CN102816549A - Silyl-terminated polyether modified polyurethane adhesive, its preparation method and application thereof - Google Patents
Silyl-terminated polyether modified polyurethane adhesive, its preparation method and application thereof Download PDFInfo
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- CN102816549A CN102816549A CN2012102360197A CN201210236019A CN102816549A CN 102816549 A CN102816549 A CN 102816549A CN 2012102360197 A CN2012102360197 A CN 2012102360197A CN 201210236019 A CN201210236019 A CN 201210236019A CN 102816549 A CN102816549 A CN 102816549A
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Abstract
The invention discloses a silyl-terminated polyether modified polyurethane adhesive which comprises the following ingredients of: by weight, 15-65 parts of a polyurethane prepolymer, 5-60 parts of silyl-terminated polyether, 0-20 parts of a plasticizer, 0.2-1 part of a catalyst, 0-45 parts of a powder filler and 0.8-3.5 parts of an auxiliary agent. The preparation method comprises the following steps of: mixing the polyurethane prepolymer, silyl-terminated polyether, a UV Stabilizer and an anti-oxidant, carrying out vacuum stirring at the temperature of 40-50 DEG C, adding the plasticizer and the powder filler under the protection of nitrogen, heating to 60-90 DEG C, stirring, cooling to 40-50 DEG C, adding a moisture scavenger and a curing catalyst, and continuously stirring so as to obtain the silyl-terminated polyether modified polyurethane adhesive. In comparison with a traditional polyurethane adhesive, the modified polyurethane adhesive provided by the invention has advantages of moderate viscosity, low plasticizer content, good low temperature flexibility, high strength, excellent weatherability and endurance, strong adhesion stress and the like, and can be used to prepare an elastic sealant.
Description
Technical field
The invention belongs to the sizing agent field, relate to a kind of modified polyurethane sizing agent and preparation method thereof, be specifically related to the adhesive for polyurethane and preparation method thereof and application of a kind of mono component wet solidifying silyl-terminated polyether modification.
Background technology
Urethane has good springiness, and advantages such as elongation is big, intensity is high, wear resistance is outstanding, resistance to acids and bases are widely used at coating, elastomerics, sizing agent and sealer etc.Yet not enough below adhesive for polyurethane exists: (1) urethane is the segmented copolymer soft by alternative, that hard segment is connected to, and two phase thermodynamics are incompatible, demonstrate microphase-separated.At low temperatures, hard section percent crystallinity increases, and soft section also can form partial crystallization, and the biphase uncompatibility is increased, and the microphase-separated degree of uniformity reduces, thereby has reduced the snappiness of material, can not satisfy the requirement that severe cold area uses; (2) with the adhesive for polyurethane cured article of aromatic isocyanate preparation, receive to be oxidized to quinone easily after sunshine and flavescence causes weathering resistance poor, the cured article physicals declines to a great extent; (3) adhesive for polyurethane is relatively poor to the wetting effect of base material, in the moisture curing process, discharges CO simultaneously
2, make inner abscess even the crackle of producing of sizing agent, so and the adhesiveproperties of base material be difficult to satisfy request for utilization.
Main at present following method of employing and technology overcome the problems referred to above:
(1) add softening agent and improve adhesive for polyurethane cured article snappiness: softening agent is main with aliphatic diacid ester class; Because the bigger and toxicity of addition own; In the life-time service process; The migration of plasticizer volatilization can endanger environment and human body, and product elasticity is reduced, and influences use properties;
The trend of using environment-friendly plasticizer and internal plasticizer to become to deal with problems as: Chinese patent CN201010593673.4, CN201010593317.2 with molecular weight at the polyphosphazene polymer ethoxylated polyhydric alcohol more than 600 as environment-friendly plasticizer, be respectively applied for plasticising organic silicon modified polyurethane and organosilicon modified polyether; Chinese patent CN02108525.0 is being that 10 ~ 24 unsaturated or sfas and carbon number are that the ester of single alcohol of 1 ~ 10 is a softening agent to the lower carbon number that contains of environment undesirable action; Chinese patent CN201010268065.6 is the internal plasticizer that 1000 ~ 5000 monohydroxy or mono amino polyethers and trifunctional isocyanate make band NCO branched chain type with molecular weight, and the sealer that obtains can keep elasticity for a long time; This type softening agent can reduce hazardous property, but its plasticization effect does not still reach the level of conventional plasticizers, and addition is big, and the intensity and the sticking power of product is all had certain influence;
