CN107698756A - A kind of silane-modified line style polyurea adhesive and its preparation and application - Google Patents
A kind of silane-modified line style polyurea adhesive and its preparation and application Download PDFInfo
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- CN107698756A CN107698756A CN201710765284.7A CN201710765284A CN107698756A CN 107698756 A CN107698756 A CN 107698756A CN 201710765284 A CN201710765284 A CN 201710765284A CN 107698756 A CN107698756 A CN 107698756A
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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
- C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
- C08G71/02—Polyureas
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
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Abstract
The invention discloses a kind of silane-modified line style polyurea adhesive and its production and use.The preparation method prepares end carbonic ester line style polyureas with one or more kinds of diamines and excessive aliphatic acid ester carbonate, is then blocked using primary amine groups silane coupler, Silante terminated line style polyureas adhesive has been prepared.This method is simple to operate, pollution-free, polyureas is no longer prepared by traditional isocyanates, eliminate diamines photochemical the step of preparing diisocyanate, save the energy, and the building-up process is gentle, substantial amounts of heat is not had to release, in building-up process will not crosslinking structure produce be more prone to so that preparing line style polyureas.The assembling that the silane-modified line style polyureas fluid sealant is applied to windshield bonds.
Description
Technical field
The invention belongs to high-molecular organic material field, and it is gluing to be related to a kind of silane-modified line style polyureas of non-isocyanate method
Agent and preparation method thereof and the application in sealant for automatic windshields formula system.
Background technology
Polyurethane material has excellent mechanical strength, toughness and anti-wear performance, is most widely used in daily life
One of high polymer material.Mainly prepared by isocyanates and polyol reaction, Molecular Design is flexible, performance formula scope
It is broad.The standby fluid sealant of polyurethane is at present using one of wide encapsulant.Polyurethane sealant has excellent
Mechanical performance, it is mainly used in the assembling of windshield.But polyurethane material ageing-resistant performance is poor, the sealing after aging
Glue cannot be guaranteed the security of automobilism.The automobile such as polyurethane sealant and glass, aluminium often uses the cementability of inorganic material
It is poor, special primary coat need to be coordinated to ensure its cementability during use, construction technology is more complicated.And prepare isocyanates
Raw material is the phosgene of severe toxicity, seriously endangers the health of people, and have larger threat to environment.And isocyanates with it is more
First alcohol can react while reaction with the moisture in surrounding environment, generate carbon dioxide, so that material internal produces
Raw abscess, reduce the mechanical property of polyurethane material.The one kind of polyureas as polyurethane material, compared to traditional polyurethane material
Material, has excellent heatproof air aging performance, is mainly prepared by isocyanates and polyamine reaction, but due to isocyanic acid
Ester and polyamine reaction are violent, and course of reaction is difficult to control, and the urea groups of generation may proceed to occur with isocyanates at 100 DEG C or so
Reaction generates biuret and gel occurs, so hardly resulting in the polyureas molecule of line style by traditional synthetic method.
Silicane-modified polyurethane adhesive is also known as SPUR adhesive, and main composition is the linear polyurethane of siloxane blocking
(also known as SPUR performed polymers), traditional synthetic method：The base polyurethane prepolymer for use as addition of siloxanes and NCO end-blockings containing amino obtains
Arrive.Molecular structural formula is shown as a formula V：
SPUR adhesive combines water resistance, the heat resistance of the high resiliency of polyurethane, low temperature flexibility, caking property and organosilicon
The advantages that, and the structure regulating of SPUR adhesive is more flexible, but because carbamate groups (- NHCOO-) are in high temperature
(>80 DEG C), oxygen it is existing under the conditions of thermo-oxidative ageing occur decompose, so SPUR adhesive is not suitable for growing in high temperature environments
Phase uses, so as to limit its use range.
