CN101735763B - Room temperature curing low-viscosity polyurethane foam adhesive and preparation method thereof - Google Patents
Room temperature curing low-viscosity polyurethane foam adhesive and preparation method thereof Download PDFInfo
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- CN101735763B CN101735763B CN 201010028016 CN201010028016A CN101735763B CN 101735763 B CN101735763 B CN 101735763B CN 201010028016 CN201010028016 CN 201010028016 CN 201010028016 A CN201010028016 A CN 201010028016A CN 101735763 B CN101735763 B CN 101735763B
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Abstract
The invention discloses a room temperature curing low-viscosity polyurethane foam adhesive consisting of polyurethane prepolymer and a morpholine catalyst. The viscosity of the adhesive is less than 600 mPa.S; in the presence of water or moisture at the temperature of between 10 and 30 DEG C, isocyanate in the polyurethane prepolymer, catalyzed by the morpholine catalyst, reacts with water or is condensed and polymerized to form CO2 gas which is foamed and cured to form a foam body; and the volume density of the foam body is 21 to 27Kg/m<3> or 15 to 29Kg/m<3>. The invention also discloses a preparation method for the adhesive. The polyurethane foam adhesive provided by the invention not only has low viscosity, good storage stability and high initial adhesion and adhesion strength of an adhesive surface, but also has low price, simple operation and moderate dryness in use, and is a new product in the field of room temperature wet curing foam adhesives.
Description
Technical field
The invention belongs to foam adhesive and preparation method thereof technical field, being specifically related to a kind of is reaction monomers with isocyanic ester, polyester polyol, polyether glycol, polyvalent alcohol, polyamine etc., with water is whipping agent, with the morpholine kind compound is curing catalysts, at room temperature the low density of fast automatic foamed solidification, low viscosity non-solvent polyurethane foam adhesive and preparation method thereof.
Background technology
Because the aerospace cause needs the high-intensity low density foam material of a large amount of uses as filling or structure unit, and some most advanced and sophisticated electronic components also adopt various low density foam materials more and more, therefore the bonding of this class A foam A material are just seemed very important.Good except requiring adhesiveproperties in these special dimensions, but also require caking agent itself can be foam type, make foam materials and caking agent form a successive integral body, therefore produce the heat subject that this class caking agent also just becomes present research.
Caking agent urethane (PU) tackiness agent of the most normal use now is to contain urethano in the molecular chain (NHCOO-) and an isocyanate group (NCO-) class tackiness agent, because its bonding force is strong, excellent property, wide in variety, suitability is wide, consumption is big, thereby has obtained widespread use in the every field of national economy, is most important kind in the eight big synthetic adhesives.Polyurethane adhesive can be divided into two types of single component and two-packs.
The mono-component polyurethane caking agent roughly have with-NCO be the end group performed polymer wet-cured type, with the encapsulant sealing (NCO) mixed type of the performed polymer of end group and polyvalent alcohol, in the urethane resin structure the five classes [Li Yongdes such as radiation-curable, hot-melting type, pressure sensitive of introducing acrylic ester monomer, Yang Yingxia. monocomponent moisture cure urethanes adhesive [J]. Chinese tackiness agent, 2003, (02)].
Bi-component polyurethane adhesive is made up of the first and second two components of packing separately, prepares by a certain percentage before the use to get final product.First component (host) is generally hydroxy-containing component, and second component (solidifying agent) is for containing the component of free isocyanate groups group.The host that also has is the base polyurethane prepolymer for use as of-NCO end group, solidifying agent is low molecular weight polyols or polyamine, first component and second component are mixed the generation urethane resin by a certain percentage, and become caking agent [Li Houtang, Fan Lidong. the development of new polyurethane adhensives and application [J]. Chinese tackiness agent, 2005, (02)].