(2) improve the adhesive for polyurethane weathering resistance, the one, in the preparation adhesive for polyurethane, add UV stabilizer and oxidation inhibitor etc., reduce the influence of light and heat oxidation to phenyl ring; Two are to use the base polyurethane prepolymer for use as with aliphatics or alicyclic isocyanate preparation, and the reactive behavior of aliphatics or alicyclic isocyanate is lower, and the production process toxic is bigger, and costs an arm and a leg, thereby its use is restricted;
(3) improve adhesive for polyurethane the sticking power of base material is mainly contained following two kinds of approach: the one, in sizing agent, add adhesion promoters such as silane coupling agent and verivate thereof; Through the migration of siloxanes to the surface; And the silanol that hydrolysis generates and the hydroxyl condensation of substrate surface form firm chemistry and connect; The 2nd, before applying sealer; Apply silane coupling agent at substrate surface earlier and improve the cohesive strength between sizing agent and the base material; Disclose a kind of silane coupling agent that can be used for adhesive for polyurethane like Chinese patent CN200880121826.6, this silane coupling agent comprises Polyaldimines ALD, POLYMETHYLENE POLYPHENYLISOCYANATE and carboxylic acid etc.; Chinese patent CN201010609456.X discloses the silane coupling agent that a kind of polyurethane sealant is used, and it comprises NCO matrix resin, catalyzer, solvent, silicane adhesion promoter etc., this silane coupling agent permeable base substrate, and bond effect is good; Above method all can be improved the sticking power of adhesive for polyurethane to a certain extent; But because the coupling agent addition is little, transition process is slow; The DeGrain that improves that causes sticking power, engineering time and cost increase when using silane coupling agent, are difficult to reach application requiring.
The silyl-terminated polyether main chain is the macromole polyethers, and end group is the siloyl group of hydrolysable group.Has Si-O-Si network cross-linked point after the curing, for system provides weather-proof, ageing-resistant, ultraviolet resistance, performance such as heat-resisting; Between the cross-linking set polyethers long-chain, for system provides flexibility, prolongation property and anti-deformational displacement ability etc.Inherit end-silicane-group structure and main chain polyether structure on its structure, combined the advantage of silicone sealant and polyurethane adhesive on the performance, be applicable to the occasion that needs good weatherability properties and excellent sealing property, and its modest viscosity, viscosity is less with change of molecular weight.
Yet, with the prepared sizing agent of silyl-terminated polyether performed polymer, to compare with adhesive for polyurethane, it is less that it solidifies back self tensile strength, influences its range of application.Usually adopt ultra-fine reinforced filling that the silyl-terminated polyether sizing agent is strengthened.Through adding 4 ~ 10 parts of reinforced fillings the tensile strength of sealer is increased substantially like Chinese patent CN200810236985.2, Chinese patent CN200510132669.7 is also through adding a spot of aerosil or black-reinforced.
Summary of the invention
The objective of the invention is to the deficiency to above-mentioned prior art, a kind of adhesive for polyurethane and preparation method thereof and application of silyl-terminated polyether modification is provided.
The present invention is in traditional adhesive for polyurethane; Add silyl-terminated polyether; Replace the part base polyurethane prepolymer for use as through silyl-terminated polyether; Through reducing the consumption of base polyurethane prepolymer for use as, utilize the good characteristics of silyl-terminated polyether snappiness, weathering resistance and sticking power, prepare a kind of sizing agent that has silyl-terminated polyether and urethane characteristics concurrently.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of adhesive for polyurethane of silyl-terminated polyether modification, in mass fraction, component is following:
Polyurethane prepolymer 15 ~ 65,
Silyl-terminated polyether 5 ~ 60,
Softening agent 0 ~ 20,
Catalyzer 0.2 ~ 1,
Powder filler 0 ~ 45,
Auxiliary agent 0.8 ~ 3.5.
Said polyurethane prepolymer be the preparation of polyvalent alcohol and isocyanate compound with the end capped prepolymer of NCO, its NCO content is 1 ~ 6%, concrete content can be regulated according to needs such as required molecular weight, hardness.
The end group of said silyl-terminated polyether is the polyoxytrimethylene ether that contains single siloxanes and/or two silicon alkoxyl groups, has following substruction general formula:
Wherein, n is the number of propylene oxide chain link; A is the number of alkoxyl group, and b is the methyl number, and a=3-b, b are 1 or 2; R representes methyl or ethyl, and molecular weight is 3000 ~ 15000.
Said softening agent is phthalic acid ester class, aliphatic dibasic acid ester or environment-friendly plasticizer; Comprise Di Iso Decyl Phthalate, DINP, tributyl citrate, diethylene glycol dibenzoate or end capped polyether, be preferably Di Iso Decyl Phthalate or DINP.
