CN102816549B - 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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- CN102816549B CN102816549B CN201210236019.7A CN201210236019A CN102816549B CN 102816549 B CN102816549 B CN 102816549B CN 201210236019 A CN201210236019 A CN 201210236019A CN 102816549 B CN102816549 B CN 102816549B
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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 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 the advantages such as elongation is large, intensity is high, wear resistance is outstanding, resistance to acids and bases, are widely used at coating, elastomerics, sizing agent and seal gum etc.Yet adhesive for polyurethane has the following disadvantages: (1) urethane is that two-phase thermodynamics is incompatible, presents microphase-separated by soft, the segmented copolymer that hard segment is connected to that replace.At low temperatures, hard section degree of crystallinity increases, and soft section also can forming section crystallization, and the uncompatibility of two-phase is increased, and microphase-separated degree of uniformity reduces, thereby has reduced the snappiness of material, can not meet the requirement that severe cold area is used; (2) the adhesive for polyurethane cured article of preparing with aromatic isocyanate, is subject to be easily oxidized to quinone after sunshine and flavescence causes weathering resistance poor, and cured article physicals declines to a great extent; (3) adhesive for polyurethane is poor to the wetting effect of base material, discharges CO in moisture curing process simultaneously
2, make the inner even crackle of abscess that produces of sizing agent, therefore be difficult to meet service requirements with the adhesiveproperties of base material.
Main following methods and the technology of adopting overcomes the problems referred to above at present:
(1) add softening agent and improve adhesive for polyurethane cured article snappiness: softening agent be take aliphatic diacid ester class as main, due to the larger and toxicity of addition own, in life-time service process, migration of plasticizer volatilization can endanger environment and human body, make product elasticity reduce simultaneously, affect 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 using molecular weight at more than 600 polyphosphazene polymer ethoxylated polyhydric alcohols as environment-friendly plasticizer, be respectively used to plasticising organic silicon modified polyurethane and organosilicon modified polyether; It is softening agent that Chinese patent CN02108525.0 be take to the lower ester that contains the single methanol that unsaturated or saturated fatty acid that carbon number is 10 ~ 24 and carbon number are 1 ~ 10 of environment undesirable action; Chinese patent CN201010268065.6 be take monohydroxy that molecular weight is 1000 ~ 5000 or mono amino polyethers and trifunctional isocyanate and is made the internal plasticizer with NCO branched chain type, and the seal gum obtaining can keep elasticity for a long time; This class softening agent can reduce hazardous property, but its plasticization effect does not still reach the level of conventional plasticizers, and addition is large, and the intensity of product and sticking power are had to certain influence;
(2) improve adhesive for polyurethane weathering resistance, the one, in preparing adhesive for polyurethane, add UV stabilizer and oxidation inhibitor etc., reduce the impact of light and heat oxidation on phenyl ring; The 2nd, use the base polyurethane prepolymer for use as of preparing with aliphatics or alicyclic isocyanate, the reactive behavior of aliphatics or alicyclic isocyanate is lower, and production process toxic is larger, and expensive, thereby its use is restricted;
(3) improve adhesive for polyurethane the sticking power of base material is mainly contained to following two kinds of approach: the one, in sizing agent, add the adhesion promoters such as silane coupling agent and derivative thereof, by siloxanes to surperficial migration, and the silanol that hydrolysis generates and the hydroxyl condensation of substrate surface, form firmly chemistry and connect; The 2nd, before coating seal gum, first at substrate surface coating silane coupling agent, improve the cohesive strength between sizing agent and base material, as Chinese patent CN200880121826.6 discloses a kind of silane coupling agent that can be used for adhesive for polyurethane, this silane coupling agent comprises Polyaldimines ALD, polyisocyanates and carboxylic acid etc.; Chinese patent CN201010609456.X discloses the silane coupling agent that a kind of polyurethane sealant is used, and it comprises isocyanate group 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 coupling agent addition is little, transition process is slow, the DeGrain that improves that causes sticking power, while using silane coupling agent, engineering time and cost increase, and are difficult to reach application requiring.