Because the polyurethane adhesive material is made up of macromolecular compound itself, its density is all greater than 1.0g/cm
3, when it is used for bonding density usually all less than 1.0g/cm
3Foam materials the time, often do not reach bonding requirements, thus people begin to explore density that foaming method reduces tackiness agent satisfy these special dimensions needs [Malin etc., Progress in Structural Foaming Adhesive [J]. Chinese tackiness agent, 1993, (03)].
As everyone knows, the curing of polyurethane adhesive all needs to add catalyzer.In order to guarantee the low density of bonding back adhesive linkage, must solve rapid solidified problem in foaming, this during just to the foamed adhesive curing reaction used catalyzer harsh requirement has been proposed.Because catalyzer is selected inappropriate words; may cause-NCO is too fast with the reaction of-OH; make whole reaction system temperature height; do not have enough time to have foamed with regard to crosslinking curing; also may cause-NCO is slow excessively with the reaction of-OH, the gas that foaming needs when adhesive bulk viscosity is also very low just reaction produce and overflow, can not get foam [Wang Jinghui after bonding; polyurethane foam catalyzer [J]. Shanghai chemical industry, 1999. (05)].
Traditional foamed adhesive curing reaction catalyst mainly contains organic tin (as dibutyl tin laurate, stannous octoate) and tertiary amine base class catalyzer (as triethylamine, diethylenetriamine, triethylenediamine).
Though the organic tin compound has good katalysis to chainpropagation and the rate of crosslinking of NCO/OH.But because its catalytic activity height, very in short duration the reaction of chainpropagation is carried out fast, cause molecular weight sharply to increase, viscosity increases sharply, and just forms the heat curing-type network polymer in 1～2 minute, and easily produces sudden and violent poly-, make temperature of reaction system too high, wayward, when carrying out industrial production, also need refrigerating unit to come, thereby increased cost to the reaction system cooling.In addition, also be unfavorable for the storage of moisture cure urethanes adhesive after this catalyzer adds, its intensity is also had a significant impact.
Though tertiary amine base class catalyzer is initiated polymerization rapidly, transfer reaction and foamable reaction are all produced effect, and can prolong foamy gelling and set time, but higher because of catalytic activity to foamable reaction, phenomenons such as cream time is short, the rise time is short, the not sticking time is long too much will appear as adding in polyethers, be that foamable reaction speed is greater than transfer reaction speed, portion gas is overflowed, and reaction is carried out slowly, is difficult for solidifying, raw material outflow, and make and occur the hollow phenomenon in the insulating pipe.[He Yan etc., the amine tin catalyst effect [J] in rigid urethane foam, chemical engineer, 1999. (06)].
In addition, more than two class catalyzer also need the heating could catalytic curing, industrial production power consumption is big, makes cost increase.
And at present commercially available room temperature moisture curing foam glue product for example unsaturated polyester ester gum, epoxy glue, polyurethane adhesive be though that three components or two-pack glue can at room temperature carry out moisture curing, but have following problems respectively:
1. unsaturated polyester ester gum whole preparation process is comparatively complicated, on the high side.Typical unsaturated polyester preparation is with 1, the 2-propylene glycol, after MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride were mixed, 150～200 ℃ of condensations were tens hours in nitrogen or carbon dioxide atmosphere, up to generating molecular weight is 1000～2500 low acid number linear resin, adds monomer dilutions such as vinylbenzene again.Add peroxide initiator during use, carry out heat cross-linking, or at room temperature be cross-linked into solid, cross-linking radiations such as also available in addition ultraviolet ray, gamma-rays, electron beam after adding cobalt salt promotor at 100 ℃.Airborne oxygen has inhibition to resin crosslinked, introduces " air-drying property " genes such as allyl ethers, benzylic ether and can give normal temperature self-drying in linear polyester chain; Introducing naphthenic hydrocarbon dibasic alcohol etc. can obtain high softening point resin.
