CN109535366A - A kind of secondary amino silanes modified polyether polymer and preparation method thereof - Google Patents
A kind of secondary amino silanes modified polyether polymer and preparation method thereof Download PDFInfo
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- CN109535366A CN109535366A CN201811372181.5A CN201811372181A CN109535366A CN 109535366 A CN109535366 A CN 109535366A CN 201811372181 A CN201811372181 A CN 201811372181A CN 109535366 A CN109535366 A CN 109535366A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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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- 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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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
This application involves a kind of preparation methods of secondary amino silanes modified polyether polymer, it includes that polyether polyol is dehydrated by (1) under 90~130 DEG C of vacuum conditions, deaerate 1~4h, then 50~80 DEG C are cooled to, diisocyanate and catalyst are added in polyether polyol, it is passed through inert gas, it stirs evenly, then reacts 1~6h at 50~90 DEG C, obtain isocyanate-terminated polyethers prepolymer；(2) the isocyanate-terminated polyethers prepolymer is mixed with secondary amino silanes; 30~90 DEG C at a temperature of and under inert gas protection react 1~6h; until system is by titration without reaction was completed in the presence of isocyano; then vacuum removal bubble at the reaction temperatures, obtains the secondary amino silanes modified polyether polymer.The application further relates to a kind of secondary amino silanes modified polyether polymer.The application further relates to a kind of secondary amino silanes.The silane modified polyether polymer preparation process of the application is easy to control, and will not generate gelatin phenomenon, and the sealant thus prepared is not susceptible to Yellowing.
Description
Technical field
This application involves sealant technical field, relate in particular to a kind of secondary amino silanes modified polyether polymer and its
Preparation method.
Background technique
In recent years, blocking modification is carried out to terminal isocyanate group polyether prepolymer with silane coupling agent and prepares silane-modified gather
The research of ether polymer is increasing.Silane modified polyether polymer is that the terminal isocyanate group of prepolymer is transformed into silane oxygen
Base, end group siloxy can occur hydrolytic crosslinking reaction, be formed by curing silane modified polyether polymer netted with Si-O-Si
The elastomer of structure.In addition, siloxy only releases a small amount of alcohol in hydrolytic crosslinking process, environmental pollution is small.It is silane-modified
Stronger chemical bonding can occur with nonporous substrate (such as glass, metal) surface after polyether polymer solidification to act on.Silane changes
Property polyether polymer can be used as the base polymer of silane-modified sealant, binder or coating, be widely used.
It is well known that silane end-cappers are played an important role in the preparation process of silane modified polyether polymer, to make
The application of silane modified polyether polymer is more easy and extensive, selects moderate and sealing end to work well Silante terminated
Agent is very crucial.In the preparation method of existing silane modified polyether polymer, some are even using isocyanate terminated base silane
Join agent and blocking modification is carried out to polyether polyol, however the price of terminal isocyanate group silane coupling agent is very expensive at present, state
Interior production application it is seldom, most of and prepared complicated from external import.Some are different using commercially available primary amine base silane opposite end
Cyanate base polyurethane prepolymer carries out blocking modification, however the primary hydrogen atom of primaquine one type of silane activity is high, there is ammonia tastes greatly,
The characteristics such as alkaline strong, when carrying out blocking modification to isocyanate-terminated polyethers/polyurethane prepolymer as end-capping reagent or stored
Easily there is gelatin phenomenon in Cheng Zhong；And Yellowing is easily occurred using the sealant of such silane modified polyether preparation.
For this purpose, this field, which is continuously needed, develops a kind of silane modified polyether polymer and preparation method thereof.
Summary of the invention
The application's is designed to provide a kind of secondary amino silanes modified polyether polymer and preparation method thereof, to solve
It is above-mentioned in the prior art the technical issues of.The application overcome in the prior art primaquine one type of silane as silicon prepared by end-capping reagent
Easily there is gelatin phenomenon in the synthesis process or during storage in alkane modified polyether polymer, and easily makes silane-modified sealant
Yellowing occurs.
In order to solve the above-mentioned technical problem, the application provides following technical proposals.
