CN1322084C - Silicane modified polyurethane cementing sealing glue and method for making same - Google Patents
Silicane modified polyurethane cementing sealing glue and method for making same Download PDFInfo
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- CN1322084C CN1322084C CNB2004100242914A CN200410024291A CN1322084C CN 1322084 C CN1322084 C CN 1322084C CN B2004100242914 A CNB2004100242914 A CN B2004100242914A CN 200410024291 A CN200410024291 A CN 200410024291A CN 1322084 C CN1322084 C CN 1322084C
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Abstract
The present invention relates to a silane modified polyurethane bonding sealant and a preparation method thereof, which belongs to the field of adhesive. The silane modified polyurethane bonding sealant comprises the components of the following proportion of portions by mass: 20 to 45 portions by mass of terminal hydroxyl radical ether, 3 to 10 portions by mass of isocyanate, 15 to 38 portions by mass of plasticizer, 15 to 50 portions by mass of inorganic filler, 0.01 to 0.1 portion by mass of silane coupling agent, 0.01 to 0.3 portion by mass of catalyst and 0.01 to 0.2 portion by mass of antioxidant. The present invention also provides a preparation method of the silane modified polyurethane bonding sealant. Due to the fact that the component formula of the silane modified polyurethane bonding sealant has no solvent component, the silane modified polyurethane bonding sealant has the advantages of no harm to environment, production and the health of users, high bonding shear strength greater than 3MPa with the inorganic materials of glass, aluminum materials, marble, and the like, and good uvioresistant stability. The silane modified polyurethane bonding sealant can be widely used for the fields of the construction of buildings, squares, highways and airports, the manufacturing industry of automobiles, ships, containers and machinery, and the technology of electrons, electric power, aviation/spaceflight and low temperature, etc.
Description
Technical field
The invention belongs to adhesive field, relate in particular to a kind of tackiness agent/seal gum based on urethane or this kind polymer derivant.
Background technology
Seal gum (Sealant) is the material that is used for filling space (cavity, joint or seam etc.).But it is the unsetting material of a kind of mobile or squeeze note in use, can seal seam by pointing, can rely on drying, temperature variation, solvent evaporates or chemically crosslinked, with the base material stable adhesion, and finalize the design gradually become that plasticity is solid-state, visco-elasticity or elaxtic seal.
Over nearly 30 years, the application of seal gum in industry such as building, building, automobile, boats and ships, electric, communication, space flight and civil area more and more widely.
That the kind of indefiniteness seal gum mainly contains is silicone based, polyurethanes, thiorubber class, acrylics, styrene-butadiene rubber(SBR) class, butyl type rubber, pitch class and oiliness caulk compound class, wherein better performances, use and mainly contain silicone based, polyurethanes and thiorubber class seal gum more widely.
Polyurethane sealant (Polyurethane Sealant) generally is divided into single component and two kinds of base types of two-pack, and single component is a moisture-curable, and two-pack is a reaction-curable.The single component sealant easy construction, but solidify slower; The two-pack seal gum has characteristics such as quick solidifying, performance are good, but needs preparation when using, and technology is comparatively complicated.
Polyurethane sealant is mainly used in industries such as civil construction, communications and transportation, in Japan, about 75～80% polyurethane sealant is because building trades such as buildings, square, highway, airport constructions, about 15% be used for machine industries such as automobile, boats and ships, freight container, about 5% be used for other industries such as electronics, electric power, aviation/space flight, low temperature technique.
China's exploitation polyurethane sealant starts from the seventies in 20th century, and the polyurethane sealant of early stage development is the two-pack tar oil type.The research and development of single component sealant is slower, to early 1990s, tackles key problems by " the Seventh Five-Year Plan ", develop one-component polyurethane sealant, the back begins the industrialized mass production one-component polyurethane sealant by technology introduction, and its product is mainly used in building trade.
Because polyurethane sealant has better physical performance and endurance quality, strong to base material adaptability, the streamline operration and the curing speed that can have the quick assembling line of suitable automobile, the assembling and the sealing of windshield have been widely used in the country of automotive industry prosperity, the sealing at crash bar, headlight, back door etc. is held concurrently bonding, makes these component joints have antirust, waterproof and dustproof, antidetonation and enhancement.
Windshield glass all is to use technique for sticking in developed country's car production, and the windshield glass that China introduces vehicle also adopts technique for sticking mostly, but the used single component polyurethane adhesive agent/seal gum of bonding windshield glass relies on import always.
At present, that can produce this class high quality single component polyurethane adhesive agent/seal gum product in the world has only minority developed country, as the EMS-TOGO company of the BOSTIK company of the SUNSTAR company of the ESSEX company of the U.S., 3M company, Japan, ponding chemical company, Yokohama Rubber company, Germany, Switzerland and SIKA company etc.
Open day is on December 25th, 2002, publication number is to disclose a kind of " preparation of wet-solidifying single-component polyurethane adhesive and application thereof " in the Chinese patent application of CN 1386815A, it is with vulcabond and polyether glycol prepared in reaction, and each raw material consumption is as follows by weight percentage:
Polyether Glycols 27.6～58.0%, polyether-tribasic alcohol 0～13.0%, 4,4 '-diphenylmethanediisocyanate 31.4～55.0%, solvent 0～20%.