Consider factors above, it is desirable to provide it is a kind of both without using isocyanates raw material, there is preferable heat-resisting oxygen again
The line style polyurea adhesive synthetic method of ageing properties and adhesive property.The country successively has patent report to use carbonic ester in the recent period
The method that polyurethane material is prepared using non-isocyanate method with polyamine：
CN102336891A is prepared for polyethylene glycol polyethylene glycol block with polyethylene glycol, expoxy propane, epoxychloropropane
Copolyether diatomic alcohol compounds, polyethylene glycol polypropylene glycol ring carbon acid is then made by ester exchange reaction with dimethyl carbonate
Ester, then nucleophilic addition occurs with diamine and has obtained non-isocyanate polyurethane, then added into epoxy resin solution
Above-mentioned non-isocyanate polyurethane carries out crosslinking hybrid reaction, has obtained described non-isocyanate polyurethane-epoxy resin material
Expect, urea groups is not contained in the material, react to obtain is entirely carbamate groups, and high temperature length is unable to so equally existing
The problem of time uses.
Polyethers has been made with polyether Glycols, epoxychloropropane, heterogeneous load potassium carbonate, KI in CN102718964A
Double manganese ester, then with diamine react, obtained non-isocyanate polyurethane, then with methyl diphenylene diisocyanate group
Divide after being mixed and sprayed, obtained non-isocyanate polyurethane spray polyurea film.The patent is mainly using non-different
Cyanic acid ester polyurethane replaces amine terminated polyether, and solution amine terminated polyether energy consumption is big, heavy-polluted problem, it is achieved thereby that green
Colour chemistry, low-carbon economy and atom economy, but the patent is not related to adhesive field.
CN104513393A prepares diamines esterdiol with diamines and cyclic carbonate, then with polyether Glycols in catalyst
In the presence of carry out ester exchange reaction, obtain poly- (ether-urethane) of thermoplastic biologically degradable.Thermoplastic poly (ether-urethane) material
The presence of substantial amounts of carbamate (- NHCOO-) group, ester group (- COO-) in material, make its be difficult to high temperature (>80 DEG C) environment
Middle long-time uses.
CN104829833A is first prepared for straight chain type and ring-like two kind two of ester with two kinds of different diamines and cyclic carbonate
Amine esterdiol, the wherein urethane diol autohemagglutination of straight chain type two is prepared into the performed polymer of different molecular weight, then with polyether Glycols and
The urethane diol of alicyclic ring type two carries out urethane exchange reaction in the presence of a catalyst, obtains the poly- (ether of biodegradable crystallization thermoplastic
Urethane) and elastomer.A large amount of carbamates in the biodegradable crystallization thermoplastic poly- (ether urethane) and elastomer (-
NHCOO-) the presence of group, ester group (- COO-), make its be difficult to high temperature (>80 DEG C) use for a long time in environment.
US9012676B2 carries out carbonylation by aromatic polyamine and diphenyl carbonate and obtains aromatic series amino first
Acid esters, thermal cracking then is carried out in the range of 200 DEG C~230 DEG C, obtained 4,4 '-'-diphenylmethane diisocyanate (MDI), and
And reacted the carbamate of binary and one or more kinds of amine, obtain HMW SPUA.The patent
Relate generally to non-isocyanate method production MDI monomer and HMW SPUA.
The silane-modified line style polyurea adhesive of non-isocyanate method in the present invention is during preparation also without making
With high toxicity and moisture-sensitive isocyanate-monomer, but carbonic ester, diamine, silane coupler are used, that is, met country
Requirement to " process for cleanly preparing ", the cost of material of product is reduced again；And no longer contain carbamate groups in system
Group (- NHCOO-), the substitute is the presence of urea groups, and urea groups has higher thermal oxidation stability compared to carbamate groups
Property, and the presence of urea groups adds the hydrogen bond content in adhesive system, so as to improve the hot-air aging resistance of adhesive
Energy and the adhesive property with base material.So as to improve the service life of adhesive under the high temperature conditions.
The content of the invention
The purpose of the embodiment of the present invention be to provide a kind of silane-modified line style polyurea adhesive of non-isocyanate method and its
Preparation method and the application in sealant formula, it is intended that solve to use in conventional silanes modified polyurethane adhesive building-up process
High toxicity isocyanates, and be unable to high temperature (>80 DEG C) under the conditions of it is long-term use of the problem of.