In the first aspect, the application provides a kind of preparation method of secondary amino silanes modified polyether polymer, the side
Method includes the following steps:
(1) polyether polyol is dehydrated under 90~130 DEG C of vacuum conditions, deaerate 1~4h, be then cooled to 50~80
DEG C, diisocyanate and catalyst are added in polyether polyol, inert gas is passed through, is stirred evenly, then at 50~90 DEG C
1~6h of lower reaction, obtains isocyanate-terminated polyethers prepolymer；
(2) the isocyanate-terminated polyethers prepolymer is mixed with secondary amino silanes, 30~90 DEG C at a temperature of and
React 1~6h under inert gas protection, until system by titration without reaction was completed in the presence of isocyano, then reacting
At a temperature of vacuum removal bubble, obtain the secondary amino silanes modified polyether polymer.
In a specific embodiment, the inert gas includes high pure nitrogen, argon gas or helium.
In a kind of embodiment of first aspect, in step (1), the isocyano and polyethers of diisocyanate are controlled
The molar ratio of the hydroxyl of polyalcohol is 1.1~2:1.
In a kind of embodiment of first aspect, in step (2), controlling secondary amino group with isocyano molar ratio is
0.9~1.2:1.
In a kind of embodiment of first aspect, secondary amino silanes modified polyether polymer as described in claim 1
Preparation method, which is characterized in that in step (1), the degree of functionality of the polyether polyol is 2 or 3, and number-average molecular weight is
6000-16000。
In a kind of embodiment of first aspect, in step (1), the diisocyanate is toluene diisocynate
Ester (TDI), methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate
One or both of (IPDI).
In a kind of embodiment of first aspect, in step (1), the catalyst is di lauric dibutyl
Tin, stannous octoate or dibutyltin diacetate.
In a kind of embodiment of first aspect, the additional amount of the catalyst accounts for polyether polyol matter in step (1)
The 0.05~0.5% of amount.
In a kind of embodiment of first aspect, in step (2), the secondary amino silanes are by the primary amino group containing end
Silane coupling agent and allyl-terminated polyether be 1:1 according to molar ratio ratio, reacted in 90 DEG C of stirring 4h obtained by.
In a kind of embodiment of first aspect, the primaryamino-silane coupling agent containing end is gamma-amino propyl three
Methoxy silane, γ aminopropyltriethoxy silane；And/or the degree of functionality of the allyl-terminated polyether is 1, number is divided equally
Son amount is 300-3000.
In a kind of embodiment of first aspect, in step (1), the dehydration, degassing temperature are 100~120
DEG C, preferably 110 DEG C；
And/or the dehydration, degassing time 1-2h, preferably 1.5h；
And/or the molar ratio of the hydroxyl of the isocyano and polyether polyol of the diisocyanate is 1.4~1.9:1,
Preferably 1.5~1.8:1；
And/or the reaction temperature of the polyether polyol and diisocyanate is 60~80 DEG C, preferably 70 DEG C；
And/or the reaction time of the polyether polyol and diisocyanate is 2~5h, preferably 3~4h；
And/or the number-average molecular weight of the polyether polyol is 7000~14000, preferably 8000~12000.
In a kind of embodiment of first aspect, in step (2), the secondary amino silanes and terminal isocyanate group
Polyether prepolymer is 1.0~1.1:1, preferably 1:1 according to secondary amino group and isocyano molar ratio；
And/or the reaction temperature of the isocyanate-terminated polyethers prepolymer and secondary amino silanes is 50~70 DEG C, compared with
It goodly is 60-70 DEG C；
And/or the reaction time of the isocyanate-terminated polyethers prepolymer and secondary amino silanes is 2~5h, preferably
Ground is 3~4h；
And/or the number-average molecular weight of the allyl-terminated polyether be 1000-3000, preferably 2000.
In second aspect, the application provides a kind of by secondary amino silanes modified polyether polymerization as described in relation to the first aspect
The preparation method of object is come the secondary amino silanes modified polyether polymer for preparing.
In a third aspect, the application provides a kind of secondary amino silanes, silane coupling agent and end by the primary amino group containing end
The ratio that allyl polyether is 1:1 according to molar ratio, obtained by 90 DEG C of stirring 4h reactions.
In a kind of embodiment of the third aspect, the primaryamino-silane coupling agent containing end is gamma-amino propyl three
Methoxy silane, γ aminopropyltriethoxy silane；And/or the degree of functionality of the allyl-terminated polyether is 1, number is divided equally
Son amount is 300-3000.
Compared with prior art, the positive effect of the present invention is that:
(1) present invention is easy using process of the secondary amino silanes coupling agent to isocyanate group polyether prepolymer blocking modification
Control, will not generate gelatin phenomenon, and product prepares favorable reproducibility, and prepared silane modified polyether/polyether polyols color
Shallowly, the sealant thus prepared is not susceptible to Yellowing.