Said catalyzer is organic tin catalyzer and/or tertiary amine catalyst, is preferably the tin class catalyzer that contains sulfydryl.
Said powder filler is one or both in lime carbonate, carbon black, white titanium pigment or the aerosil.Before adding, the powder filler needs through drying treatment, to reduce the moisture in the sizing agent.
Said auxiliary agent comprises moisture scavenger, oxidation inhibitor and UV light stabilizing agent.
Said moisture scavenger is silane coupling agent or oxazole alkanes coupling agent, comprises that (be called for short: Zoldine MS-Plus), its consumption is 0.6 ~ 2.5 mass parts to vinyltrimethoxy silane and 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3-oxazoles alkane; Said oxidation inhibitor is Hinered phenols, comprises that (be called for short: antioxidant 1010) (abbreviation: antioxidant 264), its consumption is 0.1 ~ 0.5 mass parts to four (β-(3, three grades of butyl of 5--4-hydroxy phenyl) propionic acid) pentaerythritol ester with DBPC 2,6 ditertiary butyl p cresol; Said UV light stabilizing agent is salicylate class, benzophenone class, benzotriazole category or triazines, comprises UV-531, Tinuvin 327, UV-327 or UV-1164, and its consumption is 0.1 ~ 0.5 mass parts.
The present invention also provides a kind of preparation method of adhesive for polyurethane of silyl-terminated polyether modification, may further comprise the steps:
(1) by mass fraction with mixing under polyurethane prepolymer, silyl-terminated polyether, UV light stabilizing agent and the oxidation inhibitor vacuum, be warming up to 40 ~ 50 ℃ after, continue to stir 10 ~ 30 minutes;
(2) under nitrogen protection, add softening agent and powder filler, under vacuum, be warming up to 60 ~ 90 ℃, continue to stir 1 ~ 2 hour;
(3) be cooled to 40 ~ 50 ℃, and feed nitrogen, add moisture scavenger and curing catalysts, under vacuum, continue to stir discharging after 10 ~ 30 minutes, obtain the adhesive for polyurethane of silyl-terminated polyether modification.
The present invention also provides the application of adhesive for polyurethane in the preparation elastic sealant of silyl-terminated polyether modification.
Polyurethane prepolymer according to the invention adopts the traditional method preparation; May further comprise the steps: polyol compound is warming up to 110 ~ 120 ℃ of vacuum hydro-extraction 2h, is cooled to 60 ℃ then, add isocyanate compound; Logical nitrogen protection; And the adding dibutyl tin laurate, at 80 ℃ of following reaction 3 ~ 4h, be cooled to normal temperature after discharging obtain polyurethane prepolymer.
Said polyol compound is polyether glycol, modified polyether polylol, polyester polyol or other block copolymerization polyvalent alcohols, is preferably polyether glycol, and number-average molecular weight is 2000 ~ 6000.
Said isocyanate compound is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or the xylylene diisocyanate, is preferably tolylene diisocyanate.
The present invention compared with prior art has the following advantages and beneficial effect:
(1) silyl-terminated polyether has certain plastification to system, can reduce plasticizer dosage in the sizing agent, reduces migration of plasticizer thus to sizing agent cured article over-all properties, and the toxic detrimentally affect of environment;
(2) improve the low temperature kindliness of adhesive for polyurethane, make it have lower second-order transition temperature, thereby under identical low temperature, keep better elasticity, enlarge sizing agent use range at low temperatures;
(3) silyl-terminated polyether and base polyurethane prepolymer for use as have good consistency, can realize the addition scope that silyl-terminated polyether is wide, and the elastic rubber that is provided can have bigger changes in hardness scope
(4) sizing agent obtains the stable Si-O-Si cross-linked network of the effect of heat, oxygen, moisture after solidifying, and aromatic isocyanate content reduces in the prescription, makes that the weathering resistance of sizing agent is better;
(5) siloyl group of silyl-terminated polyether is hydrolyzed into silanol; Form chemistry and physical action with the hydroxyl of substrate surface; Make sizing agent higher bonding strength arranged to base material; Need not add any adhesion promoter, perhaps need not use any silane coupling agent before the applying glue, its cohesive strength to substrate surface can satisfy application requiring.
Embodiment
Below in conjunction with embodiment and Comparative Examples the present invention is made further detailed description, but the scope that the present invention requires to protect is not limited to therewith.
Silyl-terminated polyether adopts product S203H, the S303H of Japanese KANEKA company.
The organic tin catalyzer adopts Fomrez UL-29, the Fomrez UL-6 of organosilicon company of GE Toshiba.