2. the bonding strength of epoxy glue is not enough, the gluing of surfaces selectivity is higher.Epoxy glue does not carry out when toughness reinforcing, and cured article is general crisp partially, and antistripping, cracking resistance, shock resistance are poor; The material little to polarity (as polyethylene, polypropylene, fluoroplastics etc.) bonding force is little, must carry out activation treatment to gluing of surfaces earlier; Some starting material such as reactive thinner, solidifying agent etc. also have toxicity and pungency in various degree.
3. poor, the rate of drying of water base adhesive initial bonding strength waits problem slowly.Though water accack can be eliminated the inflammable of organic solvent and murder by poisoning problem, and price is also low than solvent-based adhesive, yet in most of the cases, water accack must be antifreeze in storage and transportation, otherwise the permanent destruction of container or glue may occur.Emulsion adhesive then needs long time of drying, could set up intensity by tackify.On the other hand, the present preparation technology's level of emulsion adhesive also lags behind solvent-based adhesive greatly.
4. the solvent in the neoprene latex glue has both made foamy splicing face form the cavity because of dissolving foam, causes bonding strength to reduce again, and contaminate environment.Because neoprene latex is essentially " triphen " (benzene,toluene,xylene) solvent-based adhesive, solvent wherein not only can in use be dispersed in the air, serious environment pollution also can slowly discharge organic gas after decorations, also will bring harm for people's health.
Therefore, urgent need develop a kind of self-vulcanizing single component be easy to construction, initial bonding strength is strong, bonding strength is high, moderate drying speed, low price, especially do not corrode foamy tackiness agent [Li Yongde etc., the research [J] of monocomponent moisture cure type polyurethane seal gum catalyzer. research report, 1999, (09)].
Summary of the invention
The objective of the invention is problem at existing room temperature moisture curing foam glue existence, a kind of low-viscosity polyurethane foam adhesive of self-vulcanizing is provided, this foam adhesive can carry out the foamed solidification reaction at 10～30 ℃, and simple to operate, cheap, and ridity is moderate.
Another object of the present invention provides a kind of method for preparing the low-viscosity polyurethane foam adhesive of above-mentioned self-vulcanizing.
The low-viscosity polyurethane foam adhesive of self-vulcanizing provided by the invention is to be made of polyurethane prepolymer and morpholine class catalyzer, its viscosity＜600mPaS, when meeting water or moisture down for 10～30 ℃, can be by the isocyanic ester in the morpholine class catalyst polyurethane prepolymer and the rapid reaction of water or self polycondensation generation CO
2Gas foaming solidifies the acquisition foams.The volume density of the foams that obtained by the foam adhesive of single component form is 21～27Kg/m
3, the volume density of the foams that obtained by the foam adhesive of two-pack form is 15～29Kg/m
3
The low-viscosity polyurethane foam adhesive of the self-vulcanizing of above-mentioned single component form is to be 80～100 parts of 2000 polyoxytrimethylene dibasic alcohol by number-average molecular weight, the polyurethane prepolymer that 10～20 parts of polymerizations of 30～40 parts of diphenylmethanediisocyanates and tolylene diisocyanate obtain, 1～2 part of a morpholine class catalyzer and a condensed ethandiol mix for 5～8 parts, or be 30～50 parts of 1000 polyester diol by number-average molecular weight, number-average molecular weight is 80～100 parts of 2000 polyoxytrimethylene dibasic alcohol, number-average molecular weight is 10～20 parts of 6000 polyoxytrimethylene trivalent alcohols, 30～40 parts of diphenylmethanediisocyanates, the polyurethane prepolymer that 5～8 parts of polymerizations of hydrogenated terpene resin obtain, 2～3 parts of morpholine class catalyzer, one condensed ethandiol mixes for 8～10 parts, and umber wherein is weight part.
When the low-viscosity polyurethane foam adhesive of the self-vulcanizing of this single component form uses, be earlier with this adhesive coated on the bonding two articles surface of need, then with two articles near contact, place humidity greater than 80% moist environment, this tackiness agent just natural foaming solidifies.If environment is relatively drier, can suitably sprays less water on the bonding object of need, and then apply this caking agent.
