CN101629061B - Monocomponent moisture cure urethanes adhesive - Google Patents
Monocomponent moisture cure urethanes adhesive Download PDFInfo
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- CN101629061B CN101629061B CN 200810040535 CN200810040535A CN101629061B CN 101629061 B CN101629061 B CN 101629061B CN 200810040535 CN200810040535 CN 200810040535 CN 200810040535 A CN200810040535 A CN 200810040535A CN 101629061 B CN101629061 B CN 101629061B
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Abstract
The invention provides a monocomponent moisture cure urethanes adhesive. The adhesive comprises the following compositions in portion by weight: 100 portions of isocyanate terminated polyurethane prepolymer, 0.025 to 0.25 portion of composite catalyst, 0.001 to 0.3 portion of stabilizer, 0.5 to 2 portions of coupling agent, 0.05 to 0.30 portion of antioxidant and 0 to 25 portions of diluting agent which react and are mixed, wherein the isocyanate terminated polyurethane prepolymer is prepared by reactions of polyisocyanates which is mixed by carbodiimide modified methyl diphenylene diisocyanate or 4,4'-methyl diphenylene diisocyanate and polyaryl polymethylene isocyanate, and polyester polyol with number average molecular weight of Mn of between 400 and 2,500 or polyether polyol with number average molecular weight of Mn of between 400 and 4,000 and a chain extender. The adhesive has higher curing speed and longer applicable time, can be bonded with an aluminum alloy with shearing strength more than or equal to 8Mpa after curing at room temperature, has plump fluff and good hand feeling in electrostatic flocking products with abrasion resistance of a spinning machine roller reaching over 10,000 times.
Description
Technical field
What the present invention relates to is a kind of wet-solidifying single-component polyurethane tackiness agent and preparation method thereof, and this tackiness agent utilizes in main component in strong polar group NCO base and air or trace water or the crosslinked generation bonding strength of active hydrogen reaction on adherend surface.Be specially adapted to some metal under room temperature such as aluminium, iron, galvanized sheet or nonmetal static flocking as ABS, PVC, PC, PVC rubber member and hardwood goods etc. or bonding.
Background technology
Polyurethane adhesive has good cementability, variety diversity, outstanding oil resistant, low temperature resistant and impact resistance makes it obtain very fast development in recent decades.The wet-solidifying single-component polyurethane tackiness agent is due to its single liquid packing, and is easy to use, can not cause two components join the trouble of glue and too many or too much for use and the disadvantage of fixed waste, therefore favored by the user.But wet-solidifying single-component polyurethane tackiness agent curing speed in the past is slower, and initial bonding strength is relatively poor, and often there are the shortcoming of cementability or wear resistance deficiency in bonding strength or flock printed article, and bonding or static flocking occasion is difficult to be suitable at some.Therefore mostly adopted dual-component polyurethane adhesive or used single-component " dead front type " flocking glue of polyurethane in the occasion of having relatively high expectations in the past.Need heating when " dead front type " one-component polyurethane adhesive uses, to reach the deblocking temperature of encapsulant, make its discharge-the NCO base and then with component in the active hydrogen reaction crosslinking curing.Because use temperature is higher, can not adopt if require at room temperature bonding or flocking to solidify.
In addition in the last few years, also formed by introduce to dive solid agent such as oxazole alkanes, the compounds such as polynary amine that sealed the type wet-solidifying single-component polyurethane tackiness agent admittedly of diving in the wet-solidifying single-component polyurethane tackiness agent.When this glue is met water or moisture, the solid agent meeting of diving first generates with the moisture content reaction compound that contains active hydrogen group, and (reactivity ratio's water NCO) is high, can improve tack for this compound and isocyanato, avoid simultaneously glue-line to produce bubble, but remain at present in the higher problem of cost.
Summary of the invention
Existing market is badly in need of that the exploitation adhesiveproperties is good, easy to use, shelf-stable and curing speed wet-solidifying single-component polyurethane tackiness agent faster.
The objective of the invention is for adapting to the needs in market, improve some deficiency that existing one-component polyurethane adhesive is applied to bonding or flocking art, improve the wear resistance of bonding strength or flocking hair, and make toughness, feel and cementability reach certain balance, make simultaneously glue have curing speed and long applicable time faster.