According to the first aspect of the invention, there is provided a kind of silane-modified line style polyurea adhesive of non-isocyanate method,
I.e. hold siloxane blocking line style polyureas adhesive, itself through the following steps that obtain：Under the conditions of 60-160 DEG C (preferably
80-140 DEG C), it (such as according to mol ratio is 1 that the diamine of one or more, which is added drop-wise to excessive,:1.5~2) fat
In race's linear carbonate system, reaction obtains the line style polyureas of carbonic ester end-blocking；Then (the preferably 80- under the conditions of 80-150 DEG C
130 DEG C), the line style polyureas of carbonic ester end-blocking is reacted with primary amine groups silane coupler, the line style for obtaining end siloxane blocking is gathered
Urea adhesive.
Further, the silane-modified line style polyurea adhesive has below general formula：
(R4O)3SiR3NH[C(O)NHR2NHC(O)NHR2NH]mC(O)NHR3Si(OR4)3
(I)
R in formula2Selected from C1-C10 alkylidenes, C3-C16 cycloalkylidenes, C3-C16 ethers, preferably C3-C12 cycloalkylidenes,
C3-C16 ethers, more preferably C3-C12 ethers；
Further preferred R2For Wherein n is 1-8, preferably 1-6,
More preferably 1-4 integer；
R3Selected from C1-C10 alkylidenes, preferably C3-C5 alkylidenes；R4Selected from C1-C10 alkylidenes, preferably C1-C4 alkylidenes；
M is 1-40, preferably 1-10, more preferably 1-3 integer.
To achieve the above objectives, the present invention prepares the side of silane-modified line style polyurea adhesive using non-isocyanate method
Method, comprise the following steps that：
1) diamine of one or more at a certain temperature, is added drop-wise to excessive fat according to certain mol proportion
Temperature of reaction system is raised in race's linear carbonate system, after being added dropwise to complete to be reacted, and then removes the alcohols and water of generation,
Obtain the line style polyureas of carbonic ester end-blocking；
2) the line style polyureas of the carbonic ester end-blocking at a certain temperature, obtained in step 1) mixes with primary amine groups silane coupler
After conjunction, rise temperature of reaction system is reacted, the alcohols and water then generated in removing system, obtains holding siloxane blocking
Line style polyureas adhesive.
Wherein, the aliphatic linear carbonate used in step 1) has the structure shown in logical formula (I)：
In above formula, R1For C1-C10 aliphatic groups, preferably C1-C6 aliphatic groups, such as-CH3,-CH2CH3Deng fat
Race's group.
Wherein, the diamine used in step 1) is the structure shown in logical formula (III)：
In above formula, R2Selected from C1-C10 alkylidenes, C3-C16 cycloalkylidenes, preferably C3-C16 ethers, C3-C12 Asias cycloalkanes
Base, more preferably C3-C16 ethers, C3-C12 ethers；
Further preferred R2For
The formula of the primary amine groups silane coupler used in step 2) is：
(R4O)3SiR3NH2
(IV)
R3Selected from C1-C10 alkylidenes, preferably C3-C5；R4Selected from C1-C10 alkylidenes, preferably C1-C4, more preferably R3For-
CH2CH2CH2-, R4For-C2H5- or-CH3I.e.：APTES (KH550), 3- aminopropyl trimethoxies
Silane (KH540).
The certain temperature is 80~120 DEG C, preferably 85~95 DEG C or 85~100 DEG C.
Preferably, step 1) is carried out as follows：At 80~100 DEG C, preferably 85~95 DEG C, under nitrogen protection, by one kind or one
The diamine of the kind above is 1 according to mol ratio:1.5~2, preferably 1:1.6~1.8, it is added drop-wise to excessive aliphatic line style carbonic acid
Temperature of reaction system is raised in ester system, after being added dropwise to complete to 120~140 DEG C, preferably 125-135 DEG C, reacts 8-20h, preferably
10~12h, then vacuum removal generation alcohols and water, obtain the line style polyureas of carbonic ester end-blocking.