The day for announcing is on March 29th, 2000, and notification number is to disclose a kind of " polyurethane binder/sealant composition, its precursor and preparation method " in the Chinese patent of CN 1248606C, by weight, contains in its component:
100 parts of binder/sealant precursors;
Block agent 0.04-1.78 part;
Inert filler 32-76 part;
Inert plasticizer 24-134 part;
Other additives 1.2-3.6 part;
Inert solvent is less than 9 parts greater than 0 part.
Above-mentioned about polyurethane binder/sealant patent application or patent in the disclosed component, all contain solvent.
Solvent as used herein has benzene,toluene,xylene etc. usually, and (referring to " seal gum-technical formula is used " that publish September calendar year 2001 Chemical Industry Press Materials Science and Engineering publishing centre, Cao Yun compiles, P.19).
Because existing polyurethane binder/sealant has all used noxious solvent more or less in prescription or production process, make it have certain environmental pollution and environmental issue, the producer and user healthy brought certain infringement.
In addition, as the automobile single component polyurethane adhesive/seal gum, inorganic materials such as present like product both domestic and external and glass, aluminium do not have cementability substantially, as SIKAFLEX company 255, the product of models such as 551 of 8590 or BETASAD company of TRESTAT company, the bonding strength of itself and glass, aluminium all is close to 0, and its range of application in the automobile production industry is limited to.
Summary of the invention
Technical problem to be solved by this invention provide a kind of solvent-free, snappiness good, with the silicane-modified polyurethane joint sealant of inorganic materials cohesiveness height, ultraviolet light good stability.
The present invention also provides the preparation method of above-mentioned silicane-modified polyurethane joint sealant.
Technical scheme of the present invention is: a kind of silicane-modified polyurethane joint sealant is provided, it is characterized in that the mass fraction ratio of this silicane-modified polyurethane joint sealant component is:
End hydroxy polyether 20～45
Isocyanic ester 3～10
Softening agent 15～38
Mineral filler 15～50
Silane coupling agent 0.01～0.1
Catalyzer 0.01～0.3
Oxidation inhibitor 0.01～0.2
Wherein,
Described end hydroxy polyether is that molecular-weight average is that 4500～6000 terminal hydroxy group ternary polyoxytrimethylene ether, molecular-weight average are that 6000～8000 hydroxy-terminated polytetrahydrofuran ether, molecular-weight average are that 5500～6500 polyoxytrimethylene-castor oil polyhydric alcohol copolyether or molecular-weight average are polytetrahydrofuran-propylene oxide copolyether of 2000～4000;
Described isocyanic ester is a tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or two kinds mixture wherein;
Described softening agent is dibutyl phthalate, dioctyl phthalate (DOP), Dinonylphthalate or Di Iso Decyl Phthalate;
Described mineral filler is Shawinigan black, titanium dioxide, lime carbonate, talcum powder, 4A molecular sieve, Tai-Ace S 150, magnesium oxide, organobentonite or thermal silica;
Described silane coupling agent is anilinomethyl triethoxysilane, γ-An Bingjisanyiyangjiguiwan, 3-Racemic glycidol oxygen propyl trimethoxy silicane, two (γ-trimethoxy silicon propyl group) double sulfide or 3-(2-amino-ethyl) amine propyl trimethoxy silicane;
Described catalyzer is stannous octoate, dibutyl tin laurate, triethylene diamine, N-methylmorpholine or trolamine;
Described oxidation inhibitor is 2,6 ditertiary butyl p cresol, tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester or 4,4 '-two uncle's octyl diphenylamines.
Further, above-mentioned tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, 1, hexamethylene-diisocyanate can use separately, also wherein two kinds of mixed uses, mix when using, the blending ratio of its two kinds of mixtures is 1: 1～1.5.
The present invention also provides a kind of preparation method of above-mentioned silicane-modified polyurethane joint sealant, it is characterized in that preparation technology is followed successively by:
(1) end hydroxy polyether of getting required umber by prescription joins in the stirred autoclave, in 30～60min, be warming up to 80～100 ℃, in vacuum tightness is stirring, vacuum outgas 1～2h under 0.09 ± 0.005MPa condition, is cooled to 60～80 ℃, stops to stir and vacuumizing;
(2) isocyanic ester of the required umber of adding is warming up to 80～100 ℃ in 30～60min, reacts 2～3h under the inflated with nitrogen protective condition;
(3) softening agent of the required umber of adding is to stir 1～2h under 0.09 ± 0.005MPa condition in 80～100 ℃ of temperature and vacuum tightness;
(4) mineral filler of the required umber of adding, even back to be mixed is to stir 1～2h under 0.09 ± 0.005MPa condition in vacuum tightness, is cooled to 60～80 ℃;
(5) silane coupling agent of the required umber of adding under the inflated with nitrogen protective condition is cooled to 30～40 ℃ then;
(6) catalyzer and the oxidation inhibitor of the required umber of adding continue reaction 1～2h;
(7) viscosity of testing product reaches 11 * 10
5～13 * 10
5During mPas, stop to stir, continue to vacuumize 10～15min;
(8) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
When above-mentioned isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water bath, to add again after the fusing.