The present invention is to mix polyisocyanates and one or two or more kinds polyester polyol or polyether glycol or their mixture reaction or to make through paracyanogen ester performed polymer and composite catalyst, stablizer, oxidation inhibitor, coupling agent and the thinner of the end isocyanato of chain extension generation.The synthetic polyisocyanates of base polyurethane prepolymer for use as that wherein is used for the end isocyanato is selected the diphenylmethanediisocyanate (liquefied mdi) or 4 of Carbodiimide-Modified, the mixture of 4 '-diphenylmethanediisocyanate and many phenyl polymethine polyisocyanates (PAPI), the polyisocyanates of this mixing can contain less SA 2, the 4-MDI isomer, therefore reaction or curing speed are relatively very fast, also can adopt to contain more SAly 2,4-MDI synthesizes the base polyurethane prepolymer for use as of holding isocyanato.According to the requirement of adhesives to toughness, the weight ratio of above-mentioned MDI consumption and PAPI is 5～50: regulate in 95～50 scope, wherein with weight ratio 10～30: 90～70 is better, and average functionality is 2.45～2.65.Polyester polyol is by one or two or more kinds diprotic acid and the ethylene glycol, butyleneglycol, propylene glycol, neopentyl glycol, glycol ether, 1 in hexanodioic acid, sebacic acid, m-phthalic acid, Tetra hydro Phthalic anhydride or terephthalic acid, 6 hexylene glycols or 1, a kind of or dibasic alcohol polycondensation preparation more than two kinds in 4 Dimethylcyclohexyl glycol etc., its number-average molecular weight is 400～2500; Polyether glycol is that its number-average molecular weight is 400～4000 by one or two or more kinds the mixture in polyoxypropyleneglycol, polyoxytrimethylene-ethylene glycol, polytetrahydrofuran diol or copolyether glycol etc.; Also but the polyester polyethers mixes use.For guaranteeing that suitable cross-linking density and required performance often adopt the polyvalent alcohol of different molecular weight to mix to come synthetic, the NCO/OH mol ratio of polyisocyanates and polyvalent alcohol is generally 3: 1～and 5: 1, in the base polyurethane prepolymer for use as of end isocyanato-NCO is for well between the 9-13 % by weight of performed polymer total amount.
Composite catalyst is comprised of Primary Catalysts and promotor, Primary Catalysts is from two morpholine Anaesthetie Ethers, two (2,6 thebaine ethyls) ether, 1,2, select a kind of in 4 tri methyl piperazines, isocaprylic acid bismuth, isocaprylic acid zinc, isocaprylic acid tin or dibutyl tin laurate or two kinds, with promotor 1,3 dimethyl-2-imidazolinones form composite catalyst, the weight ratio of Primary Catalysts and promotor is 1～10: 1, and the composite catalyst consumption is 0.025～0.25 % by weight of the base polyurethane prepolymer for use as total amount of end isocyanato.
Stablizer is from H
3PO
4, select a kind of or two kinds in oleic acid, nitrobenzoic acid, 0-chloro-benzoic acid or diethyl malonate.Its consumption is 0.001～0.5 % by weight of the base polyurethane prepolymer for use as total amount of end isocyanato.
Coupling agent is to choose any one kind of them from γ-Racemic glycidol oxygen propyl trimethoxy silicane, vinyltrimethoxy silane, vinyltriethoxysilane, γ-isocyanic ester propyl trimethoxy silicane or γ-isocyanic ester propyl-triethoxysilicane.Its consumption is 0.5～2 % by weight of the base polyurethane prepolymer for use as total amount of end isocyanato.
Oxidation inhibitor is Hinered phenols or phosphate compounds, as tetramethylene (3,5 di-t-butyls-4-hydroxy phenylpropionic acid) choose any one kind of them in methyl esters (Irganox1010) or tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester (irgasfos 168) or their compound.Its consumption is 0.05～0.25 % by weight of the base polyurethane prepolymer for use as total amount of end isocyanato.