Preferably, step 2) is carried out as follows：At 80 DEG C~120 DEG C, preferably 80 DEG C~100 DEG C, under nitrogen protection, will walk
It is rapid 1) in obtained line style polyureas and the primary amine groups silane coupler of carbonic ester end-blocking according to mol ratio be 1:1~1.2, preferably 1:
1~1.05 feeds intake, mechanical mixture 1-3 hours, after preferably from about 2h, rise system temperature to 120 DEG C~140 DEG C, preferably 120 DEG C
~130 DEG C, 8~12h, preferably 9~11h are reacted, the alcohols and water then generated in vacuum removal system, obtains holding siloxanes
The line style polyureas adhesive of end-blocking.
The line style polyureas of the carbonic ester end-blocking obtained in step 1) has the structure shown in logical formula (VI)：
R1O[C(O)NHR2NHC(O)NHR2NH]mC(O)OR1
(VI)
R in formula1For C1-C10, preferably C1-C6 aliphatic groups, such as-CH3,-CH2CH3Deng aliphatic group；
R2Selected from C1-C10 alkylidenes, C3-C16 cycloalkylidenes, preferably C3-C16 ethers, C3-C12 cycloalkylidenes, C3-
C16 ethers, more preferably C3-C12 ethers；
Further preferred R2For Wherein n is 1-8, preferably 1-6,
More preferably 1-4 integer；
The line style polyureas of the siloxane blocking obtained in step 2) has the structure shown in logical formula (I)：
(R4O)3SiR3NH[C(O)NHR2NHC(O)NHR2NH]mC(O)NHR3Si(OR4)3
(I)
R in formula2Selected from C1-C10 alkylidenes, C3-C16 cycloalkylidenes, C3-C16 ethers, preferably C3-C12 cycloalkylidenes,
C3-C16 ethers, more preferably C3-C12 ethers；
Further preferred R2For Wherein n is 1-8, preferably 1-6,
More preferably 1-4 integer；
R3Selected from C1-C10 alkylidenes, preferably C3-C5 alkylidenes；R4Selected from C1-C10 alkylidenes, preferably C1-C4 alkylidenes；
M is 1-40, preferably 1-10, more preferably 1-3 integer.
Due to containing substantial amounts of urea groups in the line style polyurea system of the siloxane blocking obtained in step 2), hydrogen is also easy to produce
Key, resin viscosity is caused to rise, therefore synthesized line style polyureas viscosity is 100cp-50000cp, preferably 100cp-
30000cp。
Present invention also offers the assembling of the windshield of the line style polyureas adhesive including above-mentioned end siloxane blocking
Fluid sealant.The fluid sealant may also include usual component such as plasticizer such as diisooctyl phthalate, filler such as dioxy
SiClx, titanium dioxide, calcium carbonate etc., silane adhesion promoter, catalyst such as dibutyl tin laurate etc..
It is used to prepare automotive windshield glass invention further provides the line style polyureas adhesive of above-mentioned end siloxane blocking
Purposes in glass assembling fluid sealant.
The beneficial effects of the present invention are：
(1) in the present invention the silane-modified line style polyurea adhesive building-up process for preparing without using high toxicity and moisture-sensitive
Isocyanate-monomer, but used carbonic ester, diamine, silane coupler, that is, meet country to " process for cleanly preparing "
It is required that the cost of material of product is reduced again.
(2) line style polyureas molecule synthesized in the present invention, the more traditional diamine of building-up process and diisocyanate letter
It is single, and molecular weight is more prone to control, and there is no big calorimetric to release in building-up process, cross-linked structure will not be produced.
(3) carbamate groups (- NHCOO-) are no longer contained in the silane-modified line style polyurea system, instead
It is the presence of urea groups, urea groups has higher thermo-oxidative stability compared to carbamate groups, and the presence of urea groups adds
Hydrogen bond content in adhesive system, so as to improve the high temperature resistant performance of the adhesive.
(4) presence of urea groups adds hydrogen bond content in adhesive system, so as to improve the bonding of adhesive and base material
Performance.
Embodiment
By specific embodiment, the present invention will be further described, and embodiment of the present invention is intended only as to the present invention's
Illustrate, do not limit the scope of the invention.
Table 1 is referred in raw material and source.