The present invention also provides the another kind of preparation method of above-mentioned silicane-modified polyurethane joint sealant, it is characterized in that preparation technology is followed successively by:
(1) end hydroxy polyether and the softening agent of getting required umber by prescription joins in the stirred autoclave, is warming up to 100～120 ℃ in 30～60min, vacuum tightness be stir under 0.09 ± 0.005MPa condition, vacuum outgas 1～2h;
(2) mineral filler of the required umber of adding, continuing in vacuum tightness is to stir 1～2h under 0.09 ± 0.005MPa condition, is cooled to 60～80 ℃;
(3) isocyanic ester of the required umber of adding is warming up to 80～100 ℃ in 30～60min, is to react 2～3h under 0.09 ± 0.005MPa condition in vacuum tightness, is cooled to 60～80 ℃;
(4) silane coupling agent, catalyzer and the oxidation inhibitor of the required umber of adding under the inflated with nitrogen protective condition continue stirring reaction 1～2h;
(5) viscosity of testing product reaches 11 * 10
5～13 * 10
5During mPas, be cooled to 20～30 ℃, stop to stir, continue to vacuumize 10～15min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
When described isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water bath, to add again after the fusing.
Compared with the prior art, advantage of the present invention is:
1. no any solvent composition in its component prescription does not have harm to environment and production, user's health;
2. silane coupler modified by adding, make that inorganic materials cohesiveness such as product of the present invention and glass, aluminium, marble are good, with the shearing resistance (evaluation index of cementability) of this type of inorganic materials greater than 3MPa;
3. by adding oxidation inhibitor in the prescription, make the ultraviolet stability of product of the present invention be improved, prolong work-ing life greatly.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1:
Press following prescription and prepared silicane-modified polyurethane joint sealant:
(1) getting the 20kg molecular-weight average by prescription is that terminal hydroxy group ternary polyoxygenated third rare ether of 4500～6000 joins in the stirred autoclave, warming-in-water to 80 ℃ in 30min, in vacuum tightness is stirring, vacuum outgas 1h under the 0.09MPa condition, is cooled to 60 ℃, stops to stir and vacuumizing;
(2) add the tolylene diisocyanate of 3kg, warming-in-water to 80 ℃ in 30min is reacted 2h under the inflated with nitrogen protective condition;
(3) dibutyl phthalate of adding 15kg is to stir 1h under the 0.09MPa condition in 80 ℃ of temperature and vacuum tightness;
(4) Shawinigan black of adding 15kg, even back to be mixed is to stir 1h under the 0.09MPa condition in vacuum tightness, is cooled to 60 ℃;
(5) anilinomethyl triethoxysilane of adding 0.01kg under the inflated with nitrogen protective condition is cooled to 30 ℃ then;
(6) add the stannous octoate of 0.01kg and the 2,6 ditertiary butyl p cresol of 0.01kg, continue to stir, react 1h;
(7) viscosity of testing product reaches 11 * 10
5During mPas, stop to stir, continue to vacuumize 10min;
(8) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the silicane-modified polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index and as shown in the table with the index value contrast of external like product:
| Performance | SIKAFLEX | TRESTAT | BETASAD | AM-140 | Product of the present invention | |
| 255 | 255FC | 8590 | 551 | |||
| Density (g/ml) | 1.29 | 1.29 | 1.16 | 1.3 | 1.1 | 1.21 |
| The not sticking time (min) | 30 | 15 | 30 | 37 | 40-50 | 32 |
| Curing speed (mm/d) | 8.0 | 5.0 | 4.0 | 4.0 | 4.05 | |
| Hardness (Shao Shi A 0) | 60 | 60 | 50 | 49 | 55 | 51 |
| Stretching bonding strength (MPa) | 8.0 | 5.0 | 5.2 | 4.2 | 6.0 | 8.05 |
| Elongation (%) | 400 | 400 | 450 | 500 | 500 | 552 |
| Shearing resistance (MPa) | 5.0 | 5.0 | 5.5 | 4.0 | 4.5 | 5.0 |
| Bonding strength (MPa) with glass, aluminium | 0 | 0 | 0 | 0 | 0 | 3.1 |
| Tear strength (N/mm) | 9.0 | 12.0 | 6.4 | 17.4 | 15 | 24.5 |
As seen, the curing speed of product of the present invention, stretching bonding strength, elongation, shearing resistance and tear strength are equal to or are better than external like product, and the bonding strength of itself and glass, aluminium is far superior to external like product.
The mensuration of above-mentioned parameter is tested by the method for stipulating in the following standard:
The mensuration of GB/T528-1999 vulcanized rubber or thermoplastic elastomer tensile property;
The mensuration of GB/T529-1999 vulcanized rubber or thermoplastic elastomer tear strength;
The pocket sclerometer penetration hardness of GB/T531-1999 rubber test method;
GB/T6680-1986 fluid chemical product sampling general rule;
Q/HTM-001-2003 monocomponent moisture cure urethanes adhesive/seal gum.
In the foregoing description inflated with nitrogen protection purpose be for guarantee to be reflected at the air state of isolation under carry out, do not have strict demand so fill nitrogen pressure.
