ether resin material.
In a kind of specific embodiment, this application provides a kind of middle high-modulus silane modified polyether resin material and its
Preparation method, the preparation method include the following steps：
(1) it reacts polyether polyol and organic multiple isocyanate mixing and under certain condition, obtains polyurethane prepolymer
Body；The polyether polyols alcohol functionalities are 2-3, number-average molecular weight 4000-8000；
(2) above-mentioned base polyurethane prepolymer for use as and amino-silane terminated dose with active group are carried out at a certain temperature
Hybrid reaction is to get middle high-modulus silane modified polyether resin.
In step (1), the polyether polyol is the polyether polyol of conventional commercial, and for degree of functionality in the range of 2-3, number is equal
Molecular weight control can be used in the range of 4000-8000.Preferably, the polyether polyol for polyether polyol SD-2121,
It is one or more in polyether polyol SD-2122, polyether polyol SD-2123 and polyether polyol SD-2124.The polyethers
Polyalcohol SD-2121, SD-2122, SD-2123 and SD-2124 are preferably provided by Shanghai Dongda Chemical Co., Ltd..
In step (1), preferably, polyether polyol needs carry out dehydration degassing under higher temperature and vacuum condition
Processing.The dehydration degassing process can be carried out according to this field routine operation：I.e. under certain stirring, taken out by heating
Vacuum carries out dehydration degassing.The treatment temperature of the dehydration degassing is preferably 110-115 DEG C, during the processing of the dehydration degassing
Between can be this field Conventional Time, such as 2-3 hours.
In step (1), the organic multiple isocyanate is organic multiple isocyanate commonly used in the art.Preferably,
The organic multiple isocyanate for isophorone diisocyanate (IPDI) and/or hexamethylene diisocyanate (HDI) and/or
Toluene di-isocyanate(TDI) (TDI) and/or methyl diphenylene diisocyanate (MDI).The isophorone diisocyanate
(IPDI) can be the IPDI of this field conventional commercial specification, the preferably IPDI of Cohan creation production.The hexa-methylene two is different
Cyanate (HDI) can be the HDI of the HDI of this field conventional commercial specification, preferably Cohan creation production.The toluene diisocyanate
Acid esters (TDI) can be the TDI of this field conventional commercial specification, and preferably Yantai Juli Fine Chemical Co., Ltd. produces
TDI-80.The methyl diphenylene diisocyanate (MDI) can be the MDI of the various specifications of this field conventional commercial, preferably
Ground is the MDI-50 of Yantai Wanhua Polyurethane Co., Ltd's production.
In step (1), the temperature that the polyether polyol is mixed with isocyanates can be this field ordinary temperature, preferably
It is 30-45 DEG C.
In step (1), the temperature that the polyether polyol is reacted with isocyanates can be that such in this field reacts normal
Temperature is advised, preferably 75-85 DEG C, be more preferably 80-82 DEG C.
In step (1), the time that the polyether polyol is reacted with isocyanates can be that such in this field reacts normal
It advises the time, preferably 2-3 hours.
In step (1), the reaction generally carries out in reaction kettle commonly used in the art, and the reaction kettle one is well matched
A blender, a thermocouple thermometer, a vacuum elbow and a nitrogen inlet are had, the vacuum elbow needs to connect vacuum
The vaccum-pumping equipments such as pump, nitrogen inlet need to connect source nitrogen.
In step (1), isocyanate group (- NCO) content of the base polyurethane prepolymer for use as is preferably 0.4%-0.7%,
The percentage accounts for the percentage of base polyurethane prepolymer for use as gross mass for the quality of isocyanate group.
In one preferred embodiment of the application, the preparation process of the base polyurethane prepolymer for use as is as follows：Under stirring, in
At 110-115 DEG C, after polyether polyol is vacuumized dehydration degassing process 2-3 hours, being then cooled to 30-45 DEG C and adding in has
Machine polyisocyanate compound, is obtained by the reaction base polyurethane prepolymer for use as.
In step (2), the silane end-cappers with active group are mostly to contain amino or imino-silane end-capping reagent.
Described amino-silane terminated dose is amino silane commonly used in the art, and preferably SILQUESTA-1110 (steps figure).
In step (2), the addition equivalent of silane end-cappers is the 90%-110% of isocyanate group equivalent, preferably
98%-105%.
In step (2), the addition temperature of silane end-cappers is 70-85 DEG C, preferably 78-82 DEG C.
In step (2), the reaction time is 2-3 hours after the addition of silane end-cappers.
In a kind of specific embodiment, present invention also provides high-modulus middle made from above-mentioned preparation method is silane-modified
Polyether resin material.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the application
Example.
Embodiment
Below in conjunction with embodiments herein, clear and complete description is carried out to the technical solution of the application.Such as nothing
It illustrates, reagent used and raw material can all be bought by commercial sources.Actual conditions are not specified in the following example
Experimental method selects according to conventional methods and conditions or according to product manual.