Product to embodiment and Comparative Examples adopts following method to carry out assay determination respectively.
(1) NCO content in the base polyurethane prepolymer for use as:
Press the content that the Di-n-Butyl Amine described in the HGT 2049-1992 " NCO Determination on content in the base polyurethane prepolymer for use as "-toluene process is measured NCO in the performed polymer;
(2) second-order transition temperature:
(be called for short: the low temperature flexibility of Tg) estimating product through second-order transition temperature; Tg is low more, and low temperature flexibility is good more: adopt DMA242C type dynamic mechanical analysis appearance (NETZSCH company, Germany) under mode standard; Adopt stretching clamp in fixed frequency 1Hz, 5Hz, 10Hz and-150 ~ 0 ℃ of TRs; With the rate of extension is 5K/min, measures tan δ with the variation of temperature curve, and the peak value of getting 5Hz frequency tan δ curve obtains the second-order transition temperature of soft chain segment;
(3) sizing agent cured article tensile strength and elongation at break:
Press GB/T 528-1998 " mensuration of vulcanized rubber and TPR tensile stress-strain performance " and estimate tensile strength and elongation at break;
(4) sizing agent cured article hardness:
Press GB/T 531-1999 " the pocket sclerometer penetration hardness of rubber TP " and estimate sizing agent hardness;
(5) 180 ° of stripping tests:
Pressing GB/T 2790-1995 " 180 ° of peeling strength test methods of sizing agent ", under the situation of no primary coat, is matrix with glass, and the visual assessment sizing agent is in the destruction type of matrix surface;
(6) xanthochromia index:
After sizing agent curing; Directly place outdoor exposure 7 days; Pass through visual assessment by GB/T 1766-1995 " the evaluation scope of variable color grade "; The colour-change degree of cured article, xanthochromia index are divided into 0 grade to 5 grades, are respectively no variable color, very light discolouration, light discolouration, obviously variable color, big variable color, serious discoloration.
Embodiment 1
(1) polyurethane preformed polymer A:
In the 5L reaction kettle, add 1600g polyether glycol (number-average molecular weight 2000), be warming up to 110 ℃ of following vacuum hydro-extraction 2h, be cooled to 60 ℃ then; Add the 241.86g tolylene diisocyanate; Logical nitrogen protection, and add the 9.21g dibutyl tin laurate, react 3h down at 80 ℃; Discharging obtains polyurethane prepolymer after being cooled to normal temperature, and its NCO base content is 2.57%;
(2) adhesive for polyurethane of preparation silyl-terminated polyether modification:
In the 5L reaction kettle, add polyurethane prepolymer A, silyl-terminated polyether, Tinuvin 327, antioxidant 1010; Blend is after 10 minutes under 40 ℃ of vacuum protections; Under the inflated with nitrogen protective condition, add Di Iso Decyl Phthalate, lime carbonate and aerosil again; 70 ℃ of following vacuum protection blend 1.5 hours; Cool to 50 ℃, add vinyltrimethoxy silane and curing catalysts Fomrez UL-29 under the condition of nitrogen gas, vacuum stirring promptly obtained the adhesive for polyurethane of silyl-terminated polyether modification in 20 minutes.