The raw material of table 1 and source
Embodiment 1
(1) end carbonic ester line style polyureas is prepared：Under 90 DEG C, nitrogen protection, 0.02molHDA is dissolved into
In 0.02molIPDA, then it is slowly dropped in 0.072mol diethyl carbonate systems, after being added dropwise to complete, raises reaction system
Temperature continues the second alcohol and water of vacuum removal generation after reaction 10h, obtains the line style polyureas of carbonic ester end-blocking to 120 DEG C.
(2) the line style polyureas adhesive of siloxane blocking is prepared：Under 100 DEG C, nitrogen protection, 0.021mol 3- ammonia is taken
Base propyl-triethoxysilicane (KH550) is added in the line style polyureas of the carbonic ester end-blocking obtained in previous step, and machinery is mixed
After closing 2h, rise temperature of reaction system continues to react 10h to 120 DEG C.Then the ethanol generated in vacuum removal system, is obtained
The line style polyureas adhesive SPUA1 of siloxane blocking.
Embodiment 2
(1) end carbonic ester line style polyureas is prepared：Under 90 DEG C, nitrogen protection, by 0.03mol IPDA, 0.01mol polyethers
Amine (D230) is slowly dropped in 0.072mol diethyl carbonate systems, after being added dropwise to complete, rise temperature of reaction system to 120
DEG C, continue the second alcohol and water of vacuum removal generation after reaction 10h, obtain the line style polyureas of carbonic ester end-blocking.
(2) the line style polyureas adhesive of siloxane blocking is prepared：Under 100 DEG C, nitrogen protection, 0.021mol 3- ammonia is taken
Base propyl-triethoxysilicane (KH550) is added in the line style polyurea system of the carbonic ester end-blocking obtained in previous step, machine
After tool mixing 2h, rise temperature of reaction system continues to react 10h to 120 DEG C.Then the ethanol generated in vacuum removal system,
Obtain the line style polyureas adhesive SPUA2 of siloxane blocking.
Embodiment 3
(1) end carbonic ester line style polyureas is prepared：Under 90 DEG C, nitrogen protection, 0.02mol HDA are dissolved into 0.02mol
In 1,3- propane diamine, then it is slowly dropped in 0.072mol diethyl carbonate systems, after being added dropwise to complete, raises reaction system
Temperature continues the second alcohol and water of vacuum removal generation after reaction 10h, obtains the line style polyureas of carbonic ester end-blocking to 120 DEG C.
(2) the line style polyureas adhesive of siloxane blocking is prepared：Under 100 DEG C, nitrogen protection, 0.021mol 3- ammonia is taken
Base propyl-triethoxysilicane (KH550) is added in the line style polyurea system of the carbonic ester end-blocking obtained in previous step, machine
After tool mixing 2h, rise temperature of reaction system continues to react 10h to 120 DEG C.Then the ethanol generated in vacuum removal system,
Obtain the line style polyureas adhesive SPUA3 of siloxane blocking.
Embodiment 4
(1) end carbonic ester line style polyureas is prepared：Under 90 DEG C, nitrogen protection, by 0.02mol 1,3-BAC, 0.02mol
1,3- propane diamine is slowly dropped in 0.072mol diethyl carbonate systems, after being added dropwise to complete, rise temperature of reaction system to 120
DEG C, continue the second alcohol and water of vacuum removal generation after reaction 10h, obtain the line style polyureas of carbonic ester end-blocking.
(2) the line style polyureas adhesive of siloxane blocking is prepared：Under 100 DEG C, nitrogen protection, 0.021mol 3- ammonia is taken
Base propyl trimethoxy silicane (KH540) is added in the line style polyurea system of the carbonic ester end-blocking obtained in previous step, machine
After tool mixing 2h, rise temperature of reaction system continues to react 10h to 120 DEG C.Then the ethanol generated in vacuum removal system,
Obtain the line style polyureas adhesive SPUA4 of siloxane blocking.
Embodiment 5
(1) end carbonic ester line style polyureas is prepared：Under 90 DEG C, nitrogen protection, by 0.02mol 1,3-BAC, 0.02mol
HDA is slowly dropped in 0.072mol diethyl carbonate systems, and after being added dropwise to complete, rise temperature of reaction system continues to 120 DEG C
The second alcohol and water that vacuum removal generates after reaction 10h, obtains the line style polyureas of carbonic ester end-blocking.