In following embodiments, polyether polyol SD-2121, polyether polyol SD-2122, polyether polyol SD-2123 and
Polyether polyol SD-2124 is provided by Shanghai Dongda Chemical Co., Ltd., and degree of functionality is 2-3, and number-average molecular weight is
4000-8000.Isophorone diisocyanate (IPDI) can be the IPDI of Cohan creation production.Hexamethylene diisocyanate
(HDI) can be the HDI of Cohan creation production.Toluene di-isocyanate(TDI) (TDI) can be Yantai Juli Fine Chemical Co., Ltd.
The TDI-80 of production.Methyl diphenylene diisocyanate (MDI) is the MDI- of Yantai Wanhua Polyurethane Co., Ltd's production
50。
In following implementations, reaction carries out in a kettle.Reaction kettle generally is equipped with a blender, an electric thermo-couple temperature
Meter, a vacuum elbow and a nitrogen inlet, the vacuum elbow need to connect the vaccum-pumping equipments such as vacuum pump, nitrogen inlet
It needs to connect source nitrogen.
Embodiment 1
A kind of middle high-modulus silane modified polyether resin material, is made by following preparation method：
(1) 600g polyether polyol SD-2121 is put into reaction kettle, is warming up to 110 DEG C, stirring vacuumizes dehydration degassing 3
Hour, 40 DEG C are cooled to, then adds in 45.3g isophorone diisocyanate (IPDI), under 80 DEG C of reaction temperature, reaction
Polyase 13 hour obtains 645.3g base polyurethane prepolymer for use as；Wherein, the degree of functionality of polyether polyol SD-2121 is 2, number-average molecular weight
It is 4000；Base polyurethane prepolymer for use as-NCO content be 0.7%；
(2) by under base polyurethane prepolymer for use as stirring obtained by step (1), with 27.1g amino silanes SILQUESTA-1110
(step figure) reacted at 80 DEG C 2-3 hours to get.
Embodiment 2
A kind of middle high-modulus silane modified polyether resin material, is made by following preparation method：
(1) 600g polyether polyol SD-2122 is put into reaction kettle, is warming up to 110 DEG C, stirring vacuumizes dehydration degassing 3
Hour, 40 DEG C are cooled to, then adds in 27.7g hexamethylene diisocyanates (HDI), under 80 DEG C of reaction temperature, reaction
Polyase 13 hour obtains 627.7g base polyurethane prepolymer for use as；Wherein, the degree of functionality of polyether polyol SD-2122 is 2, number-average molecular weight
It is 5000；Base polyurethane prepolymer for use as-NCO content be 0.6%；
(2) by under base polyurethane prepolymer for use as stirring obtained by step (1), with 23.2g amino silanes SILQUESTA-1110
(step figure) reacted at 80 DEG C 2-3 hours to get.
Embodiment 3
A kind of middle high-modulus silane modified polyether resin material, is made by following preparation method：
(1) 600g polyether polyol SD-2123 is put into reaction kettle, is warming up to 110 DEG C, stirring vacuumizes dehydration degassing 3
Hour, 40 DEG C are cooled to, then adds in 24g toluene di-isocyanate(TDI)s (TDI), under 80 DEG C of reaction temperature, reactive polymeric 3 is small
When, obtain 624g base polyurethane prepolymer for use as；Wherein, the degree of functionality of polyether polyol SD-2123 is 2, number-average molecular weight 6000；It is poly-
Urethane performed polymer-NCO content be 0.5%；
(2) by under base polyurethane prepolymer for use as stirring obtained by step (1), with 19.3g amino silanes SILQUESTA-1110
(step figure) reacted at 80 DEG C 2-3 hours to get.
Embodiment 4
A kind of middle high-modulus silane modified polyether resin material, is made by following preparation method：
(1) 600g polyether polyol SD-2124 is put into reaction kettle, is warming up to 110 DEG C, stirring vacuumizes dehydration degassing 3
Hour, 40 DEG C are cooled to, then adds in 28.9g methyl diphenylene diisocyanates (MDI), under 80 DEG C of reaction temperature, instead
Polyase 13 hour is answered, obtains 628.9g base polyurethane prepolymer for use as；Wherein, the degree of functionality of polyether polyol SD-2124 is 2, the equal molecule of number
Measure is 7000；Base polyurethane prepolymer for use as-NCO content be 0.4%；
(2) by under base polyurethane prepolymer for use as stirring obtained by step (1), with 15.5g amino silanes SILQUESTA-1110
(step figure) reacted at 80 DEG C 2-3 hours to get.
Embodiment 5
A kind of middle high-modulus silane modified polyether resin material, is made by following preparation method：
(1) 300g polyether polyol SD-2123 and 300g polyether polyol SD-2124 is put into reaction kettle, is warming up to 110
DEG C, stirring vacuumizes dehydration degassing 3 hours, is cooled to 40 DEG C, then adds in 34.5g methyl diphenylene diisocyanates
(MDI), under 80 DEG C of reaction temperature, reactive polymeric 3 hours obtains 634.5g base polyurethane prepolymer for use as；Wherein, polyether polyol
The degree of functionality of SD-2123 is 2, number-average molecular weight 6000, and the degree of functionality of polyether polyol SD-2124 is 2, and number-average molecular weight is
7000；Base polyurethane prepolymer for use as-NCO content be 0.6%；
(2) by under base polyurethane prepolymer for use as stirring obtained by step (1), with 23.2g amino silanes SILQUESTA-1110
(step figure) reacted at 80 DEG C 2-3 hours to get.