The low-viscosity polyurethane foam adhesive of the self-vulcanizing of above-mentioned two-pack form is the first part polyurethane prepolymer that obtains of 70～110 parts of polymerizations of 2000 140～180 parts of polyoxytrimethylene dibasic alcohol, tolylene diisocyanate by number-average molecular weight and is made of 20～24 parts of ethylene glycol, 4～8 parts of glycerol, 20～25 parts of morpholine class catalyzer, 5～6 parts of butanediamine, 4～8 parts of second components of forming of water, the mass ratio of first component and second component is 3～6 during use, and umber wherein is weight part.
Contained morpholine class catalyzer is N-N-formyl morpholine N-or N-methyl ethyl diketone morpholine in the low-viscosity polyurethane foam adhesive of above-mentioned self-vulcanizing.
The low-viscosity polyurethane foam adhesive of the self-vulcanizing of this two-pack form is that first and second liang of components are first by weight 3～6 when using: 1 mixes, being coated on needs on the bonding two articles surface, with the close contact of two articles, place room temperature environment then, this caking agent just natural foaming solidifies.
The method of the low-viscosity polyurethane foam adhesive of the self-vulcanizing of the above-mentioned first kind of single component form of preparation provided by the invention is to be that 2000 polyoxytrimethylene dibasic alcohol stirs earlier for 80～100 parts and is warming up to 60-70 ℃ with the number-average molecular weight through processed, then with 30～40 parts of diphenylmethanediisocyanates, tolylene diisocyanate slowly is added drop-wise to wherein for 10～20 parts, and controlled temperature is at 60～70 ℃, dripped afterreaction 3～4 hours, be cooled to room temperature, add 1～2 part of morpholine class catalyzer again and a condensed ethandiol mixes for 5～8 parts, the airtight preservation in the exsiccant container of discharging splendid attire gets final product.
The method of the low-viscosity polyurethane foam adhesive of the self-vulcanizing of the above-mentioned second kind of single component form of preparation provided by the invention is to be 30～50 parts of 1000 polyester diol with the number-average molecular weight through processed, number-average molecular weight is 80～100 parts of 2000 polyoxytrimethylene dibasic alcohol, number-average molecular weight is 10～20 parts of 6000 polyoxytrimethylene trivalent alcohols, hydrogenated terpene resin stirs and is warmed up to 60-70 ℃ for 5～8 parts, drip 30～40 parts of diphenylmethanediisocyanates then, dripped afterreaction 3～4 hours, be cooled to room temperature, add 2～3 parts of morpholine class catalyzer again, one condensed ethandiol mixes for 8～10 parts, and the airtight preservation in the exsiccant container of discharging splendid attire gets final product.
Material umber used in the above method is weight part.
The method of the low-viscosity polyurethane foam adhesive of the self-vulcanizing of the two-pack form that preparation provided by the invention is above-mentioned is to be that 2000 polyoxytrimethylene dibasic alcohol stirs and be warmed up to 60-70 ℃ for 140～180 parts with the number-average molecular weight through processed, drip 70～110 parts of tolylene diisocyanates then, dripped afterreaction 3～4 hours, be cooled to room temperature, discharging, airtight being kept in the exsiccant container as first part polyurethane prepolymer; Again 20～24 parts of ethylene glycol, 4～8 parts of glycerol, 20～25 parts of morpholine class catalyzer, 5～6 parts of butanediamine, water are mixed for 4～8 parts, and place container as the second component, during use, first component and second component are pressed mass ratio 3～6 mixing and are got final product, and wherein used material umber is weight part.
Added morpholine class catalyzer is N-N-formyl morpholine N-or N-methyl ethyl diketone morpholine in the above method.