(2) the line style polyureas adhesive of siloxane blocking is prepared：Under 100 DEG C, nitrogen protection, 0.021mol 3- ammonia is taken
Base propyl trimethoxy silicane (KH540) is added in the line style polyurea system of the carbonic ester end-blocking obtained in previous step, machine
After tool mixing 2h, rise temperature of reaction system continues to react 10h to 120 DEG C.Then the ethanol generated in vacuum removal system,
Obtain the line style polyureas adhesive SPUA5 of siloxane blocking.
Embodiment 6
(1) end carbonic ester line style polyureas is prepared：Under 90 DEG C, nitrogen protection, by 0.02mol 1,3-BAC, 0.02mol
Putriscine is slowly dropped in 0.08mol dimethyl carbonate systems, after being added dropwise to complete, rise temperature of reaction system to 120
DEG C, continue the first alcohol and water of vacuum removal generation after reaction 10h, obtain the line style polyureas of carbonic ester end-blocking.
(2) the line style polyureas adhesive of siloxane blocking is prepared：Under 100 DEG C, nitrogen protection, 0.021mol 3- ammonia is taken
Base propyl trimethoxy silicane (KH540) is added in the line style polyurea system of the carbonic ester end-blocking obtained in previous step, machine
After tool mixing 2h, rise system temperature continues to react 10h to 120 DEG C.Then the methanol generated in vacuum removal system, is obtained
The line style polyureas adhesive SPUA6 of siloxane blocking.
Embodiment 7
(1) end carbonic ester line style polyureas is prepared：Under 90 DEG C, nitrogen protection, by 0.02mol HMDA, 0.02mol 1,3-
Propane diamine is slowly dropped in 0.08mol dimethyl carbonate systems, after being added dropwise to complete, raises temperature of reaction system to 120 DEG C, after
The first alcohol and water that vacuum removal generates after continuous reaction 10h, obtains the line style polyureas of carbonic ester end-blocking.
(2) the line style polyureas adhesive of siloxane blocking is prepared：Under 100 DEG C, nitrogen protection, 0.021mol 3- ammonia is taken
Base propyl trimethoxy silicane (KH540) is added in the line style polyurea system of the carbonic ester end-blocking obtained in previous step, machine
After tool mixing 2h, rise system temperature continues to react 10h to 120 DEG C.Then the methanol generated in vacuum removal system, is obtained
The line style polyureas adhesive SPUA7 of siloxane blocking.
Comparative example
The linear polyurethane adhesive of siloxane blocking is prepared in accordance with the following steps：
(1) isocyanate terminated performed polymer is prepared：It is under 70 DEG C, nitrogen protection, 0.04mol BDO is slow
It is added drop-wise in 0.04mol IPDI, 0.04mol HDI, 0.0001mol dibutyl tin laurate systems, is raised after being added dropwise to complete
Temperature of reaction system continues to obtain isocyanate terminated performed polymer after reacting 10h to 90 DEG C.
(2) the linear polyurethane adhesive of siloxane blocking is prepared：Under the conditions of 70 DEG C, nitrogen protection, mechanical mixture, take
0.021mol secondary aminosilane coupling agents SILQUESTY-9669 be slowly dropped to obtained in previous step it is isocyanate terminated pre-
In aggressiveness, rise system temperature obtains the linear polyurethane gluing of siloxane blocking to continuing after 90 DEG C to react 10h after de- vacuum
Agent-SPUR.