Embodiment 1 uses prescription (base polyurethane prepolymer for use as and silyl-terminated polyether mol ratio are 9.65:1) as follows:
Base polyurethane prepolymer for use as A (NCO=2.57%) 975g
Silyl-terminated polyether 101g
Di Iso Decyl Phthalate 194g
Lime carbonate 573g
Aerosil 84g
Vinyltrimethoxy silane 40g
Tinuvin?327 9g
Antioxidant 1010 9g
Fomrez?UL-29 15g
Embodiment 2
According to following prescription, prepare sizing agent (base polyurethane prepolymer for use as and silyl-terminated polyether mol ratio are 2.86:1) by embodiment 1 method:
Base polyurethane prepolymer for use as A (NCO=2.57%) 797g
Silyl-terminated polyether 279g
Di Iso Decyl Phthalate 194g
Lime carbonate 573g
Aerosil 84g
Vinyltrimethoxy silane 40g
Tinuvin?327 9g
Antioxidant 1010 9g
Fomrez?UL-29 15g
Embodiment 3
According to following prescription, prepare sizing agent (base polyurethane prepolymer for use as and silyl-terminated polyether mol ratio are 1:1.67) by embodiment 1 method:
Base polyurethane prepolymer for use as A (NCO=2.57%) 403g
Silyl-terminated polyether 673g
Di Iso Decyl Phthalate 194g
Lime carbonate 573g
Aerosil 84g
Vinyltrimethoxy silane 40g
Tinuvin?327 9g
Antioxidant 1010 9g
Fomrez?UL-29 15g
Comparative Examples 1
According to following prescription, prepare sizing agent (100% base polyurethane prepolymer for use as) by embodiment 1 method:
Base polyurethane prepolymer for use as A (NCO=2.57%) 1076g
Di Iso Decyl Phthalate 194g
Lime carbonate 573g
Aerosil 84g
Vinyltrimethoxy silane 40g
Tinuvin?327 9g
Antioxidant 1010 9g
Fomrez?UL-29 15g
Comparative Examples 2
According to following prescription, prepare sizing agent (100% silyl-terminated polyether) by embodiment 1 method:
Silyl-terminated polyether 1076g
Di Iso Decyl Phthalate 194g
Lime carbonate 573g
Aerosil 84g
Vinyltrimethoxy silane 40g
Tinuvin?327 9g
Antioxidant 1010 9g
Fomrez?UL-29 15g
Comparative Examples 3
According to following prescription, prepare sizing agent (base polyurethane prepolymer for use as and silyl-terminated polyether mol ratio are 2.86:1) by embodiment 1 method:
Base polyurethane prepolymer for use as A (NCO=2.57%) 797g
Di Iso Decyl Phthalate 624g
Lime carbonate 593g
Aerosil 64g
Vinyltrimethoxy silane 40g
Tinuvin?327 9g
Antioxidant 1010 9g
Fomrez?UL-29 15g
Embodiment 1 ~ 3 and the sizing agent of Comparative Examples 1 ~ 3 preparation are carried out the mensuration of physico-chemical property respectively, and the result is as shown in table 1.
The mensuration result of the physico-chemical property of table 1 embodiment 1 ~ 3 and Comparative Examples 1 ~ 3
CF: the cohesive failure rate, represent with area percentage (%) in the table.
AF: the interfacial failure rate, represent with area percentage (%) in the table.
Can know that by table 1 by embodiment 1 ~ 3, fix N CO content is 2.57%, along with the content of silyl-terminated polyether in the modified polyurethane sizing agent increases gradually:
(1) second-order transition temperature moves to low temperature, adopts-29.6 ℃ of pure base polyurethane prepolymer for use as to compare with Comparative Examples 1, and second-order transition temperature has reduced by 2.1 ℃, 5.8 ℃ and 17.6 ℃ respectively;
(2) the xanthochromia intensity of variation of cured article reduces, and compares with Comparative Examples 1, and xanthochromia index 5 grades during from pure urethane are reduced to 3 grades, 2 grades and 1 grade respectively;
(3) cohesive force of sizing agent and base material increases, and the interfacial failure of the bond damage form of 180 ° of stripping tests 80% during from pure urethane increases to 75%, 85% and 90% cohesive failure respectively;
(4) hardness is reduced to 62,51 and 45 respectively from 75 of Comparative Examples 1.
In addition, the hardness of embodiment 2 and Comparative Examples 3 is very approaching, and the latter does not add silyl-terminated polyether; Its softening agent is up to 26.6%; And the former plasticizer loading is merely 9.7%, explains that the present invention through the silyl-terminated polyether modification, can reduce plasticizer dosage in the sizing agent.
Comparative Examples 2 is the sizing agent that is only prepared by silyl-terminated polyether, can find out, with respect to the tensile strength of its 1.9 MPa, behind the adding base polyurethane prepolymer for use as, the tensile strength of sizing agent obviously improves.
Show that more than among the present invention, the adding of silyl-terminated polyether can reduce the second-order transition temperature of sizing agent, improves low temperature flexibility, reduce plasticizer dosage, improve weathering resistance, increase cohesive strength.
Embodiment 4
(1) polyurethane preformed polymer B:
In the 5L reaction kettle, add 1880g polyether glycol (number-average molecular weight 4000), be warming up to 120 ℃ of following vacuum hydro-extraction 2h, be cooled to 60 ℃ then; Add the 130.5g tolylene diisocyanate; Logical nitrogen protection, and add the 10.05g dibutyl tin laurate, react 3h down at 80 ℃; Discharging obtains polyurethane prepolymer after being cooled to normal temperature, and its NCO base content is 1.09%;
(2) adhesive for polyurethane of preparation silyl-terminated polyether modification:
In the 5L reaction kettle, add 302g polyurethane prepolymer B, 1200g silyl-terminated polyether, 7gUV-327,2g anti-aging agent-264; Blend is after 30 minutes under 40 ℃ of vacuum protections; Under the inflated with nitrogen protective condition, add carbon black 388g and aerosil 24g again; Be warming up to 60 ℃ of following vacuum protection blend 1.5 hours; Cool to 40 ℃, add 22gZoldine MS-Plus (U.S. Angus chemical company) and 20g curing catalysts Fomrez UL-29 under the condition of nitrogen gas, vacuum stirring promptly obtained the adhesive for polyurethane of silyl-terminated polyether modification in 25 minutes.