Embodiment 2:
Press following prescription and prepared silicane-modified polyurethane joint sealant:
(1) getting the 45kg molecular-weight average by prescription is that 6000～8000 hydroxy-terminated polytetrahydrofuran ether and 38kg dioctyl phthalate (DOP) join in the stirred autoclave, warming-in-water to 120 ℃ in 60min, vacuum tightness be stir under the 0.095MPa condition, vacuum outgas 2h;
(2) add the 50kg titanium dioxide, continuing in vacuum tightness is to stir 2h under the 0.095MPa condition, is cooled to 80 ℃;
(3) add 10kg 1, the 5-naphthalene diisocyanate, warming-in-water to 100 ℃ in 60min is to react 3h under the 0.095MPa condition in vacuum tightness, is cooled to 80 ℃;
(4) under the inflated with nitrogen protective condition, add 0.1kg γ-An Bingjisanyiyangjiguiwan, 0.3kg dibutyl tin laurate and 0.2kg tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, continue stirring reaction 2h;
(5) viscosity of testing product reaches 13 * 10
5During mPas, be cooled to 30 ℃, stop to stir, continue to vacuumize 15min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the silicane-modified polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Density (g/ml) | 1.22 |
| The not sticking time (min) | 40 |
| Curing speed (mm/d) | 4.02 |
| Hardness (Shao Shi A 0) | 55 |
| Stretching bonding strength (MPa) | 8.02 |
| Elongation (%) | 556 |
| Shearing resistance (MPa) | 5.02 |
| Bonding strength (MPa) with glass, aluminium | 3.5 |
| Tear strength (N/mm) | 28 |
All the other are with embodiment 1.
Embodiment 3:
Press following prescription and prepared silicane-modified polyurethane joint sealant:
(1) getting the 32.5kg molecular-weight average by prescription is that polyoxytrimethylene-castor oil polyhydric alcohol copolyether of 5500～6500 joins in the stirred autoclave, warming-in-water to 100 ℃ in 45min, in vacuum tightness is stirring, vacuum outgas 2h under the 0.085MPa condition, be cooled to 80 ℃, stop to stir and vacuumizing;
(2) add the diphenylmethanediisocyanate of 7kg, warming-in-water to 100 ℃ in 45min is reacted 3h under the inflated with nitrogen protective condition;
(3) Dinonylphthalate of adding 26.5kg is to stir 2h under the 0.09MPa condition in 80 ℃ of temperature and vacuum tightness;
(4) lime carbonate of adding 32.5kg, even back to be mixed is to stir 2h under the 0.09MPa condition in vacuum tightness, is cooled to 80 ℃;
(5) the 3-Racemic glycidol oxygen propyl trimethoxy silicane of adding 0.0325kg under the inflated with nitrogen protective condition is cooled to 40 ℃ then;
(6) add the triethylene diamine of 0.0725kg and 4,4 '-two uncle's octyl diphenylamines of 0.0575kg, continue to stir, react 2h;
(7) viscosity of testing product reaches 13 * 10
5During mPas, stop to stir, continue to vacuumize 15min;
(8) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the silicane-modified polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Density (g/ml) | 1.25 |
| The not sticking time (min) | 31 |
| Curing speed (mm/d) | 4.0 |
| Hardness (Shao Shi A 0) | 49 |
| Stretching bonding strength (MPa) | 8.05 |
| Elongation (%) | 549 |
| Shearing resistance (MPa) | 5.05 |
| Bonding strength (MPa) with glass, aluminium | 3.5 |
| Tear strength (N/mm) | 26.1 |
All the other are with embodiment 1.
Embodiment 4:
Press following prescription and prepared silicane-modified polyurethane joint sealant:
(1) getting the 38.75kg molecular-weight average by prescription is that 2000～4000 polytetrahydrofuran-propylene oxide copolyether and 32.3kg Di Iso Decyl Phthalate join in the stirred autoclave, warming-in-water to 100 ℃ in 50min, vacuum tightness be stir under the 0.092MPa condition, vacuum outgas 1h;
(2) add the 41.25kg talcum powder, continuing in vacuum tightness is to stir 1h under the 0.092MPa condition, is cooled to 60 ℃;
(3) add the 8.5kg isophorone diisocyanate, warming-in-water to 80 ℃ in 45min is to react 2h under the 0.092MPa condition in vacuum tightness, is cooled to 60 ℃;
(4) add two (γ-trimethoxy silicon propyl group) double sulfides of 0.0775kg, 0.228kg trolamine and 0.11kg4 under the inflated with nitrogen protective condition, 4 '-two uncle's octyl diphenylamines continue stirring reaction 1h;
(5) viscosity of testing product reaches 11 * 10
5During mPas, be cooled to 20 ℃, stop to stir, continue to vacuumize 10min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.By the silicane-modified polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Density (g/ml) | 1.2 |
| The not sticking time (min) | 35.2 |
| Curing speed (mm/d) | 4.01 |
| Hardness (Shao Shi A 0) | 53 |
| Stretching bonding strength (MPa) | 8.01 |
| Elongation (%) | 548 |
| Shearing resistance (MPa) | 5.1 |
| Bonding strength (MPa) with glass, aluminium | 3.1 |
| Tear strength (N/mm) | 25.7 |
All the other are with embodiment 2.
In the various embodiments described above, when the isocyanic ester that is adopted is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water bath, to add again after the fusing (following each embodiment is also identical).