Prepared SPUA and SPUR viscosity is tested using the U.S.'s winged viscosimeter of rich Le in the embodiment of the present invention, close
Application performance in sealing is contrasted according to formula as below：
Formula system is with reference to following table：
| Component | Weight |
| SPUA/SPUR | 250 |
| Diisooctyl phthalate (DIDP) | 100 |
| Silquest A-171 silane | 5 |
| Calcium carbonate (thin) | 150 |
| Calcium carbonate (thick) | 100 |
| TiO2 | 7.5 |
| SiO2 | 15 |
| Silquest silane adhesion promoters | 3.75 |
| Organotin | 0.5 |
At 60 DEG C according to above-mentioned formula mixing 1h after, obtained corresponding fluid sealant.It is first according to national standard and tests this
The surface drying time of fluid sealant and the adhesion strength with glass baseplate, the then sulphur under 23 DEG C, the indoor environment of 50% relative humidity
Change three days, vulcanize the batten after being prepared for solidification for 4 days at 50 DEG C in a conventional oven, according to corresponding national standard and standard to batten
Tested, then under the conditions of 90 DEG C, after carrying out thermo-oxidative ageing 300h, its performance is tested again.Testing standard is such as
Under：It is peel strength (GB/T 2790-1995), surface drying time (GB/T 13477), tensile strength (GB/T 528-2009), disconnected
Elongation (GB/T 528-2009), shore hardness A (GB-T 2411-2008) are split, it is as a result as shown in the table：
Table 2
As shown in Table 2, there is relatively long surface drying time and higher stripping compared to SPUR fluid sealants, SPUA fluid sealants
Intensity, tensile strength and hardness, relatively low elongation at break, but hold the tensile strength before and after SPUA fluid sealant agings and fracture
Elongation and firmness change are smaller, show preferable heatproof air aging performance.Therefore, the present invention uses non-isocyanate method
Obtained end siloxanes line style polyureas adhesive not only conforms with requirement of the country to " process for cleanly preparing ", reduces the original of product
Expect cost, and compare traditional siloxane modified polyurethane adhesive, the silicone-modified line style polyureas adhesive has more
Add excellent oxidation and heat resistant property.
Claims (10)
1. a kind of silane-modified line style polyureas adhesive, it is through the following steps that obtain：By the two of one or more
First amine is added drop-wise in excessive aliphatic linear carbonate system, is reacted at an elevated temperature, obtains the line style polyureas of carbonic ester end-blocking,
Then the line style polyureas for allowing carbonic ester to block reacts at an elevated temperature with primary amine groups silane coupler, obtains the line of end siloxane blocking
Type polyureas adhesive.
2. a kind of silane-modified line style polyureas adhesive or silane-modified line style polyureas adhesive according to claim 1,
It has below general formula：
(R4O)3SiR3NH[C(O)NHR2NHC(O)NHR2NH]mC(O)NHR3Si(OR4)3
(I)
R in formula2Selected from C1-C10 alkylidenes, C3-16 cycloalkylidenes, C3-C16 ethers；It is preferred that C3-C12 cycloalkylidenes, C3-C16
Ether, more preferably C3-C12 ethers；
Further preferred R2For Wherein n is 1-8, preferably 1-6, more
It is preferred that 1-4 integer；
R3Selected from C1-C10 alkylidenes, preferably C3-C5 alkylidenes；
R4Selected from C1-C10 alkylidenes, preferably C1-C4 alkylidenes；
M is 1-40, preferably 1-10, more preferably 1-3 integer.
3. preparing the method for the silane-modified line style polyureas adhesive described in claim 1 or 2, comprise the following steps：
1) diamine of one or more is added drop-wise in excessive aliphatic linear carbonate system, risen after being added dropwise to complete
High temperature of reaction system, is reacted, and then removes the alcohols and water of generation, obtains the line style polyureas of carbonic ester end-blocking；
2) after the line style polyureas that the carbonic ester obtained in step 1) blocks is mixed with primary amine groups silane coupler, at an elevated temperature instead
Should, the alcohols and water then generated in removing system, obtain the line style polyureas adhesive of end siloxane blocking.
4. according to the method for claim 3, wherein, the aliphatic linear carbonate used in step 1) has formula
(I) structure shown in：
In above formula, R1For C1-C10 aliphatic groups, preferably C1-C6 aliphatic groups, such as-CH3,-CH2CH3Deng fatty group
Group.