(2) the secondary amino silanes modified polyether polymer end group prepared in the present invention is siloxy, this oligomer is in room
After the lower moisture absorbed in air of temperature, hydrolytic crosslinking reaction can occur for siloxy, to make silane envelope modified polyether solidification
Form the elastomer with Si-O-Si reticular structure；And siloxy only releases a small amount of alcohol in hydrolytic crosslinking process, to ring
Border pollution is small.Secondary amino silanes modified polyether polymer can be used as the base polymer of sealant, adhesive or coating, construction
It is very convenient；And siloxy hydrolysis generates silanol, chemical bonding effect can occur with substrates such as glass, metals, improve sealing
The adhesive strength of glue, adhesive or coating and type substrate.
(3) allyl polyether participates in the solidification crosslinking of silane envelope modified polyether as reactive plasticizer, and it is netted to become Si-O-Si
A part in structure, so that manufactured silane-modified sealant has lower modulus, higher elongation at break.
Specific embodiment
Unless otherwise indicated, from context cues or belong to the convention of the prior art, otherwise number all in the application
It is all based on weight with percentage, and test and characterizing method used is all synchronous with the submission date of the application.It is being applicable in
In the case where, 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, about the synthetic technology in this field, product disclosed by these special documents
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 limit value to upper limit value of 1 unit, condition be any lower value with
There are the intervals of at least two unit between any high value.For example, if 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 the range comprising the units less than 10 (such as 1 to 5), usually regard 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
In this application for clear record.It is also pointed out that term " first " herein, " second " etc. do not limit sequencing, only
In order to distinguish the substance of different structure.
About chemical compound in use, unless explicitly stated otherwise, otherwise odd number includes all isomeric forms, otherwise also
So (for example, whole isomers that " hexane " either individually or collectively includes hexane).In addition, unless explicitly stated otherwise, otherwise using
"one", the noun that "an" 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 in the application it is all use term "comprising"s, " comprising ", or " having " composition may include appoint
What additional additive, auxiliary material or compound.On the contrary, in addition 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 for not specifically describing or listing.Unless expressly stated, otherwise term "or" refers to
Separate member listed or any combination thereof.
In a specific embodiment, the present invention provides a kind of preparation side of secondary amino silanes modified polyether polymer
Method includes the following steps:
(1) polyether polyol is dehydrated under 90~130 DEG C of vacuum conditions, deaerate 1~4h, be then cooled to 50~80
DEG C, diisocyanate and catalyst are added in polyether polyol, the isocyano and polyether polyols of diisocyanate are controlled
The molar ratio of the hydroxyl of alcohol is 1.1~2:1；It is passed through high pure nitrogen, is stirred evenly, then reacts 1~6h at 50~90 DEG C, is obtained
Isocyanate-terminated polyethers prepolymer.
(2) by the isocyanate-terminated polyethers prepolymer and secondary amino silanes according to secondary amino group and isocyano molar ratio
It is mixed for the ratio of 0.9~1.2:1, reacts 1~6h under 30~90 DEG C, high pure nitrogen protection, until system passes through titration nothing
Reaction was completed in the presence of isocyano, then vacuum removal bubble at the reaction temperatures, and it is poly- to obtain secondary amino silanes modified polyether
Close object.
In a specific embodiment, in step (1), the degree of functionality of the polyether polyol is 2 or 3, and number is divided equally
Son amount is 6000-16000.
In a specific embodiment, in step (1), the diisocyanate be toluene di-isocyanate(TDI) (TDI),
In methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI)
One or two.
In a specific embodiment, in step (1), the catalyst is dibutyl tin dilaurate, octanoic acid Asia
Tin or dibutyltin diacetate；The additional amount of the catalyst accounts for 0.05~0.5% of polyether polyol quality in step (1).
In a specific embodiment, in step (2), the secondary amino silanes are even by the silane of the primary amino group containing end
Join the ratio that agent and allyl-terminated polyether are 1:1 according to molar ratio, obtained by 90 DEG C of stirring 4h reactions；The primary amino group containing end
Silane coupling agent is gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane；The end-allyl group is poly-
The degree of functionality of ether is 1, number-average molecular weight 300-3000.
In a specific embodiment, in step (1), the dehydration, degassing temperature are preferably 100~120 DEG C,
More preferably 110 DEG C；The dehydration, degassing time are preferably 1-2h, more preferably 1.5h.
