Background technology
Urethane (PU) tackiness agent is to contain urethano in the molecular chain (NHCOO) and/or the isocyanate group (NCO) tackiness agent of class.Polyurethane adhesive has good cohesiveness because of containing a large amount of polar groups and active reactive group in its matrix resin molecule to multiple base material.By regulating its raw material and prescription, can design the polyurethane adhesive of purposes difference and bonding differing materials, become various in style, a widely used class tackiness agent so far.
Polyurethane adhesive was developed the earliest the forties in 20th century, after the eighties, obtain fast development, mainly comprised polyisocyanates solvent cement, thermoplastic polyurethane solvent cement, response type one-part solvent glue, response type two-pack solvent cement, solvent-free glue, water-dispersion glue, hot-melting type and reaction hot melt type polyurethane glue.Described response type two-pack solvent cement is made up of two components of first, second usually, and two components are separately packed, and formulated according to a certain percentage before the use, first component (host) is a hydroxy component, and second component (solidifying agent) is for containing the component of isocyanate groups.The host that also has is the polyurethane prepolymer of end group NCO, and solidifying agent is low molecular weight polyols or polyamine.
CN 1629245A and CN 1624067A disclose a kind of boiling resistant polyurethane adhesive and preparation method thereof, described tackiness agent is a kind of two component adhesive, comprise that mass percentage content is the host of 50-90% and the solidifying agent of 10-50%, described host is that polyether glycol and the hydroxyl value that 10-30 milligram KOH/ restrains is that the polyester polyol that 30-100 milligram KOH/ restrains is formed by hydroxyl value, and described solidifying agent is the polyisocyanate prepolymers that vulcabond and polyol reaction obtain.
CN 1563241A discloses a kind of nylon membrane compound polyurethane adhesive that is used for, this tackiness agent is the bi-component polyurethane adhesive of being made up of host and solidifying agent, wherein, host: the weight ratio of solidifying agent is 100: 10-20, described host comprises the polyurethane prepolymer of 30-75 weight %, the polymeric amide of 0.1-3 weight %, the organic solvent of 20-50 weight %, and described solidifying agent is polyisocyanates and polyvalent alcohol approximate 2 ratio reaction according to NCO/OH a adduct.
Two component adhesive mixes and measures cumbersomely, often occurs the proportioning mistake easily, influences use properties, and price is also higher; And monocomponent polyurethane adhesive is easy to use, need not allocate, and easily extrudes, and is stronger with the bounding force of multiple material, and is applicable to the automatic assembly line operation, so the development and utilization of monocomponent polyurethane adhesive enjoys attention.
At present, normally prepare isocyanate-terminated base polyurethane prepolymer for use as, add other auxiliary agents and filler again and prepare the moist curing urethane packaged material of single component with prepolymer method.A kind of high-solid level mono-component polyurethane method for producing elastomers is disclosed as CN 1587293A, this method comprises earlier with the polyurethane prepolymer of isocyanic ester with siloxanes that contains the isocyanic ester root and polyol reaction preparation end isocyano, through containing the silicone-modified of reactive hydrogen, used polyvalent alcohol is polyether glycol, the pure and mild epoxy polyol of polyester polyols again; Used isocyanic ester is aromatic diisocyanate and aliphatic diisocyanate; Used siloxanes is the siloxanes that contains reactive hydrogen; Used catalyzer is tin class and amines catalyst; Used solvent is not for containing the solvent of reactive hydrogen.CN 1667074A discloses a kind of polyurethanes moisture cured mono-component adhesive, the prescription of this tackiness agent comprises: by diphenylmethanediisocyanate and the polyoxypropyleneglycol and/or the polyoxytrimethylene triol of reaction mole proportioning, the prescription of this tackiness agent also comprises additive, solvent.This mono-component polyurethane packaged material is to utilize airborne moisture as crosslinking accelerator and solidified, the poor storage stability of product, and the carbonic acid gas that discharges when solidifying easily makes glue-line produce pore, reduced the mechanical property of material and the stopping property or the binding property of material, and solidified slower.
Embodiment
Polyurethane sealing package material prescription provided by the invention contains polyether glycol and MDI, wherein, described MDI for liquefaction 4,4 '-MDI.
The present invention to described liquefaction 4,4 '-content of MDI and polyether glycol has no particular limits, the corresponding content of vulcabond and polyether glycol gets final product in the conventional polyurethanes tackiness agent.Under the preferable case, be benchmark with the total amount of prescription, the content of described polyether glycol is 60-80 weight %, described liquefaction 4,4 '-content of MDI is 20-40 weight %.