the thinner of selecting be organic solvent or softening agent (have also not solubilizing agent make no-solvent type monocomponent polyurethane glue), thinner is mainly used in the base polyurethane prepolymer for use as of the higher end isocyanato of viscosity, wherein organic solvent is from the ester class, ketone, aromatic hydrocarbons, propylene glycol ether-ether class, as vinyl acetic monomer, ritalin, N-BUTYL ACETATE, acetone, butanone, toluene, dimethylbenzene, select one or two or more kinds mixture in 1-Methoxy-2-propyl acetate, softening agent is from dioctyl phthalate (DOP), dioctyl phthalate, diisobutyl phthalate, butyl benzyl phthalate, choose any one kind of them in Octyl adipate or phenyl alkylsulf or two kinds, its consumption is 0～25 % by weight of the base polyurethane prepolymer for use as total amount of end isocyanato
Obtain wet-solidifying single-component polyurethane tackiness agent of the present invention by such scheme, its modest viscosity, easy to operate, according to requirements also can sneak into a small amount of pigment or weighting agent, after gluing static flocking or bonding after, self-vulcanizing, flock printed article intensity is high, fine hair is plentiful, good hand touch, and frame roller shuttle wear resistance reaches more than ten thousand times after tested, this glue also has good adhesiveproperties to above-mentioned materials in addition, aluminium alloy shearing resistance=8MPa that self-vulcanizing 7 days, hacking are processed can reach the bonding strength of universal dual-component polyurethane adhesive.
Embodiment
In order better to implement the present invention, especially exemplified by example, it is described, but is not limitation of the present invention.
Embodiment 1:
To gather adipate glycol 1,2 propylene glycol ester 1000g and drop in reactor, cooling at 120 ℃ of lower vacuum hydro-extraction 1h, get rid of vacuum, add the MDI-100LL 96.3g of polyphenyl polymethylene polyisocyanates PAPI 135866.7g and Carbodiimide-Modified.After mixing, at N
2Progressively temperature reaction under protection in 80～85 ℃ of reaction 2h, adds chainextender 1,4 butyleneglycol 10.5g continue reaction 1h, are cooled to below 50 ℃, add each 246.7g of dehydrated solvent toluene and vinyl acetic monomer, then add respectively the coupling agent KH-560 of raw material total amount 0.5%; The stablizer phosphoric acid (reagent) of raw material total amount 0.0015%; The anti-oxidant Irganox 1010 of raw material total amount 0.05%; Promotor 1,3 dimethyl-2-imidazolinone (reagent) of the two morpholine Anaesthetie Ethers of the Primary Catalysts of raw material total amount 0.015% and raw material total amount 0.02% packs after stirring in the clean container of drying.
Make the wet-solidifying single-component polyurethane tackiness agent, be 2.5h setting time, the applicable time 3h of glue, be used for bonding (the hacking processing) of aluminium alloy, self-vulcanizing 3 days and 7 days, shearing resistance is respectively: 7.3Mpa and 11.6Mpa, after the flocking of frame roller shuttle, wear resistance is more than ten thousand times, flock printed article fine hair is plentiful, good hand touch.
Embodiment 2:
Drop into successively in mass ratio the MDI-100LL 135.5g of many phenylmethanes polyisocyanates PM-2001222g and Carbodiimide-Modified in the clean reactor of drying, after mixing, add the poly-adipate glycol DOPCP 800g and the phthalic anhydride diglycol ester 200g that have dewatered, at N
2Progressively temperature reaction under protection is reacted 2h under 80～85 ℃, add Isosorbide-5-Nitrae butyleneglycol 18.9g, continues reaction 1h.Coolingly add dehydrated organic solvent toluene and each 295g of vinyl acetic monomer, and add successively the H of raw material total amount 0.0015% according to the operation steps of embodiment 1
3PO
4The coupling agent KH-560 of raw material total amount 0.5%, the anti-oxidant Irganox 1010 of raw material total amount 0.05%, the promotor 1 of the two morpholine Anaesthetie Ethers of the catalyzer of raw material total amount 0.015% and raw material total amount 0.02%, 3 dimethyl-2-imidazolinones pack after stirring in the clean container of drying.
The wet-solidifying single-component polyurethane tackiness agent that makes, setting time 4h, the applicable time 3h of glue is used for hacking and processes the bonding of aluminium alloy, self-vulcanizing 3 days and 7 days, shearing resistance is respectively: 7.8Mpa and 11.9Mpa; After the flocking of frame roller shuttle, wear resistance is more than ten thousand times, and flock printed article fine hair is plentiful, good hand touch.
In above-mentioned adhesive formulation, the wet-solidifying single-component polyurethane tackiness agent that poly-adipate glycol glycol ether ester (polyester plasticizer D-190) with 10% replaces organic solvent toluene/vinyl acetic monomer to form, the self-vulcanizing shearing resistance of 7 days is 11.7Mpa.