In a specific embodiment, in step (1), the isocyano of the diisocyanate and polyether polyol
The molar ratio of hydroxyl is preferably 1.4~1.9:1, more preferably 1.5~1.8:1.
In a specific embodiment, in step (1), the reaction temperature of the polyether polyol and diisocyanate
Preferably 60~80 DEG C, more preferably 70 DEG C；Reaction time is preferably 2~5h, more preferably 3~4h.
In a specific embodiment, in step (1), the number-average molecular weight of the polyether polyol is preferably
7000~14000, more preferably 8000~12000.
In a specific embodiment, in step (2), the secondary amino silanes and isocyanate-terminated polyethers pre-polymerization
Object is preferably 1.0~1.1:1 according to secondary amino group and isocyano molar ratio, more preferably 1:1；
In a specific embodiment, in step (2), the isocyanate-terminated polyethers prepolymer and secondary amino group silicon
The reaction temperature of alkane is preferably 50~70 DEG C, more preferably 60-70 DEG C；Reaction time is preferably 2~5h, and more preferably 3
~4h.
In a specific embodiment, in step (2), the number-average molecular weight of the allyl-terminated polyether is preferably
1000-3000, more preferably 2000.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
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 according to conventional methods and conditions, or is selected according to product manual.
Embodiment 1:
(1) in the four-hole boiling flask equipped with blender, constant pressure funnel and gas-guide tube, it is equal that 100 numbers are sequentially added
The allyl-terminated polyether (S1010, Shanghai Dongda Chemical Co., Ltd.) that molecular weight is 1000, is passed through nitrogen and starts to stir, 40
Gamma-amino propyl trimethoxy silicane, the molar ratio of allyl-terminated polyether and gamma-amino propyl trimethoxy silicane are added dropwise at DEG C
It for 1:1, is added dropwise in 30 minutes, then heats to 90 DEG C, reacted 4h, obtain secondary amino silanes coupling agent.
(2) polyether polyol (C2160, Shanghai Dongda Chemical Co., Ltd.) of 100 number average molecular weights 16000 is existed
Under 110 DEG C of vacuum conditions be dehydrated, deaerate 2h, be then cooled to 60 DEG C, sequentially add TDI (isocyano of diisocyanate with
The molar ratio of the hydroxyl of polyether polyol is 2:1), dibutyl tin dilaurate (account for polyether polyol quality 0.1%), is passed through
High pure nitrogen stirs evenly as reaction protection gas, reacts 1h at 90 DEG C, obtain isocyanate-terminated polyethers prepolymer, NCO
Content is 0.5%；
(3) secondary amino silanes in the isocyanate-terminated polyethers prepolymer synthesized in step (2) and step (1) are coupled
Agent is reacted according to the ratio that secondary amino group and isocyano molar ratio are 1:1, is stirred to react under 30 DEG C, high pure nitrogen protection
6h；Until system by titration without reaction was completed in the presence of isocyano, it is poly- to obtain colorless and transparent secondary amino silanes modified polyether
Close object, viscosity 30000mPas.
Embodiment 2:
(1) in the four-hole boiling flask equipped with blender, constant pressure funnel and gas-guide tube, it is equal that 100 numbers are sequentially added
The allyl-terminated polyether that molecular weight is 1000, is passed through nitrogen and starts to stir, and gamma-amino propyl-triethoxysilicane is added dropwise at 40 DEG C
The molar ratio of alkane, allyl-terminated polyether and γ aminopropyltriethoxy silane is 1:1, is added dropwise in 30 minutes, then rises
Temperature reacts 4h, obtains secondary amino silanes coupling agent to 90 DEG C.
(2) by the polyether polyol (C2060, Shanghai Dongda Chemical Co., Ltd.) of 100 number average molecular weights 6000 110
Dehydration, degassing 2h, are then cooled to 60 DEG C, sequentially add the TDI (isocyano and polyethers of diisocyanate under DEG C vacuum condition
The molar ratio of the hydroxyl of polyalcohol is 1.3:1), dibutyl tin dilaurate (account for polyether polyol quality 0.1%), is passed through height
Pure nitrogen gas stirs evenly as reaction protection gas, reacts 6h at 50 DEG C, obtain isocyanate-terminated polyethers prepolymer, NCO contains
Amount is 0.4%；
(3) secondary amino silanes in the isocyanate-terminated polyethers prepolymer synthesized in step (2) and step (1) are coupled
Agent is reacted according to the ratio that secondary amino group and isocyano molar ratio are 1.2:1, is stirred under 90 DEG C, high pure nitrogen protection anti-
Answer 1h；Until system by titration without reaction was completed in the presence of isocyano, obtain colorless and transparent secondary amino silanes modified polyether
Polymer, viscosity 90000mPas.