Described liquefaction 4,4 '-MDI can be the liquefaction 4 that obtains in various manners, 4 '-MDI, be preferably carbodiimide-ketone urea imine modified 4 in the specific embodiment of the invention, 4 '-MDI, the commodity of this vulcabond are called MDI-100HL.Described carbodiimide-ketone urea is imine modified 4,4 '-MDI can be commercially available, and also can in all sorts of ways prepares.Carbodiimide described in the embodiment of the invention-ketone urea is imine modified 4,4 '-MDI (MDI-100HL) provides by the magnificent urethane in Yantai ten thousand company, and the content of isocyanate group described in the product is 28-30 weight %.
Polyether glycol of the present invention can be the mixture of polyether Glycols, polyether-tribasic alcohol or polyether Glycols and polyether-tribasic alcohol.Described polyether Glycols for example is the polyether Glycols (trade names are Dio1-2000) of 54-58 milligram KOH/ gram, acid number≤0.05 milligram KOH/ gram for hydroxyl value, and described polyether-tribasic alcohol is that polyether-tribasic alcohol (trade names are 330N) or the hydroxyl value that 32-36 milligram KOH/ gram, acid number≤0.05 milligram KOH/ restrain is the polyether-tribasic alcohol (trade names are 3050) or their mixture of 54-58 milligram KOH/ gram, acid number≤0.05 milligram KOH/ gram for hydroxyl value for example.Above-mentioned polyether glycol all can be available from the big chemical industrial company in east, Shandong.Preferred described polyether glycol is polyether Glycols Dio1-2000 in the specific embodiment of the invention, or one or both the mixture in polyether Glycols Dio1-2000 and polyether-tribasic alcohol 330N, the polyether-tribasic alcohol 3050, wherein the content of polyether Glycols Dio1-2000 in mixture preferably is not less than 50 weight %, more preferably 60-100 weight %.
Under the preferable case, the prescription of polyurethane sealing package material of the present invention also comprises silane end-cappers.Described silane end-cappers can be the polyurethane sealant various silane that contain reactive hydrogen commonly used, the present invention is preferably aminosilane, described aminosilane can be the mixture of secondary amino group silane or primary amino silane and secondary amino group silane, and described secondary amino group silane is preferably N-methyl-gamma-amino isobutyl-Trimethoxy silane, N-ethyl-gamma-amino isobutyl-Trimethoxy silane, N-phenyl-γ-An Bingjisanjiayangjiguiwan, N-phenyl-γ-aminopropyl dimethoxy silane, γ-sulfenyl propyl trimethoxy silicane, dichloromethyl triethoxyl silane; Described primary amino silane is preferably γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan etc.In the described silane end-cappers, the weight ratio of primary amino silane and secondary amino group silane is preferably 0-0.6: 1, and 0.2-0.5 more preferably: 1.Because above-mentioned aminosilane can react with the reaction product (polyurethane prepolymer) of polyether glycol and liquefaction MDI, make the polyurethane sealing package material replace the cured with isocyanates mechanism of mono-component polyurethane with silane-cure mechanism, and setting up period does not discharge gas, thereby can avoid polyurethane sealing package material of the prior art because CO
2Gas residue causes the problem of material binding property and mechanical properties decrease in packaged material.Therefore, preferably contain amino-silane terminated dose in the packaged material prescription of the present invention.
Under the preferable case, also contain other various auxiliary agents in the polyurethane sealing package material prescription provided by the invention.Described auxiliary agent comprises one or more in softening agent, mineral filler, siccative, curing catalyst, antioxidant, the anti ultraviolet agent.
Described softening agent can be the various softening agent that are suitable for the polyurethane sealing package material, be preferably the bialkyl ortho phthalate class, as in dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, the dioctyl phthalate (DOP) one or more.Total amount with the packaged material prescription is a benchmark, and the content of softening agent is preferably 0-25 weight %, more preferably 15-20 weight %.
Described mineral filler can be through surface-treated carbon black, white carbon black, light calcium carbonate, treated carbonates, aerosil, talcum powder.Total amount with the packaged material prescription is a benchmark, and the content of mineral filler is preferably 0-15 weight %.
Described siccative is preferably the silicane siccative, and described silicane siccative is preferably trialkyl silane, as in Trimethoxy silane, triethoxyl silane, the γ-An Bingjisanyiyangjiguiwan one or more.Because the silicane siccative helps improving the stability in storage of packaged material of the present invention, therefore, preferably contains the silicane siccative in the packaged material prescription of the present invention.Total amount with the packaged material prescription is a benchmark, and the content of silicane siccative is preferably 0-0.5 weight %, more preferably 0.1-0.3 weight %.