This method is to be that 2000 polyoxytrimethylene dibasic alcohol stirs and be warmed up to 60-70 ℃ for 140～180 parts with the weight-average molecular weight through processed, drip 70～110 parts of tolylene diisocyanates then, dripped afterreaction 3～4 hours, be cooled to room temperature, discharging, airtight being kept in the exsiccant container as first part polyurethane prepolymer; Again 20～24 parts of ethylene glycol, 4～8 parts of glycerol, 20～25 parts of morpholine class catalyzer, 5～6 parts of butanediamine, water are mixed for 4～8 parts, and place container as the second component, during use, first component and second component are pressed mass ratio 3～6 mixing and are got final product,
The present invention compared with prior art has the following advantages:
1, because polyurethane foam adhesive provided by the invention is to adopt the base-material of polyurethane prepolymer as caking agent, and be curing catalysts with the morpholine kind compound, thereby not only provide a kind of new product for room temperature moisture curing foam adhesive field, and this caking agent is cheap, and is simple to operate during use, ridity is moderate.
2, because polyurethane foam adhesive provided by the invention does not contain organic solvent, thereby the gained foam adhesive not only can not corrode foam, clean environment firendly, and bonding plane initial bonding strength, bonding strength etc. can match in excellence or beauty with existing room temperature moisture curing foam adhesive product.
3, because polyurethane foam adhesive provided by the invention is that the employing morpholine kind compound is a curing catalysts, thereby it not only has stronger katalysis to foamed solidification, also make the caking agent viscosity＜600mPaS that is obtained (according to ROOKFIELD DV-III, SC4-18,25 ℃, shearing rate 39.6s
-1Record), both be convenient to constructing operation, again caking agent is produced good preservation stability.
4, the employed starting material of preparation method provided by the invention are the commercially available prod, cheaply be easy to get, and technology is simple, and easy handling, thereby simplified whole technological process, saved production cost greatly.
Embodiment
Embodiment
Provide embodiment below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field must belong to protection scope of the present invention according to the invention described above content to some nonessential improvement and the adjustment that the present invention did.
In addition, what deserves to be explained is also that the used material umber of each embodiment is weight part in the table, MDI is a diphenylmethanediisocyanate, and TDI is a tolylene diisocyanate.
Embodiment 1-10
Earlier be that 2000 polyoxytrimethylene dibasic alcohol joins in the reactor with number-average molecular weight, stir and intensification simultaneously, treat that fluid temperature is raised to 75 ℃, open vacuum system, make the vacuum tightness gradual slow in the still rise to 80mmHg, the control reactor temperature kept 4 hours at 110 ℃, below the water content to 0.06% of the polyoxytrimethylene dibasic alcohol in still, stop to heat and vacuumizing.
To join in the reactor through the polyoxytrimethylene dibasic alcohol of processed, stir also and slowly be warmed up to 60～70 ℃, then MDI and TDI through metering slowly are added drop-wise in the still, and the control temperature in the kettle is at 60～70 ℃, dripped afterreaction 3～4 hours, cool to room temperature.Add morpholine class catalyzer, a condensed ethandiol again, mix, the discharging splendid attire is in exsiccant metal bucket or plastic barrel, and airtight preservation gets final product.
During use, the caking agent that obtains opened and be coated on to be needed on the bonding two articles surface, then with two articles near contact, and place humidity greater than 80% moist environment, this caking agent just natural foaming solidifies.If environment is relatively drier, can suitably sprays less water on the bonding object of need, and then apply this caking agent.
More than the concrete component kind of each embodiment, proportioning and bonding after volume density see Table 1.
Embodiment 11-22
Earlier be that 1000 polyester diol, number-average molecular weight are that 2000 polyoxytrimethylene dibasic alcohol and number-average molecular weight are that 6000 polyoxytrimethylene trivalent alcohol joins in the reactor with number-average molecular weight, stir and intensification simultaneously, treat that fluid temperature is raised to 80 ℃, open vacuum system, make the vacuum tightness gradual slow in the still rise to 100mmHg, the control reactor temperature is at 120 ℃, kept 3 hours, below the water content to 0.06% of the polyoxytrimethylene dibasic alcohol in still, stop to heat and vacuumizing.