Embodiment 3:
(1) in the four-hole boiling flask equipped with blender, constant pressure funnel and gas-guide tube, it is equal that 100 numbers are sequentially added
The allyl-terminated polyether (S1003, Shanghai Dongda Chemical Co., Ltd.) that molecular weight is 300, is passed through nitrogen and starts to stir, and 40 DEG C
Lower dropwise addition gamma-amino propyl trimethoxy silicane, the molar ratio of allyl-terminated polyether and gamma-amino propyl trimethoxy silicane are
1:1 is added dropwise in 30 minutes, then heats to 90 DEG C, reacts 4h, obtains secondary amino silanes coupling agent.
(2) by the polyether polyol (C2080, Shanghai Dongda Chemical Co., Ltd.) of 100 number average molecular weights 8000 110
Dehydration, degassing 2h, are then cooled to 60 DEG C, sequentially add the HDI (isocyano and polyethers of diisocyanate under DEG C vacuum condition
The molar ratio of the hydroxyl of polyalcohol is 1.4:1), dibutyl tin dilaurate (account for polyether polyol quality 0.1%), is passed through height
Pure nitrogen gas stirs evenly as reaction protection gas, reacts 5h at 60 DEG C, obtain isocyanate-terminated polyethers prepolymer, NCO contains
Amount is 0.4%；
(3) secondary amino silanes in the isocyanate-terminated polyethers prepolymer synthesized in step (2) and step (1) are coupled
Agent is reacted according to the ratio that secondary amino group and isocyano molar ratio are 1.1:1, is stirred under 70 DEG C, high pure nitrogen protection anti-
Answer 2h；Until system by titration without reaction was completed in the presence of isocyano, obtain colorless and transparent secondary amino silanes modified polyether
Polymer, viscosity 80000mPas.
Embodiment 4:
(1) in the four-hole boiling flask equipped with blender, constant pressure funnel and gas-guide tube, it is equal that 100 numbers are sequentially added
The allyl-terminated polyether (S1006, Shanghai Dongda Chemical Co., Ltd.) that molecular weight is 600, is passed through nitrogen and starts to stir, and 40 DEG C
The molar ratio of lower dropwise addition γ aminopropyltriethoxy silane, allyl-terminated polyether and γ aminopropyltriethoxy silane is
1:1 is added dropwise in 30 minutes, then heats to 90 DEG C, reacts 4h, obtains secondary amino silanes coupling agent.
(2) polyether polyol (C2140, Shanghai Dongda Chemical Co., Ltd.) of 100 number average molecular weights 14000 is existed
Under 110 DEG C of vacuum conditions be dehydrated, deaerate 2h, be then cooled to 60 DEG C, sequentially add IPDI (isocyano of diisocyanate with
The molar ratio of the hydroxyl of polyether polyol is 1.9:1), dibutyl tin dilaurate (account for polyether polyol quality 0.1%), is led to
Enter high pure nitrogen as reaction protection gas, stir evenly, react 2h at 80 DEG C, obtain isocyanate-terminated polyethers prepolymer,
NCO content is 0.5%；
(3) secondary amino silanes in the isocyanate-terminated polyethers prepolymer synthesized in step (2) and step (1) are coupled
Agent is reacted according to the ratio that secondary amino group and isocyano molar ratio are 0.9:1, is stirred under 50 DEG C, high pure nitrogen protection anti-
Answer 5h；Until system by titration without reaction was completed in the presence of isocyano, obtain colorless and transparent secondary amino silanes modified polyether
Polymer, viscosity 35000mPas.
Embodiment 5:
(1) in the four-hole boiling flask equipped with blender, constant pressure funnel and gas-guide tube, it is equal that 100 numbers are sequentially added
The allyl-terminated polyether (S1020, Shanghai Dongda Chemical Co., Ltd.) that molecular weight is 2000, is passed through nitrogen and starts to stir, 40
Gamma-amino propyl trimethoxy silicane, the molar ratio of allyl-terminated polyether and gamma-amino propyl trimethoxy silicane are added dropwise at DEG C
It for 1:1, is added dropwise in 30 minutes, then heats to 90 DEG C, reacted 4h, obtain secondary amino silanes coupling agent.