Curing catalyst of the present invention can be the various polyurethane sealing package material solidified catalyzer of the present invention that help, as 2, and one or more in 2-dimorpholine benzyl ethyl ether, N-ethylmorpholine, stannous octoate, the dibutyl tin laurate.Total amount with the packaged material prescription is a benchmark, and the content of curing catalyst can be 0.03-0.1 weight %.
Described antioxidant can be one or more in butylated hydroxytoluene, 3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid pentaerythritol esters (abbreviation antioxidant 1010), thio-2 acid SUNSOFT Q-182S (being called for short oxidation inhibitor DSTP), phosphorous acid esters, composite antioxidant PKY, the dihydroxyphenyl propane.Total amount with prescription is a benchmark, and the content of described antioxidant can be 0-0.1 weight %.
Described anti ultraviolet agent can be Alpha-hydroxy-4-oxy-octyl benzophenone (being called for short UV-531), UV770 or their mixture.Total amount with prescription is a benchmark, and the content of described anti ultraviolet agent can be 0-0.1 weight %.
Polyurethane sealing package material provided by the invention is made by a kind of prescription reaction, and wherein, described prescription is a prescription provided by the invention.It is to stir 1-3 hour under 0.06-0.09 MPa, temperature are 80-120 ℃ polyether glycol in vacuum tightness earlier that described reaction preferably includes, then 60-90 ℃ of following and liquefaction 4,4 '-MDI contact reacts 2-5 hour, obtaining isocyanate group content is 1.5-3.0 weight % polyurethane prepolymer.Described polyether glycol and liquefaction 4,4 '-it is 1.5-3 that the charge weight of MDI compares: 1.The polyurethane prepolymer of gained add or do not add other auxiliary agents and filler after just can be used as packaged material.But the adhesive property of this packaged material is good inadequately.Therefore, the reaction of preferred described preparation polyurethane sealing package material also comprises silane end-cappers and above-mentioned polyurethane prepolymer contact reacts, obtains the better polyurethane sealing package material of curing performance.The feeding quantity of described silane end-cappers be polyether glycol and liquefaction 4,4 '-the 8-18 weight % of the reinforced total amount of MDI.The catalytic time is preferably 1-2 hour, catalytic condition be above-mentioned polyether glycol with liquefaction 4,4 '-the catalytic condition of MDI gets final product.Auxiliary agents such as softening agent of the present invention, siccative, curing catalyst can according to the required performance of polyurethane sealing package material with or not with above-mentioned reaction product contact reacts.Described catalytic condition and concrete operations have been conventionally known to one of skill in the art, do not repeat them here.Vacuum tightness of the present invention is meant the absolute value (being gauge pressure) of the difference of absolute pressure and barometric point.
Among the present invention, the content of described isocyanato can for example can adopt the Di-n-Butyl Amine titration measuring with well known to a person skilled in the art the whole bag of tricks mensuration.The concrete operations of described Di-n-Butyl Amine volumetry have been conventionally known to one of skill in the art, and the present invention does not repeat them here.
The following examples will the invention will be further described.
Embodiment 1
The packaged material that present embodiment is used to that polyurethane sealing package material prescription provided by the invention is described and contains this prescription.
Dropping into 3 kilograms of polyethers Dio1-2000 and 2 kilograms of polyether-tribasic alcohol 330N in the reactor that thermometer, agitator and condensing works are housed that has vacuum dewatering plant, is to stir under 0.09 MPa, temperature are 110 ℃ to dewater 2 hours in vacuum tightness; Reactor is cooled to 45 ℃ then, add afterwards 2.2 kilograms of carbodiimide-ketone urea imine modified 4,4 '-MDI, slowly be warming up to 80 ℃, insulation reaction 3 hours; Drop into 0.8 kilogram of N-ethyl-gamma-amino isobutyl-Trimethoxy silane then, continue reaction till titration does not go out isocyanate groups, the degassing is to there not being bubble; Add 1.2 kilograms of dioctyl phthalate (DOP)s again, continue reaction and being cooled to 40 ℃ after 1 hour, add then 0.03 kilogram 2,2 '-the dimorpholine benzyl ethyl ether, stir fast back discharging and sealing are preserved.
Embodiment 2
The packaged material that present embodiment is used to that polyurethane sealing package material prescription provided by the invention is described and contains this prescription.