Silyl-terminated polyether main chain is macromole polyethers, and end group is the silylation of hydrolysable group.After solidifying, there is Si-O-Si network cross-linked point, for system provides weather-proof, ageing-resistant, ultraviolet resistance, the performance such as heat-resisting; Between cross-linking set, be polyethers long-chain, for system provides flexibility, prolongation property and anti-deformational displacement ability etc.In its structure, inherit end-silicane-group structure and main chain polyether structure, in performance, combined the advantage of silicone sealant and polyurethane adhesive, be applicable to need the occasion of good weatherability properties and excellent sealing, and its modest viscosity, viscosity is less with the variation of molecular weight.
Yet, with the prepared sizing agent of silyl-terminated polyether performed polymer, compare with adhesive for polyurethane, its solidify after self tensile strength less, affect its range of application.Conventionally adopt ultra-fine reinforced filling to strengthen silyl-terminated polyether sizing agent.If Chinese patent CN200810236985.2 is by adding 4 ~ 10 parts of reinforced fillings that the tensile strength of seal gum is increased substantially, Chinese patent CN200510132669.7 is also by adding a small amount of aerosil or black-reinforced.
Summary of the invention
The object of the invention is to for above-mentioned the deficiencies in the 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, by silyl-terminated polyether, replace part base polyurethane prepolymer for use as, by reducing the consumption of base polyurethane prepolymer for use as, utilize the feature that silyl-terminated polyether snappiness, weathering resistance and sticking power are good, prepare a kind of sizing agent that has silyl-terminated polyether and urethane feature concurrently.
In order to achieve the above object, the present invention has adopted following technical scheme:
An adhesive for polyurethane for silyl-terminated polyether modification, in mass fraction, component is as follows:
Polyurethane prepolymer 15 ~ 65,
Silyl-terminated polyether 5 ~ 60,
Softening agent 0 ~ 20,
Catalyzer 0.2 ~ 1,
Powder stuffing 0 ~ 45,
Auxiliary agent 0.8 ~ 3.5.
Described polyurethane prepolymer is the prepolymer with NCO end-blocking prepared by polyvalent alcohol and isocyanate compound, and its NCO content is 1 ~ 6%, and concrete content can need to regulate according to required molecular weight, hardness etc.
The end group of described silyl-terminated polyether is the polyoxytrimethylene ether that contains single siloxanes and/or two silicon alkoxyl groups, has following basic structure general formula:
Wherein, n is the number of propylene oxide chain link; A is the number of alkoxyl group, and b is methyl number, a=3-b, and b is 1 or 2; R represents methyl or ethyl, and molecular weight is 3000 ~ 15000.
Described softening agent is Phthalates, aliphatic dibasic acid ester or environment-friendly plasticizer, comprise Di Iso Decyl Phthalate, diisononyl phthalate, tributyl citrate, diethylene glycol dibenzoate or end capped polyether, be preferably Di Iso Decyl Phthalate or diisononyl phthalate.
Described catalyzer is organic tin catalyzer and/or tertiary amine catalyst, is preferably the tin class catalyzer containing sulfydryl.
Described powder stuffing is one or both in calcium carbonate, carbon black, titanium dioxide or aerosil.Powder stuffing needs through drying treatment before adding, to reduce the moisture in sizing agent.
Described auxiliary agent comprises moisture scavenger, oxidation inhibitor and UV light stabilizing agent.
Described moisture scavenger is silane coupling agent or oxazole alkanes coupling agent, comprise vinyltrimethoxy silane and 3-Ethyl-2-Methyl-2-(3-methyl butyl)-1,3-oxazolidine (is called for short: Zoldine MS-Plus), its consumption is 0.6 ~ 2.5 mass parts; Described oxidation inhibitor is Hinered phenols, comprise four (β-(3, antioxidant 1010) and 2,6 ditertiary butyl p cresol (abbreviation: antioxidant 264), its consumption is 0.1 ~ 0.5 mass parts tri-grades of butyl-4-hydroxy phenyls of 5-) propionic acid) pentaerythritol ester (is called for short:; Described 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, comprises the following steps:
(1) by mass fraction, will under polyurethane prepolymer, silyl-terminated polyether, UV light stabilizing agent and oxidation inhibitor vacuum, be uniformly mixed, be warming up to after 40 ~ 50 ℃, continue to stir 10 ~ 30 minutes;
(2) under nitrogen protection, add softening agent and powder stuffing, under vacuum, be warming up to 60 ~ 90 ℃, continue to stir 1 ~ 2 hour;
(3) be cooled to 40 ~ 50 ℃, and pass into 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 goes back the application of silylation polyether-modified adhesive for polyurethane in providing end in preparing elastic sealant.