To join in the reactor through polyester diol, polyoxytrimethylene dibasic alcohol and the polyoxytrimethylene trivalent alcohol of processed, add hydrogenated terpene resin then, stir also and slowly be warmed up to 60～70 ℃, to slowly be added drop-wise in the still through the MDI of metering again, and the control temperature in the kettle is at 60～70 ℃, dripped afterreaction 3～4 hours, cool to room temperature.Add morpholine class catalyzer, a condensed ethandiol again, mix, the discharging splendid attire is in exsiccant metal bucket or plastic barrel, and airtight preservation gets final product.
During use, the caking agent that obtains opened and be coated on to be needed on the bonding two articles surface, then with two articles near contact, and place humidity greater than 80% moist environment, this caking agent just natural foaming solidifies.If environment is relatively drier, can suitably sprays less water on the bonding object of need, and then apply this caking agent.
More than the concrete component kind of each embodiment, proportioning and bonding after volume density see Table 2.
Embodiment 23-37
Earlier be that 2000 polyoxytrimethylene dibasic alcohol joins in the reactor with number-average molecular weight, stir and intensification simultaneously, treat that fluid temperature is raised to 70 ℃, open vacuum system, make the vacuum tightness gradual slow in the still rise to 50mmHg, the control reactor temperature kept 3.5 hours at 150 ℃, below the water content to 0.06% of the polyoxytrimethylene dibasic alcohol in still, stop to heat and vacuumizing.
To join in the reactor through the polyoxytrimethylene dibasic alcohol of processed, stir also and slowly be warmed up to 60～70 ℃, slowly be added drop-wise to TDI in the still then, and the control temperature in the kettle is at 60～70 ℃, dripped afterreaction 3～4 hours, the cool to room temperature discharging, airtight being kept in exsiccant metal bucket or the vial as the first component.
Ethylene glycol, glycerol, morpholine class catalyzer, butanediamine and water joined in the container mix, place a metal bucket or vial as the second component.
During use, caking agent first, second two components that obtain 3～6 are mixed by weight, being coated on needs on the bonding two articles face, with the close contact of two articles, places room temperature environment then, and this caking agent just natural foaming solidifies.
More than the concrete component kind of each embodiment, proportioning and bonding after volume density see Table 3.
Table 1
| Embodiment | The polyoxytrimethylene dibasic alcohol | MDI | TDI | One condensed ethandiol | The N-N-formyl morpholine N- | N-methyl ethyl diketone morpholine | Volume density/Kg.m -3 |
| 1 | 80 | 30 | 10 | 5 | 1 | - | 21 |
| 2 | 80 | 35 | 15 | 6 | 1.5 | - | 22 |
| 3 | 80 | 40 | 20 | 8 | - | 1 | 24 |
| 4 | 90 | 35 | 17 | 6 | - | 2 | 25 |
| 5 | 90 | 30 | 20 | 5 | 2 | - | 24 |
| 6 | 90 | 37 | 10 | 7 | 1.5 | - | 23 |
| 7 | 90 | 40 | 13 | 8 | - | 1.5 | 25 |
| 8 | 100 | 38 | 15 | 5 | - | 2 | 26 |
| 9 | 100 | 33 | 18 | 6 | 1 | - | 27 |
| 10 | 100 | 40 | 10 | 7 | - | 1 | 25 |
Table 2
| Embodiment | Polyester diol | Polyoxypropyleneglycol | The polyoxytrimethylene triol | MDI | Hydrogenated terpene resin | One condensed ethandiol | N-methyl ethyl diketone morpholine | The N-N-formyl morpholine N- | Volume density/Kg.m -3 |
| 11 | 30 | 80 | 10 | 30 | 5 | 8 | 2 | - | 21 |