Embodiment 5:
Press following prescription and prepared silicane-modified polyurethane joint sealant:
(1) getting the 26.3kg molecular-weight average by prescription is that terminal hydroxy group ternary polyoxygenated third rare ether of 4500～6000 joins in the stirred autoclave, warming-in-water to 95 ℃ in 40min, in vacuum tightness is stirring, vacuum outgas 1.75h under the 0.085MPa condition, is cooled to 75 ℃, stops to stir and vacuumizing;
(2) add 1 of 5kg, 5-naphthalene diisocyanate dioctyl phthalate (DOP), warming-in-water to 95 ℃ in 45min is reacted 1.8h under the inflated with nitrogen protective condition;
(3) dioctyl phthalate (DOP) of adding 20.1kg is to stir 1.75h under the 0.085MPa condition in 75 ℃ of temperature and vacuum tightness;
(4) the 4A molecular sieve of adding 23.8kg, even back to be mixed is to stir 1.8h under the 0.09MPa condition in vacuum tightness, is cooled to 75 ℃;
(5) 3-(2-amino-ethyl) the amine propyl trimethoxy silicane of adding 0.033kg under the inflated with nitrogen protective condition is cooled to 27 ℃ then;
(6) add the N-methylmorpholine of 0.073kg and the 2,6 ditertiary butyl p cresol of 0.058kg, continue to stir, react 1.75h;
(7) viscosity of testing product reaches 12.5 * 10
5During mPas, stop to stir, continue to vacuumize 13min;
(8) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the silicane-modified polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as shown in the table:
| Density (g/ml) | 1.21 |
| The not sticking time (min) | 25 |
| Curing speed (mm/d) | 4.01 |
| Hardness (Shao Shi A 0) | 45 |
| Stretching bonding strength (MPa) | 8.1 |
| Elongation (%) | 552 |
| Shearing resistance (MPa) | 5.03 |
| Bonding strength (MPa) with glass, aluminium | 3.1 |
| Tear strength (N/mm) | 25 |
All the other are with embodiment 1.
Embodiment 6:
Press following prescription and prepared silicane-modified polyurethane joint sealant:
(1) getting the 38.75kg molecular-weight average by prescription is that 6000～8000 hydroxy-terminated polytetrahydrofuran ether and 32.25kg dioctyl phthalate (DOP) join in the stirred autoclave, warming-in-water to 115 ℃ in 50min, vacuum tightness be stir under the 0.095MPa condition, vacuum outgas 1.5h;
(2) add 41kg Tai-Ace S 150, continuing in vacuum tightness is to stir 1.2h under the 0.095MPa condition, is cooled to 70 ℃;
(3) add 8.5kg1, the 5-naphthalene diisocyanate, warming-in-water to 90 ℃ in 45min is to react 2.5h under the 0.095MPa condition in vacuum tightness, is cooled to 70 ℃;
(4) under the inflated with nitrogen protective condition, add 0.055kg γ-An Bingjisanyiyangjiguiwan, 0.228kg dibutyl tin laurate and 0.153kg tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester, continue stirring reaction 1.5h;
(5) viscosity of testing product reaches 12 * 10
5During mPas, be cooled to 25 ℃, stop to stir, continue to vacuumize 12min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the silicane-modified polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Density (g/ml) | 1.25 |
| The not sticking time (min) | 32 |
| Curing speed (mm/d) | 4.0 |
| Hardness (Shao Shi A 0) | 45 |
| Stretching bonding strength (MPa) | 8.01 |
| Elongation (%) | 550 |
| Shearing resistance (MPa) | 5.0 |
| Bonding strength (MPa) with glass, aluminium | 3.05 |
| Tear strength (N/mm) | 26 |
All the other are with embodiment 2.
Embodiment 7:
Press following prescription and prepared silicane-modified polyurethane joint sealant:
(1) getting the 32.5kg molecular-weight average by prescription is that polyoxytrimethylene-castor oil polyhydric alcohol copolyether of 5500～6500 joins in the stirred autoclave, warming-in-water to 85 ℃ in 30min, in vacuum tightness is stirring, vacuum outgas 1.3h under the 0.09MPa condition, be cooled to 65 ℃, stop to stir and vacuumizing;
(2) add 1 of 7kg, the 5-naphthalene diisocyanate, warming-in-water to 85 ℃ in 35min is reacted 2.3h under the inflated with nitrogen protective condition;
(3) Dinonylphthalate of adding 26.5kg is to stir 1.2h under the 0.09MPa condition in 80 ℃ of temperature and vacuum tightness;
(4) magnesium oxide of adding 32.5kg, even back to be mixed is to stir 1.5h under the 0.09MPa condition in vacuum tightness, is cooled to 65 ℃;
(5) γ-An Bingjisanyiyangjiguiwan of adding 0.0325kg under the inflated with nitrogen protective condition is cooled to 33 ℃ then;
(6) add the N-methylmorpholine of 0.0725kg and tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester of 0.0575kg, continue to stir, react 1.25h;
(7) viscosity of testing product reaches 11.5 * 10
5During mPas, stop to stir, continue to vacuumize 12min;
(8) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the silicane-modified polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Density (g/ml) | 1.21 |
| The not sticking time (min) | 41 |
| Curing speed (mm/d) | 4.02 |
| Hardness (Shao Shi A 0) | 55 |
| Stretching bonding strength (MPa) | 8.01 |
| Elongation (%) | 550 |
| Shearing resistance (MPa) | 5.01 |
| Bonding strength (MPa) with glass, aluminium | 3.1 |
| Tear strength (N/mm) | 26 |
All the other are with embodiment 1.