Polyurethane prepolymer of the present invention adopts traditional method preparation; comprise the following steps: polyol compound is warming up to 110 ~ 120 ℃ of vacuum hydro-extraction 2h; then be cooled to 60 ℃; add isocyanate compound; logical nitrogen protection; and add dibutyl tin laurate, at 80 ℃, react 3 ~ 4h, be cooled to normal temperature after discharging obtain polyurethane prepolymer.
Described 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.
Described isocyanate compound is one or more in tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate or 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 the consumption of softening agent in sizing agent, reduces thus migration of plasticizer to sizing agent cured article over-all properties, and the detrimentally affect of the toxicity of environment;
(2) improve the low temperature kindliness of adhesive for polyurethane, make it have lower second-order transition temperature, thereby keep better elasticity under identical low temperature, expand sizing agent use range at low temperatures;
(3) silyl-terminated polyether and base polyurethane prepolymer for use as have good consistency, can realize the wide addition scope of silyl-terminated polyether, and the elastic rubber providing can have larger 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 in formula, aromatic isocyanate content reduces, and makes the weathering resistance of sizing agent better;
(5) silylation of silyl-terminated polyether is hydrolyzed into silanol, form chemistry and physical action with the hydroxyl of substrate surface, make sizing agent have higher cohesive strength to base material, do not need to add any adhesion promoter, or before applying glue, do not need to use any silane coupling agent, it can meet application requiring to the cohesive strength of substrate surface.
Embodiment
Below in conjunction with embodiment and comparative example, the present invention is described in further detail, but the scope of protection of present invention is not limited to therewith.
Silyl-terminated polyether adopts product S203H, the S303H of Japanese KANEKA company.
Organic tin catalyzer adopts Fomrez UL-29, the Fomrez UL-6 of organosilicon company of GE Toshiba.
To the product of embodiment and comparative example, adopt respectively following methods to analyze mensuration.
(1) NCO content in base polyurethane prepolymer for use as:
Press the content that the Di-n-Butyl Amine described in HGT 2049-1992 " mensuration of isocyanate group content in base polyurethane prepolymer for use as "-toluene process is measured NCO in performed polymer;
(2) second-order transition temperature:
By second-order transition temperature, (be called for short: the low temperature flexibility of Tg) evaluating product, Tg is lower, low temperature flexibility is better: adopt DMA242C type dynamic mechanical analysis instrument (NETZSCH company, Germany) under mode standard, adopt stretching clamp in fixed frequency 1Hz, 5Hz, 10Hz and-150 ~ 0 ℃ of temperature ranges, take rate of extension as 5K/min, measure tan δ variation with temperature curve, 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 thermoplastic elastomer tensile stress-strain performance " and evaluate tensile strength and elongation at break;
(4) sizing agent cured article hardness:
Press GB/T 531-1999 " the pocket sclerometer penetration hardness of rubber test method " and evaluate sizing agent hardness;
(5) 180 ° of stripping tests:
Press GB/T 2790-1995 " 180 ° of peeling strength test methods of sizing agent ", without primary coat in the situation that, take glass as matrix, visual assessment sizing agent is in the destruction type of matrix surface;
(6) xanthochromia index:
After sizing agent is solidified, directly place outdoor exposure 7 days, by GB/T 1766-1995 " the evaluation scope of variable color grade ", pass through visual assessment, the colour-change degree of cured article, xanthochromia index is divided into 0 grade to 5 grades, is respectively without variable color, very light discolouration, light discolouration, obviously variable color, larger variable color, serious discoloration.
embodiment 1
(1) polyurethane preformed polymer A:
In 5L reactor, add 1600g polyether glycol (number-average molecular weight 2000), be warming up to vacuum hydro-extraction 2h at 110 ℃, then be cooled to 60 ℃, add 241.86g tolylene diisocyanate, logical nitrogen protection, and add 9.21g dibutyl tin laurate, at 80 ℃, react 3h, after being cooled to normal temperature, discharging obtains polyurethane prepolymer, and its NCO base content is 2.57%;
(2) prepare the adhesive for polyurethane of silyl-terminated polyether modification:
In 5L reactor, add polyurethane prepolymer A, silyl-terminated polyether, Tinuvin 327, antioxidant 1010; under 40 ℃ of vacuum protections, blend is after 10 minutes; under inflated with nitrogen protective condition, add again Di Iso Decyl Phthalate, calcium carbonate and aerosil; at 70 ℃, vacuum protection blend is 1.5 hours; cool to 50 ℃; under condition of nitrogen gas, add vinyltrimethoxy silane and curing catalysts Fomrez UL-29, vacuum stirring obtains the adhesive for polyurethane of silyl-terminated polyether modification for 20 minutes.