Dropping into 3 kilograms of polyether Glycols Dio1-2000 and 2 kilograms of polyether-tribasic alcohols 3050 in the reactor that thermometer, agitator and condensing works are housed that has vacuum dewatering plant, is to stir under 0.07 MPa, temperature are 100 ℃ to dewater 3 hours in vacuum tightness; Reactor is cooled to 45 ℃ then, add afterwards 2.2 kilograms of liquefaction 4,4 that obtain with the liquefaction of carbodiimide-ketone urea imines '-MDI, slowly be warming up to 85 ℃, insulation reaction 3 hours; Drop into 0.9 kilogram of N-ethyl-gamma-amino isobutyl-Trimethoxy silane then, continue reaction till titration does not go out isocyanate groups, the degassing is to there not being bubble; Add 1.2 kilograms of dibutyl phthalates again, continue reaction and being cooled to 40 ℃ after 1 hour, add then 0.1 kilogram of triethyl silicane and 0.04 kilogram 2,2 '-the dimorpholine benzyl ethyl ether, stir fast back discharging and sealing are preserved.
Embodiment 3
The packaged material that present embodiment is used to that polyurethane sealing package material prescription provided by the invention is described and contains this prescription.
Dropping into 5 kilograms of polyether Glycols Dio1-2000 in the reactor that thermometer, agitator and condensing works are housed that has vacuum dewatering plant, is to stir under 0.08 MPa, temperature are 110 ℃ to dewater 2 hours in vacuum tightness; Reactor is cooled to 45 ℃ then, add afterwards 2 kilograms of liquefaction 4,4 that obtain with the liquefaction of carbodiimide-ketone urea imines '-MDI, slowly be warming up to 80 ℃, insulation reaction 3 hours; Add 0.2 kilogram of γ-An Bingjisanyiyangjiguiwan and 0.5 kilogram of N-ethyl-gamma-amino isobutyl-Trimethoxy silane then, continue reaction till titration does not go out isocyanate groups, the degassing is to there not being bubble; Add 0.9 kilogram of dioctyl phthalate (DOP) again, continue reaction and being cooled to 40 ℃ after 1 hour, add then 0.08 kilogram of trimethyl silane, 0.04 kilogram 2,2 '-the dimorpholine benzyl ethyl ether, stir fast back discharging and sealing are preserved.
Embodiment 4
The packaged material that present embodiment is used to that polyurethane sealing package material prescription provided by the invention is described and contains this prescription.
Dropping into 2.5 kilograms of polyether Glycols Dio1-2000 and 1 kilogram of polyether-tribasic alcohol 3050 in the reactor that thermometer, agitator and condensing works are housed that has vacuum dewatering plant, is to stir under 0.09 MPa, temperature are 110 ℃ to dewater 2 hours in vacuum tightness; Reactor is cooled to 45 ℃ then, add afterwards 1.7 kilograms of liquefaction 4,4 that obtain with the liquefaction of carbodiimide-ketone urea imines '-MDI, slowly be warming up to 75 ℃, insulation reaction 4 hours; Add 0.8 kilogram of N-ethyl-gamma-amino isobutyl-Trimethoxy silane then, continue reaction till titration does not go out isocyanate groups, the degassing is to there not being bubble; Add 0.8 kilogram of dioctyl phthalate (DOP) again, continue reaction and be cooled to 40 ℃ after 1 hour, add then 0.06 kilogram of trimethyl silane, 0.03 kilogram 2,2 '-dimorpholine benzyl ethyl ether and 0.01 kilogram of butylated hydroxytoluene, stir fast back discharging and sealing are preserved.
Embodiment 5
The packaged material that present embodiment is used to that polyurethane sealing package material prescription provided by the invention is described and contains this prescription.
Adding 3 kilograms of polyether Glycols Dio1-2000 and 1.5 kilograms of polyether-tribasic alcohol 330N in the reactor that thermometer, agitator and condensing works are housed that has vacuum dewatering plant, is that 0.09 MPa, temperature are to stir under 110 ℃ of conditions to dewater 2 hours in vacuum tightness; Reactor is cooled to 45 ℃ then, add afterwards 2.1 kilograms of liquefaction 4,4 that obtain with the liquefaction of carbodiimide-ketone urea imines '-MDI, slowly be warming up to 80 ℃, insulation reaction 3 hours; Add 0.2 kilogram of γ-An Bingjisanyiyangjiguiwan and 0.6 kilogram of N-ethyl-gamma-amino isobutyl-Trimethoxy silane then, continue reaction till titration does not go out isocyanate groups, the degassing is to there not being bubble; Add 1.5 kilograms of dioctyl phthalate (DOP)s again, continue reaction and be cooled to 40 ℃ after 1 hour, add 0.3 kilogram of treated carbonates, 0.1 kilogram of aerosil, 0.03 kilogram of thio-2 acid SUNSOFT Q-182S, UV7700.02 kilogram then respectively, stir fast, the degassing is not to there being bubble, and discharging and sealing are preserved.