Wherein, the diamine used in step 1) is the structure shown in logical formula (III)：
H2N-R2-NH2
(III)
In above formula, R2Selected from C1-C10 alkylidenes, C3-16 cycloalkylidenes, C3-C16 ethers；It is preferred that C3-C12 cycloalkylidenes, C3-
C16 ethers, more preferably C3-C12 ethers；
Further preferred R2For
The formula of the primary amine groups silane coupler used in step 2) is：
(R4O)3SiR3NH2
(IV)
R3Selected from C1-C10 alkylidenes, preferably C3-C5 alkylidenes；
R4Selected from C1-C10 alkylidenes, preferably C1-C4 alkylidenes,
More preferably R3For-CH2CH2CH2-, R4For-C2H5- or-CH3I.e.：APTES (KH550), 3- ammonia
Base propyl trimethoxy silicane (KH540).
5. the method according to claim 3 or 4, wherein, diamine is according to diamine:Aliphatic linear carbonate mol ratio
For 1:1.5~2 are added drop-wise in excessive aliphatic linear carbonate system.
6. according to the method any one of claim 3-5, wherein, step 1) is carried out as follows：At 80~100 DEG C, nitrogen
Under protection, by one or more diamine according to mol ratio be 1:1.5~2, preferably 1:1.6~1.8 are added drop-wise to excess
Aliphatic linear carbonate system in, temperature of reaction system is raised after being added dropwise to complete to 120~140 DEG C, preferably 125-135
DEG C, the alcohols and water that vacuum removal generates after reaction 8-20h, preferably 10~12h, obtain the line style polyureas of carbonic ester end-blocking.
7. according to the method any one of claim 3-6, wherein, the line style polyureas and primary that carbonic ester blocks in step 2)
Amino containing silane coupling agent mol ratio is 1:1~1.2.
8. according to the method any one of claim 3-7, wherein, step 2) is carried out as follows：At 80 DEG C~100 DEG C,
Under nitrogen protection, it is according to mol ratio with primary amine groups silane coupler by the line style polyureas that the carbonic ester obtained in step 1) blocks
1:1~1.2, preferably 1:1~1.05 feeds intake, mixing 1-3 hours, and after preferably 2h, rise system temperature is anti-to 120 DEG C~130 DEG C
10~12h is answered, the alcohols and water then generated in vacuum removal system, obtains the line style polyureas adhesive of end siloxane blocking.
9. the windshield assembling fluid sealant including the silane-modified line style polyureas adhesive described in claim 1 or 2.
10. silane-modified line style polyureas adhesive according to claim 1 or 2 is close for preparing windshield assembling
In sealing.
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| CN116253876A (en) * | 2022-12-19 | 2023-06-13 | 北京东方雨虹防水技术股份有限公司 | Non-isocyanate polyurea material and preparation method and application thereof |
| CN116284788A (en) * | 2023-03-15 | 2023-06-23 | 山东共聚有机硅技术研究院有限公司 | Preparation method and application of end-ring carbonate modified polysiloxane |
| CN116284798A (en) * | 2023-03-15 | 2023-06-23 | 山东共聚有机硅技术研究院有限公司 | Preparation method of polyurethane modified organosilicon tackifier and application of polyurethane modified organosilicon tackifier in silicone rubber |
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| CN108587548A (en) * | 2018-05-11 | 2018-09-28 | 万华化学集团股份有限公司 | A kind of Silante terminated modified polycarbonate polyurethane adhesive resin and its preparation method and application |
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| CN116253876A (en) * | 2022-12-19 | 2023-06-13 | 北京东方雨虹防水技术股份有限公司 | Non-isocyanate polyurea material and preparation method and application thereof |
| CN116253876B (en) * | 2022-12-19 | 2024-04-26 | 北京东方雨虹防水技术股份有限公司 | Non-isocyanate polyurea material and preparation method and application thereof |
| CN116284788A (en) * | 2023-03-15 | 2023-06-23 | 山东共聚有机硅技术研究院有限公司 | Preparation method and application of end-ring carbonate modified polysiloxane |
| CN116284798A (en) * | 2023-03-15 | 2023-06-23 | 山东共聚有机硅技术研究院有限公司 | Preparation method of polyurethane modified organosilicon tackifier and application of polyurethane modified organosilicon tackifier in silicone rubber |
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