Embodiment 8:
Press following prescription and prepared silicane-modified polyurethane joint sealant:
(1) getting the 35kg molecular-weight average by prescription is that 6000～8000 hydroxy-terminated polytetrahydrofuran ether and 22kg dibutyl phthalate join in the stirred autoclave, warming-in-water to 110 ℃ in 50min; In vacuum tightness is stirring, vacuum outgas 1.25h under the 0.095MPa condition;
(2) add 41.25kg magnesium oxide, continuing in vacuum tightness is to stir 1.3h under the 0.095MPa condition, is cooled to 65 ℃;
(3) add 8.5kg1, hexamethylene-diisocyanate, warming-in-water to 85 ℃ in 50min; In vacuum tightness is to react 2.25h under the 0.095MPa condition, is cooled to 65 ℃;
(4) add 0.0775kg3-Racemic glycidol oxygen propyl trimethoxy silicane, 0.27kg trolamine and 0.02kg2 under the inflated with nitrogen protective condition, the 6-ditertbutylparacresol continues stirring reaction 1.25h;
(5) viscosity of testing product reaches 11.5 * 10
5During mPas, be cooled to 22 ℃; Stop to stir, continue to vacuumize 12min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the silicane-modified polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Density (g/ml) | 1.21 |
| The not sticking time (min) | 38 |
| Curing speed (mm/d) | 4.01 |
| Hardness (Shao Shi A 0) | 54 |
| Stretching bonding strength (MPa) | 8.02 |
| Elongation (%) | 552 |
| Shearing resistance (MPa) | 5.2 |
| Bonding strength (MPa) with glass, aluminium | 3.3 |
| Tear strength (N/mm) | 25.2 |
All the other are with embodiment 2.
Embodiment 9:
Press following prescription and prepared silicane-modified polyurethane joint sealant:
(1) getting the 26.3kg molecular-weight average by prescription is that polytetrahydrofuran-propylene oxide copolyether of 2000～4000 joins in the stirred autoclave, warming-in-water to 90 ℃ in 50min; In vacuum tightness is stirring, vacuum outgas 1.5h under the 0.085MPa condition, is cooled to 70 ℃; Stop to stir and vacuumizing;
(2) add the diphenylmethanediisocyanate of 5kg, warming-in-water to 90 ℃ in 50min; Under the inflated with nitrogen protective condition, react 2.5h;
(3) Di Iso Decyl Phthalate of adding 20.1kg is to stir 1.5h under the 0.085MPa condition in 90 ℃ of temperature and vacuum tightness;
(4) organobentonite of adding 23.8kg, even back to be mixed is to stir 1.5h under the 0.09MPa condition in vacuum tightness; Be cooled to 70 ℃;
(5) two (γ-trimethoxy silicon propyl group) double sulfides of adding 0.033kg under the inflated with nitrogen protective condition are cooled to 35 ℃ then;
(6) add the dibutyl tin laurate of 0.073kg and 4,4 '-two uncle's octyl diphenylamines of 0.058kg, continue to stir, react 1.5h;
(7) viscosity of testing product reaches 12.5 * 10
5During mPas, stop to stir, continue to vacuumize 12.5min;
(8) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the silicane-modified polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as shown in the table:
| Density (g/ml) | 1.2 |
| The not sticking time (min) | 40 |
| Curing speed (mm/d) | 4.0 |
| Hardness (Shao Shi A 0) | 50 |
| Stretching bonding strength (MPa) | 8.0 |
| Elongation (%) | 550 |
| Shearing resistance (MPa) | 5.0 |
| Bonding strength (MPa) with glass, aluminium | 3.3 |
| Tear strength (N/mm) | 25.2 |
All the other are with embodiment 1.
Embodiment 10:
Press following prescription and prepared silicane-modified polyurethane joint sealant:
(1) getting the 45kg molecular-weight average by prescription is that 5500～6500 polyoxytrimethylene-castor oil polyhydric alcohol copolyether and 15kg Di Iso Decyl Phthalate join in the stirred autoclave, warming-in-water to 117 ℃ in 45min; In vacuum tightness is stirring, vacuum outgas 1.75h under the 0.09MPa condition;
(2) add the 50kg thermal silica, continuing in vacuum tightness is to stir 1.75h under the 0.09MPa condition, is cooled to 75 ℃;
(3) add the 5kg isophorone diisocyanate, warming-in-water to 95 ℃ in 45min; In vacuum tightness is to react 2.75h under the 0.09MPa condition, is cooled to 75 ℃;
(4) add 0.1kg anilinomethyl triethoxysilane, 0.3kg stannous octoate and 0.2kg2 under the inflated with nitrogen protective condition, the 6-ditertbutylparacresol continues stirring reaction 1.75h;
(5) viscosity of testing product reaches 12.5 * 10
5During mPas, be cooled to 27.5 ℃; Stop to stir, continue to vacuumize 13.5min;
(6) inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
By the silicane-modified polyurethane joint sealant that above-mentioned prescription and technology make, its performance physical and chemical index is as follows:
| Density (g/ml) | 1.21 |
| The not sticking time (min) | 35 |
| Curing speed (mm/d) | 4.02 |
| Hardness (Shao Shi A 0) | 55 |
| Stretching bonding strength (MPa) | 8.03 |
| Elongation (%) | 555 |
| Shearing resistance (MPa) | 5.02 |
| Bonding strength (MPa) with glass, aluminium | 3.02 |
| Tear strength (N/mm) | 25 |
All the other are with embodiment 2.