Embodiment 6
The packaged material that present embodiment is used to that polyurethane sealing package material prescription provided by the invention is described and contains this prescription.
Dropping into 3 kilograms of polyether Glycols Dio1-2000 and 2 kilograms of polyethers 3050 in the reactor that thermometer, agitator and condensing works are housed that has vacuum dewatering plant, is to stir under 0.09 MPa, temperature are 110 ℃ to dewater 2 hours in vacuum tightness; Reactor is cooled to 50 ℃ then, add 2.8 kilograms of liquefaction 4 of liquefying and obtaining afterwards with carbodiimide-ketone urea imines, 4 '-MDI, slowly be warming up to 80 ℃, insulation reaction 3.5 hours adds 1.0 kilograms of N-phenyl-γ-An Bingjisanjiayangjiguiwans then, continue reaction till titration does not go out isocyanate groups, the degassing is not to there being bubble, adds 0.02 kilogram 2,2 '-dimorpholine benzyl ethyl ether stir fast back discharging and sealing preservation.
Embodiment 7
The packaged material that present embodiment is used to that polyurethane sealing package material prescription provided by the invention is described and contains this prescription.
Dropping into 3 kilograms of polyether Glycols Dio1-2000 and 2 kilograms of polyethers 3050 in the reactor that thermometer, agitator and condensing works are housed that has vacuum dewatering plant, is to stir under 0.09 MPa, temperature are 110 ℃ to dewater 2 hours in vacuum tightness; Reactor is cooled to 50 ℃ then, add afterwards 2.8 kilograms of liquefaction 4,4 that obtain with the liquefaction of carbodiimide-ketone urea imines '-MDI, slowly be warming up to 80 ℃, insulation reaction after 3 hours discharging and sealing preserve.
Comparative Examples 1
The packaged material that this Comparative Examples is used to that single-component moisture curing polyurethane packaged material prescription of the prior art is described and contains this prescription.
The step that repeats embodiment 7 prepares the single-component moisture curing polyurethane packaged material, different is to adopt without pure 4 of liquefaction modification, 4 '-mixing solutions of MDI 1.5 kilograms (BASF Aktiengesellschaft provides) and acetone replace carbodiimide-ketone urea imine modified 4,4 '-MDI.
Performance test
Stability in storage, set time, breaking tenacity, elongation at break and 180 ° of stripping strengths of the polyurethane sealing package material that mensuration embodiment 1-7 and Comparative Examples 1 make, test result is as shown in table 1 below.Viscosity did not have the time of considerable change to represent when wherein, described stability in storage was preserved with 25 ℃ of lower seals; Described set time is for being that 25 ℃, relative humidity are the required time of completely solidified under the condition of 80% г H with the polyurethane sealing package material of 1 mm thick in temperature.Described surface drying time is for being that 25 ℃, relative humidity are that the condition lower surface of 80% г H solidifies the required time with the polyurethane sealing package material of 1 mm thick in temperature.Adopt GB/5766-86 plastics fracture strength test method to measure the breaking tenacity of polyurethane sealing package material; Adopt GB/T1040-92 plastic tensile method for testing performance to measure the elongation at break of polyurethane sealing package material; Adopt 180 ° of peeling strength test methods of GB/T5766/-1995 sizing agent to measure the stripping strength of polyurethane sealing package material.
Table 1
Example number |
Stability in storage (moon) |
Set time (hour) |
Surface drying time (minute) |
Breaking tenacity (MPa) |
Elongation at break (%) |
180 ° of stripping strengths (thousand Ns/rice) |
Embodiment 1 |
≥9 |
4.6 |
15 |
6.75 |
630 |
12.8 |
Embodiment 2 |
≥9 |
4.0 |
13 |
6.50 |
625 |
12.4 |
Embodiment 3 |
≥9 |
3.8 |
10 |
6.42 |
615 |
11.7 |
Embodiment 4 |
≥9 |
5.0 |
20 |
6.05 |
600 |
11.2 |
Embodiment 5 |
≥9 |
4.2 |
14 |
6.62 |
620 |
12.4 |
Embodiment 6 |
≥9 |
4.6 |
18 |
6.56 |
610 |
11.6 |
Embodiment 7 |
≥9 |
17 |
23 |
4.98 |
450 |
9.0 |
Comparative Examples 1 |
5 |
18 |
35 |
4.86 |
430 |
8.8 |
From the result of last table 1 as can be seen, polyurethane sealing package material provided by the invention has good stability in storage and curing performance, also has excellent mechanical mechanics property simultaneously, can satisfy various application needs.