Through mensuration, the adhesive for polyurethane of the silyl-terminated polyether modification of embodiment 4 preparations, its second-order transition temperature is-54.6 ℃; Tensile strength is 2.7MPa, and elongation at break is 524%, and hardness is 40; The xanthochromia index is that 0,180 ° of stripping test bond damage form is CF90.
Embodiment 5
(1) polyurethane preformed polymer C:
In the 5L reaction kettle, add 1680g polyether glycol (number-average molecular weight 4000), be warming up to 115 ℃ of following vacuum hydro-extraction 2h, be cooled to 60 ℃ then; Add the 212.3g tolylene diisocyanate; Logical nitrogen protection, and add the 9.45g dibutyl tin laurate, react 3.5h down at 80 ℃; Discharging obtains polyurethane prepolymer after being cooled to normal temperature, and its NCO base content is 3.48%;
(2) adhesive for polyurethane of preparation silyl-terminated polyether modification:
In the 5L reaction kettle, add 349.2g polyurethane prepolymer C, 436g silyl-terminated polyether, 2gUV-1164,10g anti-aging agent-264; Blend is after 15 minutes under 45 ℃ of vacuum protections; Under the inflated with nitrogen protective condition, add tributyl citrate 247g, lime carbonate 595g, white titanium pigment 214g and aerosil 86g again; 90 ℃ of following vacuum protection blend 2 hours; Cool to 40 ℃, add vinyltrimethoxy silane 49.8g and 11g curing catalysts Fomrez UL-29 under the condition of nitrogen gas, vacuum stirring promptly obtained the adhesive for polyurethane of silyl-terminated polyether modification in 30 minutes.
Through mensuration, the adhesive for polyurethane of the silyl-terminated polyether modification of embodiment 5 preparations, its second-order transition temperature is-42.6 ℃; Tensile strength is 4.1MPa, and elongation at break is 463%, and hardness is 47; The xanthochromia index is that 1,180 ° of stripping test bond damage form is CF85.
Embodiment 6
(1) polyurethane preformed polymer D:
In the 5L reaction kettle, add 1800g polyether glycol (number-average molecular weight 6000), be warming up to 115 ℃ of following vacuum hydro-extraction 2h, be cooled to 60 ℃ then; Add the 315g tolylene diisocyanate; Logical nitrogen protection, and add the 10.6g dibutyl tin laurate, react 4h down at 80 ℃; Discharging obtains polyurethane prepolymer after being cooled to normal temperature, and its NCO base content is 5.92%;
(2) adhesive for polyurethane of preparation silyl-terminated polyether modification:
In the 5L reaction kettle, add 1300g polyurethane prepolymer D, 273g silyl-terminated polyether, 10gUV-531,4g antioxidant 1010; Blend is after 30 minutes under 50 ℃ of vacuum protections; Under the inflated with nitrogen protective condition, add end capped polyether 397g again,, cool to 45 ℃ 80 ℃ of following vacuum protection blend 1 hour; Add vinyltrimethoxy silane 12g and 4g curing catalysts Fomrez UL-6 under the condition of nitrogen gas, vacuum stirring promptly obtained the adhesive for polyurethane of silyl-terminated polyether modification in 10 minutes.
Through mensuration, the adhesive for polyurethane of the silyl-terminated polyether modification of embodiment 6 preparations, second-order transition temperature is-33.6 ℃; Tensile strength is 6.7MPa, and elongation at break is 364%, and hardness is 58; The xanthochromia index is that 3,180 ° of stripping test bond damage forms are CF75.
Claims (10)
1. the adhesive for polyurethane of a silyl-terminated polyether modification is characterized in that, in mass fraction, component is following:
Polyurethane prepolymer 15 ~ 65,
Silyl-terminated polyether 5 ~ 60,
Softening agent 0 ~ 20,
Catalyzer 0.2 ~ 1,
Powder filler 0 ~ 45,
Auxiliary agent 0.8 ~ 3.5.
2. adhesive for polyurethane according to claim 1 is characterized in that, said polyurethane prepolymer be the preparation of polyvalent alcohol and isocyanate compound with the end capped prepolymer of NCO, its NCO content is 1 ~ 6%.