Embodiment 1 is used formula following (base polyurethane prepolymer for use as and silyl-terminated polyether mol ratio are 9.65:1):
Base polyurethane prepolymer for use as A(NCO=2.57%) 975g
Silyl-terminated polyether 101g
Di Iso Decyl Phthalate 194g
Calcium carbonate 573g
Aerosil 84g
Vinyltrimethoxy silane 40g
Tinuvin 327 9g
Antioxidant 1010 9g
Fomrez UL-29 15g
embodiment 2
According to following formula, by embodiment 1 method, prepare sizing agent (base polyurethane prepolymer for use as and silyl-terminated polyether mol ratio are 2.86:1):
Base polyurethane prepolymer for use as A(NCO=2.57%) 797g
Silyl-terminated polyether 279g
Di Iso Decyl Phthalate 194g
Calcium carbonate 573g
Aerosil 84g
Vinyltrimethoxy silane 40g
Tinuvin 327 9g
Antioxidant 1010 9g
Fomrez UL-29 15g
embodiment 3
According to following formula, by embodiment 1 method, prepare sizing agent (base polyurethane prepolymer for use as and silyl-terminated polyether mol ratio are 1:1.67):
Base polyurethane prepolymer for use as A(NCO=2.57%) 403g
Silyl-terminated polyether 673g
Di Iso Decyl Phthalate 194g
Calcium carbonate 573g
Aerosil 84g
Vinyltrimethoxy silane 40g
Tinuvin 327 9g
Antioxidant 1010 9g
Fomrez UL-29 15g
comparative example 1
According to following formula, by embodiment 1 method, prepare sizing agent (100% base polyurethane prepolymer for use as):
Base polyurethane prepolymer for use as A(NCO=2.57%) 1076g
Di Iso Decyl Phthalate 194g
Calcium carbonate 573g
Aerosil 84g
Vinyltrimethoxy silane 40g
Tinuvin 327 9g
Antioxidant 1010 9g
Fomrez UL-29 15g
comparative example 2
According to following formula, by embodiment 1 method, prepare sizing agent (100% silyl-terminated polyether):
Silyl-terminated polyether 1076g
Di Iso Decyl Phthalate 194g
Calcium carbonate 573g
Aerosil 84g
Vinyltrimethoxy silane 40g
Tinuvin 327 9g
Antioxidant 1010 9g
Fomrez UL-29 15g
comparative example 3
According to following formula, by embodiment 1 method, prepare sizing agent (base polyurethane prepolymer for use as and silyl-terminated polyether mol ratio are 2.86:1):
Base polyurethane prepolymer for use as A(NCO=2.57%) 797g
Di Iso Decyl Phthalate 624g
Calcium carbonate 593g
Aerosil 64g
Vinyltrimethoxy silane 40g
Tinuvin 327 9g
Antioxidant 1010 9g
Fomrez UL-29 15g
Sizing agent to embodiment 1 ~ 3 and comparative example 1 ~ 3 preparation carries out respectively the mensuration of physico-chemical property, and result is as shown in table 1.
The measurement result of the physico-chemical property of table 1 embodiment 1 ~ 3 and comparative example 1 ~ 3
CF: cohesive failure rate, represents with area percentage (%) in table.
AF: interfacial failure rate, represents with area percentage (%) in table.
As shown in Table 1, by embodiment 1 ~ 3, fix N CO content is 2.57%, along with the content of silyl-terminated polyether in 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 example 1, and second-order transition temperature has reduced respectively 2.1 ℃, 5.8 ℃ and 17.6 ℃;
(2) the xanthochromia intensity of variation of cured article reduces, and compares with comparative example 1, and during from pure urethane 5 grades of xanthochromia index, are reduced to respectively 3 grades, 2 grades and 1 grade;
(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 is increased to respectively 75%, 85% and 90% cohesive failure;
(4) hardness is reduced to respectively 62,51 and 45 from 75 of comparative example 1.