(2) polyether polyol (C2100, Shanghai Dongda Chemical Co., Ltd.) of 100 number average molecular weights 10000 is existed
Under 110 DEG C of vacuum conditions be dehydrated, deaerate 2h, be then cooled to 60 DEG C, sequentially add IPDI (isocyano of diisocyanate with
The molar ratio of the hydroxyl of polyether polyol is 1.5:1), dibutyl tin dilaurate (account for polyether polyol quality 0.1%), is led to
Enter high pure nitrogen as reaction protection gas, stir evenly, react 3h at 70 DEG C, obtain isocyanate-terminated polyethers prepolymer,
NCO content is 0.4%；
(3) secondary amino silanes in the isocyanate-terminated polyethers prepolymer synthesized in step (2) and step (1) are coupled
Agent is reacted according to the ratio that secondary amino group and isocyano molar ratio are 1:1, is stirred to react under 60 DEG C, high pure nitrogen protection
4h；Until system by titration without reaction was completed in the presence of isocyano, it is poly- to obtain colorless and transparent secondary amino silanes modified polyether
Close object, viscosity 75000mPas.
Embodiment 6:
(1) in the four-hole boiling flask equipped with blender, constant pressure funnel and gas-guide tube, it is equal that 100 numbers are sequentially added
The allyl-terminated polyether (S1030, Shanghai Dongda Chemical Co., Ltd.) that molecular weight is 3000, is passed through nitrogen and starts to stir, 40
Gamma-amino propyl trimethoxy silicane, the molar ratio of allyl-terminated polyether and gamma-amino propyl trimethoxy silicane are added dropwise at DEG C
It for 1:1, is added dropwise in 30 minutes, then heats to 90 DEG C, reacted 4h, obtain secondary amino silanes coupling agent.
(2) polyether polyol (C2120, Shanghai Dongda Chemical Co., Ltd.) of 100 number average molecular weights 12000 is existed
Under 110 DEG C of vacuum conditions be dehydrated, deaerate 2h, be then cooled to 60 DEG C, sequentially add IPDI (isocyano of diisocyanate with
The molar ratio of the hydroxyl of polyether polyol is 1.8:1), dibutyl tin dilaurate (account for polyether polyol quality 0.1%), is led to
Enter high pure nitrogen as reaction protection gas, stir evenly, react 4h at 70 DEG C, obtain isocyanate-terminated polyethers prepolymer,
NCO content is 0.55%；
(3) secondary amino silanes in the isocyanate-terminated polyethers prepolymer synthesized in step (2) and step (1) are coupled
Agent is reacted according to the ratio that secondary amino group and isocyano molar ratio are 1:1, is stirred to react under 60 DEG C, high pure nitrogen protection
3h；Until system by titration without reaction was completed in the presence of isocyano, it is poly- to obtain colorless and transparent secondary amino silanes modified polyether
Close object, viscosity 46000mPas.
Embodiment 7:
(1) in the four-hole boiling flask equipped with blender, constant pressure funnel and gas-guide tube, it is equal that 100 numbers are sequentially added
The allyl-terminated polyether (S1020, Shanghai Dongda Chemical Co., Ltd.) that molecular weight is 2000, is passed through nitrogen and starts to stir, 40
Gamma-amino propyl trimethoxy silicane, the molar ratio of allyl-terminated polyether and gamma-amino propyl trimethoxy silicane are added dropwise at DEG C
It for 1:1, is added dropwise in 30 minutes, then heats to 90 DEG C, reacted 4h, obtain secondary amino silanes coupling agent.
(2) by the polyether polyol (C2080, Shanghai Dongda Chemical Co., Ltd.) of 100 number average molecular weights 8000 110
Dehydration, degassing 2h, are then cooled to 60 DEG C under DEG C vacuum condition, sequentially add the IPDI (isocyano of diisocyanate and poly-
The molar ratio of the hydroxyl of ethoxylated polyhydric alcohol is 1.7:1), dibutyl tin dilaurate (account for polyether polyol quality 0.1%), is passed through
High pure nitrogen stirs evenly as reaction protection gas, reacts 4h at 60 DEG C, obtain isocyanate-terminated polyethers prepolymer, NCO
Content is 0.7%；
(3) secondary amino silanes in the isocyanate-terminated polyethers prepolymer synthesized in step (2) and step (1) are coupled
Agent is reacted according to the ratio that secondary amino group and isocyano molar ratio are 1:1, is stirred to react under 50 DEG C, high pure nitrogen protection
4h；Until system by titration without reaction was completed in the presence of isocyano, it is poly- to obtain colorless and transparent secondary amino silanes modified polyether
Close object, viscosity 34000mPas.