3. adhesive for polyurethane according to claim 2 is characterized in that, said silyl-terminated polyether is the polyoxytrimethylene ether that end group contains single siloxanes and/or two silicon alkoxyl groups, has following substruction general formula:
Wherein, n is the number of propylene oxide chain link; A is the number of alkoxyl group, and b is the methyl number, and a=3-b, b are 1 or 2; R representes methyl or ethyl, and molecular weight is 3000 ~ 15000.
4. adhesive for polyurethane according to claim 3 is characterized in that said softening agent is phthalic acid ester class, aliphatic dibasic acid ester or environment-friendly plasticizer, is preferably Di Iso Decyl Phthalate or DINP.
5. adhesive for polyurethane according to claim 4 is characterized in that said catalyzer is organic tin catalyzer and/or tertiary amine catalyst, is preferably the tin class catalyzer that contains sulfydryl.
6. adhesive for polyurethane according to claim 5 is characterized in that, said powder filler is one or both in lime carbonate, carbon black, white titanium pigment or the aerosil.
7. adhesive for polyurethane according to claim 6 is characterized in that said auxiliary agent comprises moisture scavenger, oxidation inhibitor and UV light stabilizing agent.
8. adhesive for polyurethane according to claim 7 is characterized in that, said moisture scavenger is silane coupling agent or oxazole alkanes, and its consumption is 0.6 ~ 2.5 mass parts; Said oxidation inhibitor is Hinered phenols, and its consumption is 0.1 ~ 0.5 mass parts; Said UV light stabilizing agent is salicylate class, benzophenone class, benzotriazole category or triazines, and its consumption is 0.1 ~ 0.5 mass parts.
9. the preparation method of the described modified polyurethane sizing agent of one of claim 1 ~ 8 is characterized in that, may further comprise the steps:
(1) by mass fraction with mixing under polyurethane prepolymer, silyl-terminated polyether, UV light stabilizing agent and the oxidation inhibitor vacuum, be warming up to 40 ~ 50 ℃ after, continue to stir 10 ~ 30 minutes;
(2) under nitrogen protection, add softening agent and powder filler, under vacuum, be warming up to 60 ~ 90 ℃, continue to stir 1 ~ 2 hour;
(3) be cooled to 40 ~ 50 ℃, and feed nitrogen, add moisture scavenger and curing catalysts, under vacuum, continue to stir discharging after 10 ~ 30 minutes, obtain the adhesive for polyurethane of silyl-terminated polyether modification.
10. the application of the described modified polyurethane sizing agent of one of claim 1 ~ 8 in the preparation elastic sealant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210236019.7A CN102816549B (en) | 2012-07-10 | 2012-07-10 | Silyl-terminated polyether modified polyurethane adhesive, its preparation method and application thereof |
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| CN201210236019.7A CN102816549B (en) | 2012-07-10 | 2012-07-10 | Silyl-terminated polyether modified polyurethane adhesive, its preparation method and application thereof |
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| CN102816549A true CN102816549A (en) | 2012-12-12 |
| CN102816549B CN102816549B (en) | 2014-02-26 |
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| CN201210236019.7A Expired - Fee Related CN102816549B (en) | 2012-07-10 | 2012-07-10 | Silyl-terminated polyether modified polyurethane adhesive, its preparation method and application thereof |
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| CN103173182A (en) * | 2013-03-23 | 2013-06-26 | 广东新展化工新材料有限公司 | Organic silicon modified polyurethane sealant and preparation method thereof |
| CN104087238A (en) * | 2014-06-18 | 2014-10-08 | 广州新展化工新材料有限公司 | Antifouling sealing material and preparation method thereof |
| CN104087231A (en) * | 2014-06-18 | 2014-10-08 | 广州新展化工新材料有限公司 | Silicyl-terminated modified polyurethane sealant and preparation method thereof |
| CN104087226A (en) * | 2014-06-18 | 2014-10-08 | 广州新展化工新材料有限公司 | Modified polyether sealant and preparation method thereof |