In addition, the hardness of embodiment 2 and comparative example 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 only 9.7%, illustrate that the present invention, by silyl-terminated polyether modification, can reduce the consumption of softening agent in sizing agent.
The sizing agent of comparative example 2 for only being prepared by silyl-terminated polyether, can find out, with respect to the tensile strength of its 1.9 MPa, add after base polyurethane prepolymer for use as, the tensile strength of sizing agent obviously improves.
More than show, in the present invention, silyl-terminated polyether add the second-order transition temperature that can reduce sizing agent, improve low temperature flexibility, reduce the consumption of softening agent, improve weathering resistance, increase cohesive strength.
embodiment 4
(1) polyurethane preformed polymer B:
In 5L reactor, add 1880g polyether glycol (number-average molecular weight 4000), be warming up to vacuum hydro-extraction 2h at 120 ℃, then be cooled to 60 ℃, add 130.5g tolylene diisocyanate, logical nitrogen protection, and add 10.05g dibutyl tin laurate, at 80 ℃, react 3h, after being cooled to normal temperature, discharging obtains polyurethane prepolymer, and its NCO base content is 1.09%;
(2) prepare the adhesive for polyurethane of silyl-terminated polyether modification:
In 5L reactor, add 302g polyurethane prepolymer B, 1200g silyl-terminated polyether, 7gUV-327,2g anti-aging agent-264; under 40 ℃ of vacuum protections, blend is after 30 minutes; under inflated with nitrogen protective condition, add again carbon black 388g and aerosil 24g; be warming up at 60 ℃ vacuum protection blend 1.5 hours; cool to 40 ℃; under condition of nitrogen gas, add 22gZoldine MS-Plus(U.S. Angus chemical company) and 20g curing catalysts Fomrez UL-29, vacuum stirring obtains the adhesive for polyurethane of silyl-terminated polyether modification for 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, xanthochromia index is that 0,180 ° of stripping test bond damage form is CF90.
embodiment 5
(1) polyurethane preformed polymer C:
In 5L reactor, add 1680g polyether glycol (number-average molecular weight 4000), be warming up to vacuum hydro-extraction 2h at 115 ℃, then be cooled to 60 ℃, add 212.3g tolylene diisocyanate, logical nitrogen protection, and add 9.45g dibutyl tin laurate, at 80 ℃, react 3.5h, after being cooled to normal temperature, discharging obtains polyurethane prepolymer, and its NCO base content is 3.48%;
(2) prepare the adhesive for polyurethane of silyl-terminated polyether modification:
In 5L reactor, add 349.2g polyurethane prepolymer C, 436g silyl-terminated polyether, 2gUV-1164, 10g anti-aging agent-264, under 45 ℃ of vacuum protections, blend is after 15 minutes, under inflated with nitrogen protective condition, add again tributyl citrate 247g, calcium carbonate 595g, titanium dioxide 214g and aerosil 86g, at 90 ℃, vacuum protection blend is 2 hours, cool to 40 ℃, under condition of nitrogen gas, add vinyltrimethoxy silane 49.8g and 11g curing catalysts Fomrez UL-29, vacuum stirring obtains the adhesive for polyurethane of silyl-terminated polyether modification for 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, xanthochromia index is that 1,180 ° of stripping test bond damage form is CF85.
embodiment 6
(1) polyurethane preformed polymer D:
In 5L reactor, add 1800g polyether glycol (number-average molecular weight 6000), be warming up to vacuum hydro-extraction 2h at 115 ℃, then be cooled to 60 ℃, add 315g tolylene diisocyanate, logical nitrogen protection, and add 10.6g dibutyl tin laurate, at 80 ℃, react 4h, after being cooled to normal temperature, discharging obtains polyurethane prepolymer, and its NCO base content is 5.92%;
(2) prepare the adhesive for polyurethane of silyl-terminated polyether modification:
In 5L reactor, add 1300g polyurethane prepolymer D, 273g silyl-terminated polyether, 10gUV-531,4g antioxidant 1010; under 50 ℃ of vacuum protections, blend is after 30 minutes; under inflated with nitrogen protective condition, add again end capped polyether 397g; at 80 ℃, vacuum protection blend is 1 hour; cool to 45 ℃; under condition of nitrogen gas, add vinyltrimethoxy silane 12g and 4g curing catalysts Fomrez UL-6, vacuum stirring obtains the adhesive for polyurethane of silyl-terminated polyether modification for 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, xanthochromia index is that 3,180 ° of stripping test bond damage forms are CF75.