Comparative example 1:
(1) by the polyether polyol (C2080, Shanghai Dongda Chemical Co., Ltd.) of 100 number average molecular weights 8000 110
Dehydration, degassing 2h, are then cooled to 60 DEG C under DEG C vacuum condition, sequentially add the IPDI (isocyano of diisocyanate and poly-
The molar ratio of the hydroxyl of ethoxylated polyhydric alcohol is 1.7:1), dibutyl tin dilaurate (account for polyether polyol quality 0.1%), is passed through
High pure nitrogen stirs evenly as reaction protection gas, reacts 4h at 60 DEG C, obtain isocyanate-terminated polyethers prepolymer, NCO
Content is 0.7%；
(2) the isocyanate-terminated polyethers prepolymer synthesized in step (1) is pressed with gamma-amino propyl trimethoxy silicane
The ratio for being 1:1 according to isocyano and silane molar ratio is reacted, and is stirred to react 3h under 40 DEG C, high pure nitrogen protection；Directly
Yellow transparent silane modified polyether polymer is obtained, viscosity is without reaction was completed in the presence of isocyano by titration to system
55000mPa·s。
Embodiment 8-14:
Silane is prepared as follows using each silane modified polyether polymer obtained in Examples 1 to 7 respectively
Modified polyether seal glue.
(1) it stocks up: stocking up according to the mass percentage composition of silane modified polyether seal glue；
(2) carry out mixture manufacturing using double planetary blender: by nanometer calcium carbonate (40%), active coarse whiting (19%),
Secondary amino silanes modified polyether polymer (22%), dioctyl phthalate (17%), β-(aminoethyl)-γ-aminopropyl three
Methoxy silane (0.9%) puts into material cylinder, stirs evenly；
(3) vinyltrimethoxysilane (1%) is added, high-speed stirred does not have particle to being uniformly dispersed in material；
(4) heat preservation is vacuumized 1~3 hour；
(5) 30~60 DEG C are cooled to, vacuum is stopped；
(6) dibutyl tin dilaurate (0.1%) is added, deaeration plastic emitting after mixing evenly.
Comparative example 2:
It is close to prepare silane modified polyether as follows using silane modified polyether polymer obtained in comparative example 1
Sealing.
(1) it stocks up: stocking up according to the mass percentage composition of silane modified polyether seal glue；
(2) carry out mixture manufacturing using double planetary blender: by nanometer calcium carbonate (40%), active coarse whiting (19%),
Secondary amino silanes modified polyether polymer (22%), dioctyl phthalate (17%), β-(aminoethyl)-γ-aminopropyl three
Methoxy silane (0.9%) puts into material cylinder, stirs evenly；
(3) vinyltrimethoxysilane (1%) is added, high-speed stirred does not have particle to being uniformly dispersed in material；
(4) heat preservation is vacuumized 1~3 hour；
(5) 30~60 DEG C are cooled to, vacuum is stopped；
(6) dibutyl tin dilaurate (0.1%) is added, deaeration plastic emitting after mixing evenly.
To embodiment 8-14 and the resulting silane modified polyether seal glue of comparative example 2, measurement surface drying time, 100% are stretched surely
Intensity, tensile strength and elongation rate of tensile failure.
For surface drying time, by " the 5th part of building sealant method of testing materials: surface drying GB/T 13477.5-2002-
The measurement of time " in 8.2B law regulation test.
For tensile strength, 100% stretching strength and elongation rate of tensile failure, by GB/T528-2009- " vulcanized rubber or thermoplastic
Property rubber tensile ess-strain performance measurement " regulation test；
Test result is listed in table 1.
The effect data of each embodiment of table 1.
The above-mentioned description to embodiment is that this Shen can be understood and applied for the ease of those skilled in the art
Please.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without paying creative labor.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 modifies within all scope of the present application.