| 12 | 30 | 95 | 15 | 35 | 6 | 9 | 2.5 | - | 23 |
| 13 | 30 | 100 | 20 | 40 | 7 | 10 | - | 2 | 26 |
| 14 | 30 | 85 | 15 | 33 | 8 | 9 | - | 2.5 | 22 |
| 15 | 40 | 100 | 13 | 38 | 7 | 10 | 3 | - | 26 |
| 16 | 40 | 90 | 18 | 30 | 8 | 8 | 2.5 | - | 24 |
| 17 | 40 | 80 | 20 | 35 | 5 | 8.5 | - | 3 | 23 |
| 18 | 40 | 95 | 10 | 40 | 6 | 9 | - | 3 | 25 |
| 19 | 50 | 100 | 15 | 33 | 8 | 10 | 2 | - | 27 |
| 20 | 50 | 85 | 20 | 30 | 7 | 8 | - | 2 | 25 |
| 21 | 50 | 90 | 13 | 35 | 5 | 9 | 2.5 | - | 26 |
| 22 | 50 | 100 | 10 | 40 | 6 | 8 | - | 2.5 | 27 |
Table 3
Claims (8)
1. the low-viscosity polyurethane foam adhesive of a self-vulcanizing, this caking agent is to be 80～100 parts of 2000 polyoxytrimethylene dibasic alcohol by number-average molecular weight, the polyurethane prepolymer that 10～20 parts of polymerizations of 30～40 parts of diphenylmethanediisocyanates and tolylene diisocyanate obtain, 1～2 part of a morpholine class catalyzer and a condensed ethandiol mix for 5～8 parts, or be 30～50 parts of 1000 polyester diol by number-average molecular weight, number-average molecular weight is 80～100 parts of 2000 polyoxytrimethylene dibasic alcohol, number-average molecular weight is 10～20 parts of 6000 polyoxytrimethylene trivalent alcohols, 30～40 parts of diphenylmethanediisocyanates, the polyurethane prepolymer that 5～8 parts of polymerizations of hydrogenated terpene resin obtain, 2～3 parts of morpholine class catalyzer, one condensed ethandiol mixes for 8～10 parts, this caking agent is according to ROOKFIELD DV-III, SC4-18, at 25 ℃, shearing rate is 39.6s
-1Record its viscosity＜600mPaS, when meeting water or moisture down for 10～30 ℃, by the isocyanic ester in the morpholine class catalyst polyurethane prepolymer and water reaction or self polycondensation generation CO
2Gas foaming solidifies the acquisition foams, and the volume density of these foams is 21～27Kg/m
3, wherein the umber of each material is weight part.
2. the low-viscosity polyurethane foam adhesive of self-vulcanizing according to claim 1, contained morpholine class catalyzer is N-N-formyl morpholine N-or N-methyl ethyl diketone morpholine in this caking agent.
3. the low-viscosity polyurethane foam adhesive of a self-vulcanizing, this caking agent is the first part polyurethane prepolymer that obtains of 70～110 parts of polymerizations of 2000 140～180 parts of polyoxytrimethylene dibasic alcohol, tolylene diisocyanate by number-average molecular weight and is made of 20～24 parts of ethylene glycol, 4～8 parts of glycerol, 20～25 parts of morpholine class catalyzer, 5～6 parts of butanediamine, 4～8 parts of second components of forming of water, the mass ratio of first component and second component is 3～6 during use, this caking agent is according to ROOKFIELD DV-III, SC4-18, at 25 ℃, shearing rate is 39.6s
-1Record its viscosity＜600mPaS, when meeting water or moisture down for 10～30 ℃, by the isocyanic ester in the morpholine class catalyst polyurethane prepolymer and water reaction or self polycondensation generation CO
2Gas foaming solidifies the acquisition foams, and the volume density of these foams is 15～29Kg/m
3, wherein the umber of each material is weight part.
4. the low-viscosity polyurethane foam adhesive of self-vulcanizing according to claim 3, contained morpholine class catalyzer is N-N-formyl morpholine N-or N-methyl ethyl diketone morpholine in this caking agent.