Claims (7)
1. an adhesive for polyurethane for silyl-terminated polyether modification, is characterized in that, in mass fraction, component is as follows:
Polyurethane prepolymer 15 ~ 65,
Silyl-terminated polyether 5 ~ 60,
Softening agent 0 ~ 20,
Catalyzer 0.2 ~ 1,
Powder stuffing 0 ~ 45,
Auxiliary agent 0.8 ~ 3.5;
Described polyurethane prepolymer is the prepolymer with NCO end-blocking prepared by polyvalent alcohol and isocyanate compound, and its NCO content is 1 ~ 6%;
Described auxiliary agent comprises moisture scavenger, oxidation inhibitor and UV light stabilizing agent;
Described silyl-terminated polyether is the polyoxytrimethylene ether that end group contains single siloxanes and/or two silicon alkoxyl groups, has following basic structure general formula:
Wherein, n is the number of propylene oxide chain link; A is the number of alkoxyl group, and b is methyl number, a=3-b, and b is 1 or 2; R represents methyl or ethyl, and molecular weight is 3000 ~ 15000.
2. adhesive for polyurethane according to claim 1, is characterized in that, described softening agent is Phthalates, aliphatic dibasic acid ester or environment-friendly plasticizer.
3. adhesive for polyurethane according to claim 2, is characterized in that, described catalyzer is organic tin catalyzer and/or tertiary amine catalyst.
4. adhesive for polyurethane according to claim 3, is characterized in that, described powder stuffing is one or both in calcium carbonate, carbon black, titanium dioxide or aerosil.
5. adhesive for polyurethane according to claim 1, is characterized in that, described moisture scavenger is silane coupling agent or oxazole alkanes, and its consumption is 0.6 ~ 2.5 mass parts; Described oxidation inhibitor is Hinered phenols, and its consumption is 0.1 ~ 0.5 mass parts; Described UV light stabilizing agent is salicylate class, benzophenone class, benzotriazole category or triazines, and its consumption is 0.1 ~ 0.5 mass parts.
6. the preparation method of the modified polyurethane sizing agent described in one of claim 1 ~ 5, is characterized in that, comprises the following steps:
(1) by mass fraction, will under polyurethane prepolymer, silyl-terminated polyether, UV light stabilizing agent and oxidation inhibitor vacuum, be uniformly mixed, be warming up to after 40 ~ 50 ℃, continue to stir 10 ~ 30 minutes;
(2) under nitrogen protection, add softening agent and powder stuffing, under vacuum, be warming up to 60 ~ 90 ℃, continue to stir 1 ~ 2 hour;
(3) be cooled to 40 ~ 50 ℃, and pass into 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.
7. the application of the modified polyurethane sizing agent described in one of claim 1 ~ 5 in preparing elastic sealant.
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|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| CN106753170B (en) * | 2016-12-06 | 2020-06-12 | 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 |
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| CN109575870B (en) * | 2018-11-14 | 2020-05-22 | 华南理工大学 | Modified siloxane-terminated polyurethane sealant and preparation method thereof |
| CN109535366B (en) * | 2018-11-16 | 2021-05-07 | 上海东大化学有限公司 | Secondary amino silane modified polyether polymer 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 |
| CN112552870B (en) * | 2020-12-29 | 2022-08-02 | 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 |
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| CN1995140A (en) * | 2005-12-28 | 2007-07-11 | 北京市天山新材料技术公司 | Single component silane modified polyether seal glue and its preparation method |
| CN101760173A (en) * | 2008-12-24 | 2010-06-30 | 湖北回天胶业股份有限公司 | One-component silicyl polyether sealing adhesive and preparation method thereof |
| CN102086368A (en) * | 2010-12-17 | 2011-06-08 | 广州新展有机硅有限公司 | Environmentally-friendly organosilicon-modified polyurethane adhesive sealant |
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