Embodiment 11:
The isocyanic ester that is adopted is 1.5kg tolylene diisocyanate and 1.5kg 1, the 5-naphthalene diisocyanate; Mineral filler is 5kg Shawinigan black, 5kg titanium dioxide and 5kg lime carbonate;
All the other are with embodiment 1.
Embodiment 12:
The isocyanic ester that is adopted is 5kg 1,5-naphthalene diisocyanate and 5kg diphenylmethanediisocyanate; Mineral filler is 20kg talcum powder, 5kg magnesium oxide and 25kg organobentonite;
All the other are with embodiment 2.
Embodiment 13:
The isocyanic ester that is adopted is 3kg tolylene diisocyanate and 4.5kg 1, the 5-naphthalene diisocyanate; Mineral filler is 10kg titanium dioxide, 14kg lime carbonate and 26kg talcum powder;
All the other are with embodiment 3.
Embodiment 14:
The isocyanic ester that is adopted is 3.5kg isophorone diisocyanate and 4.5kg hexamethylene diisocyanate; Mineral filler is 20kg talcum powder, 4kg4A molecular sieve and 16kg Tai-Ace S 150;
All the other are with embodiment 4.
Embodiment 15:
The isocyanic ester that is adopted is 2kg tolylene diisocyanate and 2.5kg diphenylmethanediisocyanate; Mineral filler is 6kg Tai-Ace S 150,8kg magnesium oxide and 3.5kg organobentonite;
All the other are with embodiment 5.
Embodiment 16:
The isocyanic ester that is adopted is 4kg 1,5-naphthalene diisocyanate and 5.2kg hexamethylene diisocyanate;
Mineral filler is 10kg thermal silica, 11kg talcum powder, 2kg4A molecular sieve and 15kg organobentonite;
All the other are with embodiment 6.
Embodiment 17:
The isocyanic ester that is adopted is 3kg tolylene diisocyanate and 4.4kg isophorone diisocyanate;
Mineral filler is 20kg Shawinigan black, 22kg lime carbonate, 7kg talcum powder, 2kg4A molecular sieve and 2kg magnesium oxide;
All the other are with embodiment 7.
Embodiment 18:
The isocyanic ester that is adopted is 3.5kg diphenylmethanediisocyanate and 4.5kg hexamethylene diisocyanate;
Mineral filler is 11kg Shawinigan black, 10kg titanium dioxide, 7kg talcum powder, 5kg4A molecular sieve and 8kg organobentonite;
All the other are with embodiment 8.
The present invention can be widely used in fields such as buildings, square, highway, airport construction, automobile, boats and ships, freight container, machine industry, electronics, electric power, aviation/space flight, low temperature technique.
Claims (4)
1. the preparation method of a silicane-modified polyurethane joint sealant is characterized in that
(1) the mass fraction ratio of this silicane-modified polyurethane joint sealant component is:
End hydroxy polyether 20～45
Isocyanic ester 3～10
Softening agent 15～38
Mineral filler 15～50
Silane coupling agent 0.01～0.1
Catalyzer 0.01～0.3
Oxidation inhibitor 0.01～0.2
Wherein,
Described end hydroxy polyether is that molecular-weight average is that 4500～6000 terminal hydroxy group ternary polyoxytrimethylene ether, molecular-weight average are that 6000～8000 hydroxy-terminated polytetrahydrofuran ether, molecular-weight average are that 5500～6500 polyoxytrimethylene-castor oil polyhydric alcohol copolyether or molecular-weight average are polytetrahydrofuran-propylene oxide copolyether of 2000～4000;
Described isocyanic ester is a tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or two kinds mixture wherein;
Described softening agent is dibutyl phthalate, dioctyl phthalate (DOP), Dinonylphthalate or Di Iso Decyl Phthalate;
Described mineral filler is Shawinigan black, titanium dioxide, lime carbonate, talcum powder, 4A molecular sieve, Tai-Ace S 150, magnesium oxide, organobentonite or thermal silica;
Described silane coupling agent is anilinomethyl triethoxysilane, γ-An Bingjisanyiyangjiguiwan, 3-Racemic glycidol oxygen propyl trimethoxy silicane, two (γ-trimethoxy silicon propyl group) double sulfide or 3-(2-amino-ethyl) amine propyl trimethoxy silicane;
Described catalyzer is stannous octoate, dibutyl tin laurate, triethylene diamine, N-methylmorpholine or trolamine;
Described oxidation inhibitor is 2,6 ditertiary butyl p cresol, tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester or 4,4 '-two uncle's octyl diphenylamines;
(2) its preparation technology is followed successively by:
1. the end hydroxy polyether of getting required umber by prescription joins among the stirring reaction Fu, in 30～60min, be warming up to 80～100 ℃, in vacuum tightness is stirring, vacuum outgas 1～2h under 0.09 ± 0.005MPa condition, is cooled to 60～80 ℃, stops to stir and vacuumizing;
2. the isocyanic ester that adds required umber is warming up to 80～100 ℃ in 30～60min, react 2～3h under the inflated with nitrogen protective condition;
3. the softening agent that adds required umber is to stir 1～2h under 0.09 ± 0.005MPa condition in 80～100 ℃ of temperature and vacuum tightness;
4. the mineral filler that adds required umber, even back to be mixed is to stir 1～2h under 0.09 ± 0.005MPa condition in vacuum tightness, is cooled to 60～80 ℃;
5. under the inflated with nitrogen protective condition, add the silane coupling agent of required umber, be cooled to 30～40 ℃ then;
6. the catalyzer and the oxidation inhibitor that add required umber continue reaction 1～2h;
7. the viscosity of testing product reaches 11 * 10
5～13 * 10
5During mPas, stop to stir, continue to vacuumize 10～15min;
8. inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
2. according to the preparation method of the described silicane-modified polyurethane joint sealant of claim 1, it is characterized in that described tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, 1, hexamethylene-diisocyanate can use separately, also wherein two kinds of mixing are used, mix when using, the blending ratio of its two kinds of mixtures is 1: 1～1.5.