Embodiment 3:
In the formula of embodiment 1, except replace with the catalyzer dibutyl tin laurate of raw material total amount 0.015% two morpholine Anaesthetie Ethers and stablizer phosphoric acid consumption by 0.0015% of raw material total amount increase to the raw material total amount 0.012%, other formula and operating process and embodiment 1 are identical.
The wet-solidifying single-component polyurethane tackiness agent that obtains, setting time 2h, the applicable time is 4h, shearing resistance 7 days was 9.5Mpa; Gel time foreshortens to 17 ' 26 relatively "; Flock printed article fine hair is plentiful, good hand touch.
Embodiment 4:
press the composition and engineering process of embodiment 1 front with polyvalent alcohol and polyisocyanates, react 2h under 80～85 ℃, add chainextender 1, 4 butyleneglycols react 1h again, be cooled to 60 ℃ of left and right, the stablizer oleic acid that adds total amount 0.2%, react 30min at this temperature, vacuumize degassing 10min, cooling, composition and engineering according to embodiment 1 adds organic solvent again, coupling agent, oxidation inhibitor, catalyzer and promotor, make the wet-solidifying single-component polyurethane tackiness agent, be about 3h setting time, applicable time 4.5h, be used for hacking and process the bonding of aluminium alloy, self-vulcanizing 7 days, shearing resistance is 8.9Mpa, after the flocking of frame roller shuttle, wear resistance is more than ten thousand times, this glue self-vulcanizing 5 days, birch compression shear strength: 96.2Mpa, gel time is 20 ' 40 relatively ".
Embodiment 5:
The p-nitrobenzoic acid of stablizer oleic acid in embodiment 4 with total amount 0.15% replaced, make the wet-solidifying single-component polyurethane tackiness agent, be 3h setting time, the applicable time of glue is 2h, be used for hacking and process the bonding of aluminium alloy, self-vulcanizing 3 days and 7 days, shearing resistance is respectively 6.9Mpa and 9.1Mpa.
Embodiment 6:
Polyether glycol N210700g, N220150g and N204150g are dropped into reactor, under 120 ℃, decompression dehydration 1h, cooling, get rid of vacuum, many many methyl of the phenyl polyisocyanates PAPI 1351070g and the liquefied mdi Desmodur 2460M119g that measure are in advance added in polyether glycol, mix, at N
2Progressively temperature reaction under protection is reacted 2h under 60～70 ℃, add the oleic acid of 3.3g; continue reaction 0.5h; vacuum outgas 10min is cooled to below 40 ℃, adds KH-56010.9g; antioxidant 1010 1.1g; the two morpholine Anaesthetie Ether 0.33g of catalyzer, and 1,3 dimethyl-2-imidazolinone 0.44g; stir, pack in the clean container of drying.
The non-solvent single-component moisture cure urethanes adhesive that makes, setting time 3h, the applicable time 3h of glue is used for the bonding of aluminium alloy, self-vulcanizing 3 days and 7 days, shearing resistance is respectively 8Mpa and 9.7Mpa.
Raw material production producer in above-described embodiment is as follows:
Polyphenyl polymethylene polyisocyanates PAPI135 is Dow Chemical company (DOW Chem) product.The diphenylmethanediisocyanate MDI-100LL of Carbodiimide-Modified is Yantai ten thousand magnificent urethane stock company product.Coupling agent KH-560 is Nanjing dawn Chemical Group company product.Anti-oxidant Irganox 1010 is the Ciba fine chemicals product.The two morpholine Anaesthetie Ethers of Primary Catalysts are the meticulous product that changes into scientific and technological institute in Beijing.Many phenylmethanes polyisocyanates PM-200 is Yantai ten thousand magnificent urethane company product.Phthalic anhydride diglycol ester Mn570 is Nanjing, Nanjing Si Taipan chemical company product.Polyester plasticizer D190 is Shanghai Fu Mao chemical company product.Liquefied mdi Desmodur2460M is Bayer A.G's product.Polyether glycol N210, N220, N240 are Shanghai Gaoqiao petrochemical complex company limited products.