Effect example
At 25 DEG C, the middle high-modulus silane modified polyether resin material viscosity of embodiment 1-5 is measured respectively, is tested simultaneously
Its with catalyst dibutyltin dilaurylate after mixing, in air moisture solidification maintenance after a week the surface drying time of gel,
Elongation at break is with tensile strength, and test result is as follows shown in table.
The above-mentioned description to embodiment is understood that for the ease of those skilled in the art and using this Shen
Please.Person skilled in the art obviously easily can make various modifications, and described herein to these embodiments
General Principle is applied in other embodiments without paying performing creative labour.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and changes within all scope of the present application.
Claims (10)
1. a kind of method for preparing middle high-modulus silane modified polyether resin material, the method includes following step：
S1：At a temperature of 65-95 DEG C, polyether polyol is made to react for the first predetermined time with organic multiple isocyanate, is gathered
Urethane performed polymer；And
S2：At a temperature of 65-90 DEG C and in an inert atmosphere, the base polyurethane prepolymer for use as is made to react second with silane end-cappers
Predetermined time obtains the middle high-modulus silane modified polyether resin material；
Wherein described polyether polyol degree of functionality is 2-3, number-average molecular weight 4000-8000.
2. the method for high-modulus silane modified polyether resin material in preparation as described in claim 1, which is characterized in that described
Method carries out dehydration degassing process before being additionally included in step S1 to the polyether polyol.
3. the method for high-modulus silane modified polyether resin material in preparation as claimed in claim 2, which is characterized in that institute
State polyether polyol carry out dehydration degassing process include under vacuum and at a temperature of 110-120 DEG C, by the polyethers
The polynary dehydration of alcohols degassing process third predetermined time.
4. the method for high-modulus silane modified polyether resin material in the preparation as described in any one of claim 1-3, special
Sign is that the organic multiple isocyanate includes isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate
One or more of acid esters or methyl diphenylene diisocyanate.
5. the method for high-modulus silane modified polyether resin material in preparation as described in claim 1, which is characterized in that in step
In rapid S1, isocyanate group (- NCO) content of the base polyurethane prepolymer for use as is 0.4%-0.7%, and the percentage is isocyanic acid
The quality of ester group accounts for the percentage of base polyurethane prepolymer for use as gross mass.
6. the method for high-modulus silane modified polyether resin material in preparation as described in claim 1, which is characterized in that described
Step S1 is included under stirring, and at a temperature of 110-115 DEG C, polyether polyol is vacuumized dehydration degassing process 2-3
After hour, then it is cooled to 30-45 DEG C and adds in organic polyisocyanate compound, and reacted at a temperature of 65-95 DEG C
To base polyurethane prepolymer for use as.
7. the method for high-modulus silane modified polyether resin material in preparation as described in claim 1, which is characterized in that in step
In rapid S2, the silane end-cappers are the silane end-cappers containing amino or imino group.
8. the method for high-modulus silane modified polyether resin material in preparation as described in claim 1, which is characterized in that in step
It in rapid S2, is counted on the basis of quality, the addition equivalent of silane end-cappers is the 90%-110% of isocyanate group.
9. a kind of side of high-modulus silane modified polyether resin material in preparation by as described in any one of claim 1-8
Middle high-modulus silane modified polyether resin material prepared by method.
10. high-modulus silane modified polyether resin material in as claimed in claim 9, which is characterized in that the middle high-modulus
Silane modified polyether resin material is mixed with catalyst dibutyltin dilaurylate and moisture solidification conserves after a week in air
The modulus of gel is 1.37-1.8mPa.
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Cited By (1)
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| CN110734730A (en) * | 2018-07-20 | 2020-01-31 | 东莞市博君来胶粘材料科技有限公司 | silane modified polyether two-component sealant and preparation method thereof |
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| EP2501762B1 (en) * | 2009-11-16 | 2016-07-13 | Saint-Gobain Isover | Use of an adhesive and sealant system for bonding of vapour barrier films |
| CN106833481A (en) * | 2017-02-06 | 2017-06-13 | 山东诺威新材料有限公司 | Environment-friendly type organosilicon modified polyether seal glue and preparation method thereof |
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| EP2501762B1 (en) * | 2009-11-16 | 2016-07-13 | Saint-Gobain Isover | Use of an adhesive and sealant system for bonding of vapour barrier films |
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| CN110734730A (en) * | 2018-07-20 | 2020-01-31 | 东莞市博君来胶粘材料科技有限公司 | silane modified polyether two-component sealant and preparation method thereof |
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