3. the preparation method of a silicane-modified polyurethane joint sealant is characterized in that
(1) the mass fraction ratio of this silicane-modified polyurethane joint sealant component is:
End hydroxy polyether 20～45
Isocyanic ester 3～10
Softening agent 15～38
Mineral filler 15～50
Silane coupling agent 0.01～0.1
Catalyzer 0.01～0.3
Oxidation inhibitor 0.01～0.2
Wherein,
Described end hydroxy polyether is that molecular-weight average is that 4500～6000 terminal hydroxy group ternary polyoxytrimethylene ether, molecular-weight average are that 6000～8000 hydroxy-terminated polytetrahydrofuran ether, molecular-weight average are that 5500～6500 polyoxytrimethylene-castor oil polyhydric alcohol copolyether or molecular-weight average are polytetrahydrofuran-propylene oxide copolyether of 2000～4000;
Described isocyanic ester is a tolylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, or two kinds mixture wherein;
Described softening agent is dibutyl phthalate, dioctyl phthalate (DOP), Dinonylphthalate or Di Iso Decyl Phthalate;
Described mineral filler is Shawinigan black, titanium dioxide, lime carbonate, talcum powder, 4A molecular sieve, Tai-Ace S 150, magnesium oxide, organobentonite or thermal silica;
Described silane coupling agent is anilinomethyl triethoxysilane, γ-An Bingjisanyiyangjiguiwan, 3-Racemic glycidol oxygen propyl trimethoxy silicane, two (γ-trimethoxy silicon propyl group) double sulfide or 3-(2-amino-ethyl) amine propyl trimethoxy silicane;
Described catalyzer is stannous octoate, dibutyl tin laurate, triethylene diamine, N-methylmorpholine or trolamine:
Described oxidation inhibitor is 2,6 ditertiary butyl p cresol, tetramethylene β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid pentaerythritol ester or 4,4 '-two uncle's octyl diphenylamines;
(2) its preparation technology is followed successively by:
1. end hydroxy polyether and the softening agent of getting required umber by prescription joins in the stirred autoclave, is warming up to 100～120 ℃ in 30～60min, vacuum tightness be stir under 0.09 ± 0.005MPa condition, vacuum outgas 1～2h;
2. the mineral filler that adds required umber, continuing in vacuum tightness is to stir 1～2h under 0.09 ± 0.005MPa condition, is cooled to 60～80 ℃;
3. the isocyanic ester that adds required umber is warming up to 80～100 ℃ in 30～60min, be to react 2～3h under 0.09 ± 0.005MPa condition in vacuum tightness, is cooled to 60～80 ℃;
4. under the inflated with nitrogen protective condition, add silane coupling agent, catalyzer and the oxidation inhibitor of required umber, continue stirring reaction 1～2h;
5. the viscosity of testing product reaches 11 * 10
5～13 * 10
5During mPas, be cooled to 20～30 ℃, stop to stir, continue to vacuumize 10～15min;
6. inflated with nitrogen is removed vacuum to normal pressure, and material goes out still then, through check, divide packing and make finished product.
4. according to the preparation method of the described silicane-modified polyurethane joint sealant of claim 3, when it is characterized in that described isocyanic ester is solid aromatic family isocyanic ester, need in 60～80 ℃ hot water bath, to add again after the fusing.
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| CN101402845B (en) * | 2008-11-11 | 2011-05-18 | 北京市化学工业研究院 | Process for producing flame-proof fluid sealant for construction |
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| CN104194708A (en) * | 2014-09-26 | 2014-12-10 | 北京化工大学常州先进材料研究院 | Preparation of dual-curing organosilicon modified polyurethane adhesive |
| CN105418873A (en) * | 2015-12-15 | 2016-03-23 | 苏州国泰科技发展有限公司 | Silane-modified polyurethane sealant |
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| CN111364892B (en) * | 2020-03-11 | 2022-02-25 | 盐城耀晖人防防护设备科技有限公司 | Civil air defense door processing technology based on right-angle civil air defense profile steel and vulcanized fusion joint rubber strip |
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| CN1245507A (en) * | 1997-01-29 | 2000-02-23 | 爱赛克斯特种产品公司 | Polyurethane sealant compositions |
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| CN1245507A (en) * | 1997-01-29 | 2000-02-23 | 爱赛克斯特种产品公司 | Polyurethane sealant compositions |
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