Claims (9)
1. monocomponent moisture cure urethanes adhesive is characterized in that forming and comprises base polyurethane prepolymer for use as 100 weight parts, composite catalyst 0.025～0.25 weight part, stablizer 0.001～0.3 weight part, oxidation inhibitor 0.05～0.3 weight part, coupling agent 0.5～2 weight part and thinner 0～2.5 weight part of holding isocyanato; The base polyurethane prepolymer for use as of described end isocyanato is take weight ratio as 10～30: the polyester polyol of the diphenylmethanediisocyanate of 90～70 Carbodiimide-Modified and the mixture of polyphenyl polymethylene polyisocyanates and one or two or more kinds different molecular weight or polyether glycol and chainextender reaction form.
2. monocomponent moisture cure urethanes adhesive according to claim 1, the diphenylmethanediisocyanate that it is characterized in that described Carbodiimide-Modified is 4 of Carbodiimide-Modified, 4 '-diphenylmethanediisocyanate.
3. monocomponent moisture cure urethanes adhesive according to claim 1, it is characterized in that described polyester polyol is a kind of from hexanodioic acid, sebacic acid, m-phthalic acid, terephthalic acid or Tetra hydro Phthalic anhydride or two kinds and ethylene glycol, butyleneglycol, propylene glycol, neopentyl glycol, glycol ether, 1,6 hexylene glycols or 1, select one or two or more kinds dibasic alcohol polycondensation preparation in 4 Dimethylcyclohexyl glycol, its number-average molecular weight is 400-2500; Polyether glycol is one or two or more kinds the mixture in polyoxypropyleneglycol, polyoxytrimethylene-ethylene glycol, polytetrahydrofuran diol and copolyether glycol thereof, and its number-average molecular weight is 400-4000.
4. monocomponent moisture cure urethanes adhesive according to claim 1, it is characterized in that described chainextender is from 1, choose any one kind of them in 4 butyleneglycols, ethylene glycol, 1,6 hexylene glycol or glycol ether, its consumption is 0～2.5 % by weight of the base polyurethane prepolymer for use as total amount of end isocyanato.
5. monocomponent moisture cure urethanes adhesive according to claim 1, it is characterized in that described composite catalyst is comprised of Primary Catalysts and promotor, Primary Catalysts is from two morpholine Anaesthetie Ethers, two (2,6 thebaine ethyls) ether, 1,2,4 tri methyl piperazines are selected a kind of or two kinds in isocaprylic acid bismuth, isocaprylic acid zinc, isocaprylic acid tin or dibutyl tin laurate, promotor is 1,3 dimethyl-2-imidazolinone; The weight ratio of Primary Catalysts and promotor is 1～10: 1.
6. monocomponent moisture cure urethanes adhesive according to claim 1, is characterized in that described stablizer is from H
3PO
4, select a kind of or two kinds in oleic acid, nitrobenzoic acid, chloro phenylformic acid or diethyl malonate.
7. monocomponent moisture cure urethanes adhesive according to claim 1, is characterized in that described coupling agent is to choose any one kind of them from γ-Racemic glycidol oxygen propyl trimethoxy silicane, vinyltrimethoxy silane, vinyltriethoxysilane, γ-isocyanic ester propyl trimethoxy silicane or γ-isocyanic ester propyl-triethoxysilicane.
8. monocomponent moisture cure urethanes adhesive according to claim 1, it is characterized in that described oxidation inhibitor is from tetramethylene (3,5 di-t-butyls-4-hydroxy phenylpropionic acid) choose any one kind of them in methyl esters or tricresyl phosphite (2,4 di-tert-butyl-phenyl) ester or their compound.
9. monocomponent moisture cure urethanes adhesive according to claim 1, it is characterized in that described thinner is organic solvent or softening agent, wherein organic solvent is to select one or two or more kinds mixture from vinyl acetic monomer, N-BUTYL ACETATE, acetone, butanone, toluene, dimethylbenzene or 1-Methoxy-2-propyl acetate; Softening agent is to select the mixture of one or two or more kinds from dioctyl phthalate (DOP), dioctyl phthalate, phthalic acid fourth Bian ester, Octyl adipate, poly-adipate glycol glycol ether ester or phenyl alkylsulf.
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| CN 200810040535 CN101629061B (en) | 2008-07-14 | 2008-07-14 | Monocomponent moisture cure urethanes adhesive |
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| CN 200810040535 CN101629061B (en) | 2008-07-14 | 2008-07-14 | Monocomponent moisture cure urethanes adhesive |
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| CN101629061B true CN101629061B (en) | 2013-06-05 |
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