| CN106753170A (en) * | 2016-12-06 | 2017-05-31 | 东莞市新懿电子材料技术有限公司 | One-component moisture-curable elastic adhesive |
| CN107142070A (en) * | 2017-05-12 | 2017-09-08 | 武汉方成科技新材料有限公司 | Solvent-free double-constituent polyurethane compound adhesive |
| CN107955120A (en) * | 2016-10-17 | 2018-04-24 | 海口未来技术研究院 | Organic silicon modified polyurethane adhesive, its preparation method and application |
| CN107987773A (en) * | 2017-12-19 | 2018-05-04 | 上海德联化工有限公司 | A kind of automobile using composite polyurethane glass cement and preparation method thereof |
| CN109535366A (en) * | 2018-11-16 | 2019-03-29 | 上海东大化学有限公司 | A kind of secondary amino silanes modified polyether polymer and preparation method thereof |
| CN109575870A (en) * | 2018-11-14 | 2019-04-05 | 华南理工大学 | A kind of polyurethane sealant and preparation method thereof of modified siloxane sealing end |
| CN109897589A (en) * | 2019-01-23 | 2019-06-18 | 雨中情防水技术集团有限责任公司 | A kind of high-elastic sealant of environment-friendly type and preparation method thereof |
| CN112552870A (en) * | 2020-12-29 | 2021-03-26 | 烟台信友新材料有限公司 | High-strength high-hardness UV/moisture dual-curing MS glue and preparation method thereof |
| CN112999926A (en) * | 2021-03-31 | 2021-06-22 | 珠海市景晟包装材料有限公司 | Preparation method of sealant |
| CN114644902A (en) * | 2020-12-21 | 2022-06-21 | 南通天洋新材料有限公司 | Preparation method of reactive polyurethane hot melt adhesive |
| CN115678478A (en) * | 2022-02-22 | 2023-02-03 | 浙江星华反光材料有限公司 | Elastic single-component moisture-curing adhesive and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103173182A (en) * | 2013-03-23 | 2013-06-26 | 广东新展化工新材料有限公司 | Organic silicon modified polyurethane sealant and preparation method thereof |
| CN103173182B (en) * | 2013-03-23 | 2014-12-24 | 广东新展化工新材料有限公司 | Organic silicon modified polyurethane sealant and preparation method thereof |
| CN104087238A (en) * | 2014-06-18 | 2014-10-08 | 广州新展化工新材料有限公司 | Antifouling sealing material and preparation method thereof |
| CN104087231A (en) * | 2014-06-18 | 2014-10-08 | 广州新展化工新材料有限公司 | Silicyl-terminated modified polyurethane sealant and preparation method thereof |
| CN104087226A (en) * | 2014-06-18 | 2014-10-08 | 广州新展化工新材料有限公司 | Modified polyether sealant and preparation method thereof |
| CN107955120A (en) * | 2016-10-17 | 2018-04-24 | 海口未来技术研究院 | Organic silicon modified polyurethane adhesive, its preparation method and application |
| CN106753170A (en) * | 2016-12-06 | 2017-05-31 | 东莞市新懿电子材料技术有限公司 | One-component moisture-curable elastic adhesive |
| CN107142070A (en) * | 2017-05-12 | 2017-09-08 | 武汉方成科技新材料有限公司 | Solvent-free double-constituent polyurethane compound adhesive |
| CN107987773A (en) * | 2017-12-19 | 2018-05-04 | 上海德联化工有限公司 | A kind of automobile using composite polyurethane glass cement and preparation method thereof |
| CN109575870A (en) * | 2018-11-14 | 2019-04-05 | 华南理工大学 | A kind of polyurethane sealant and preparation method thereof of modified siloxane sealing end |
| CN109535366A (en) * | 2018-11-16 | 2019-03-29 | 上海东大化学有限公司 | A kind of secondary amino silanes modified polyether polymer and preparation method thereof |
| CN109897589A (en) * | 2019-01-23 | 2019-06-18 | 雨中情防水技术集团有限责任公司 | A kind of high-elastic sealant of environment-friendly type and preparation method thereof |
| CN109897589B (en) * | 2019-01-23 | 2021-08-03 | 雨中情防水技术集团股份有限公司 | Environment-friendly high-elasticity sealant and preparation method thereof |
| CN114644902A (en) * | 2020-12-21 | 2022-06-21 | 南通天洋新材料有限公司 | Preparation method of reactive polyurethane hot melt adhesive |
| CN112552870A (en) * | 2020-12-29 | 2021-03-26 | 烟台信友新材料有限公司 | High-strength high-hardness UV/moisture dual-curing MS glue and preparation method thereof |
| CN112999926A (en) * | 2021-03-31 | 2021-06-22 | 珠海市景晟包装材料有限公司 | Preparation method of sealant |
| CN115678478A (en) * | 2022-02-22 | 2023-02-03 | 浙江星华反光材料有限公司 | Elastic single-component moisture-curing adhesive and application thereof |
| CN115678478B (en) * | 2022-02-22 | 2024-04-30 | 浙江星华反光材料有限公司 | Elastic single-component moisture-curing adhesive and application thereof |
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