Claims (14)
1. a kind of preparation method of secondary amino silanes modified polyether polymer, described method includes following steps:
(1) polyether polyol is dehydrated under 90~130 DEG C of vacuum conditions, deaerate 1~4h, is then cooled to 50~80 DEG C, will
Diisocyanate and catalyst are added in polyether polyol, are passed through inert gas, are stirred evenly, then are reacted at 50~90 DEG C
1~6h obtains isocyanate-terminated polyethers prepolymer；
(2) the isocyanate-terminated polyethers prepolymer is mixed with secondary amino silanes, 30~90 DEG C at a temperature of and lazy
Property gas shield under react 1~6h, until system by titration without reaction was completed in the presence of isocyano, then in reaction temperature
Lower vacuum removal bubble obtains the secondary amino silanes modified polyether polymer.
2. the preparation method of secondary amino silanes modified polyether polymer as described in claim 1, which is characterized in that in step
(1) in, the molar ratio for controlling the isocyano of diisocyanate and the hydroxyl of polyether polyol is 1.1~2:1.
3. the preparation method of secondary amino silanes modified polyether polymer as described in claim 1, which is characterized in that in step
(2) in, control secondary amino group and isocyano molar ratio are 0.9~1.2:1.
4. the preparation method of secondary amino silanes modified polyether polymer as described in claim 1, which is characterized in that in step
(1) in, the degree of functionality of the polyether polyol is 2 or 3, number-average molecular weight 6000-16000.
5. the preparation method of secondary amino silanes modified polyether polymer as described in claim 1, which is characterized in that in step
(1) in, the diisocyanate is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexa-methylene diisocyanate
One or both of ester and isophorone diisocyanate.
6. the preparation method of secondary amino silanes modified polyether polymer as described in claim 1, which is characterized in that in step
(1) in, the catalyst is dibutyl tin dilaurate, stannous octoate or dibutyltin diacetate.
7. the preparation method of secondary amino silanes modified polyether polymer as described in claim 1, which is characterized in that the catalysis
The additional amount of agent accounts for 0.05~0.5% of polyether polyol quality in step (1).
8. the preparation method of secondary amino silanes modified polyether polymer as described in claim 1, which is characterized in that in step
(2) in, the secondary amino silanes be by containing end primary amino group silane coupling agent and allyl-terminated polyether according to molar ratio be 1:1
Ratio, obtained by 90 DEG C of stirring 4h reaction.
9. the preparation method of secondary amino silanes modified polyether polymer as claimed in claim 8, which is characterized in that described contains
Holding primaryamino-silane coupling agent is gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane；And/or institute
The degree of functionality for the allyl-terminated polyether stated is 1, number-average molecular weight 300-3000.
10. the preparation method of secondary amino silanes modified polyether polymer as described in claim 1, which is characterized in that in step
(1) in, the dehydration, degassing temperature are 100~120 DEG C, preferably 110 DEG C；
And/or the dehydration, degassing time 1-2h, preferably 1.5h；
And/or the molar ratio of the hydroxyl of the isocyano and polyether polyol of the diisocyanate is 1.4~1.9:1, preferably
Ground is 1.5~1.8:1；
And/or the reaction temperature of the polyether polyol and diisocyanate is 60~80 DEG C, preferably 70 DEG C；
And/or the reaction time of the polyether polyol and diisocyanate is 2~5h, preferably 3~4h；
And/or the number-average molecular weight of the polyether polyol is 7000~14000, preferably 8000~12000.
11. the preparation method of secondary amino silanes modified polyether polymer as described in claim 1, which is characterized in that in step
(2) in, the secondary amino silanes are 1.0 according to secondary amino group and isocyano molar ratio with isocyanate-terminated polyethers prepolymer
~1.1:1, preferably 1:1；
And/or the reaction temperature of the isocyanate-terminated polyethers prepolymer and secondary amino silanes is 50~70 DEG C, preferably
It is 60-70 DEG C；
And/or the reaction time of the isocyanate-terminated polyethers prepolymer and secondary amino silanes be 2~5h, preferably 3
~4h；
And/or the number-average molecular weight of the allyl-terminated polyether be 1000-3000, preferably 2000.
12. a kind of preparation method by secondary amino silanes modified polyether polymer such as of any of claims 1-11
Come the secondary amino silanes modified polyether polymer prepared.
It according to molar ratio is 1:1 by the silane coupling agent and allyl-terminated polyether of the primary amino group containing end 13. a kind of secondary amino silanes
Ratio, obtained by 90 DEG C of stirring 4h reaction.
14. secondary amino silanes as claimed in claim 13, which is characterized in that the described primaryamino-silane coupling agent containing end is
Gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane；And/or the official of the allyl-terminated polyether
Energy degree is 1, number-average molecular weight 300-3000.
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