5. method for preparing the low-viscosity polyurethane foam adhesive of the described self-vulcanizing of claim 1, this method is to be that 2000 polyoxytrimethylene dibasic alcohol stirs earlier for 80～100 parts and is warming up to 60-70 ℃ with the number-average molecular weight through processed, then with 30～40 parts of diphenylmethanediisocyanates, tolylene diisocyanate slowly is added drop-wise to wherein for 10～20 parts, and controlled temperature is at 60～70 ℃, dripped afterreaction 3～4 hours, be cooled to room temperature, add 1～2 part of morpholine class catalyzer again and a condensed ethandiol mixes for 5～8 parts, the airtight preservation in the exsiccant container of discharging splendid attire gets final product, or will be 30～50 parts of 1000 polyester diol through the number-average molecular weight of processed, number-average molecular weight is 80～100 parts of 2000 polyoxytrimethylene dibasic alcohol, number-average molecular weight is 10～20 parts of 6000 polyoxytrimethylene trivalent alcohols, hydrogenated terpene resin stirs and is warmed up to 60-70 ℃ for 5～8 parts, drip 30～40 parts of diphenylmethanediisocyanates then, dripped afterreaction 3～4 hours, be cooled to room temperature, add 2～3 parts of morpholine class catalyzer again, one condensed ethandiol mixes for 8～10 parts, the airtight preservation in the exsiccant container of discharging splendid attire gets final product, and wherein used material umber is weight part.
6. the method for preparing room temperature solidified low-viscosity polyurethane foam adhesive according to claim 5, added morpholine class catalyzer is N-N-formyl morpholine N-or N-methyl ethyl diketone morpholine in this method.
7. method for preparing the low-viscosity polyurethane foam adhesive of the described self-vulcanizing of claim 3, this method is to be that 2000 polyoxytrimethylene dibasic alcohol stirs and be warmed up to 60-70 ℃ for 140～180 parts with the number-average molecular weight through processed, drip 70～110 parts of tolylene diisocyanates then, dripped afterreaction 3～4 hours, be cooled to room temperature, discharging, airtight being kept in the exsiccant container as first part polyurethane prepolymer; Again 20～24 parts of ethylene glycol, 4～8 parts of glycerol, 20～25 parts of morpholine class catalyzer, 5～6 parts of butanediamine, water are mixed for 4～8 parts, and place container as the second component, during use, first component and second component are pressed mass ratio 3～6 mixing and are got final product, and wherein used material umber is weight part.
8. the method for preparing room temperature solidified low-viscosity polyurethane foam adhesive according to claim 7, added morpholine class catalyzer is N-N-formyl morpholine N-or N-methyl ethyl diketone morpholine in this method.
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| CN 201010028016 CN101735763B (en) | 2010-01-05 | 2010-01-05 | Room temperature curing low-viscosity polyurethane foam adhesive and preparation method thereof |
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| CN101735763B true CN101735763B (en) | 2013-07-24 |
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Cited By (1)
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| JP7066483B2 (en) | 2017-03-31 | 2022-05-13 | トーレ プラスティックス （アメリカ） インコーポレイテッド | Coextruded crosslinked polyolefin foam with TPU cap layer |
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| US11007761B2 (en) | 2017-03-31 | 2021-05-18 | Toray Plastics (America), Inc. | Method of making coextruded, cross-linked polyolefin foam with TPU cap layers |
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| CN110092886A (en) * | 2019-05-16 | 2019-08-06 | 高鼎精细化工(昆山)有限公司 | The applicable moisture reaction type polyurethane resin and preparation method thereof of low temperature environment |
| CN110564332B (en) * | 2019-09-24 | 2020-07-31 | 苏州世华新材料科技股份有限公司 | Elastic pressure-sensitive adhesive layer, pressure-sensitive adhesive tape and preparation method of pressure-sensitive adhesive tape |
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