CN104861917A - Water-based polyurethane adhesive and preparation method thereof - Google Patents
Water-based polyurethane adhesive and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a water-based polyurethane adhesive and a preparation method thereof. The preparation method is characterized by comprising the following steps: mixing and emulsifying a non-water-soluble blocked isocyanate curing agent and a polyurethane prepolymer, thereby obtaining the water-based polyurethane adhesive, wherein the non-water-soluble blocked isocyanate curing agent serves as the core, and the polyurethane prepolymer serves as the shell; or mixing and emulsifying a polyurethane prepolymer of which the NCO terminal group is blocked by a blocking agent and the non-water-soluble blocked isocyanate curing agent, thereby obtaining the water-based polyurethane adhesive, wherein the non-water-soluble blocked isocyanate curing agent serves as the core, and the polyurethane prepolymer of which the NCO terminal group is blocked by the blocking agent serves as the shell; or mixing and emulsifying a prepolymer of which the NCO terminal group is blocked by a blocking agent and non-water-soluble polyamine, thereby obtaining the water-based polyurethane adhesive, wherein the non-water-soluble polyamine serves as the core, and the polyurethane prepolymer of which the NCO terminal group is blocked by the blocking agent serves as the shell. According to the water-based polyurethane adhesive disclosed by the invention, the double components are stably stored under the mixing condition at normal temperature, the construction process is simple, the manual labor is not consumed compared with the conventional double-component polyurethane due to the operations of mixing and metering, and hazards of release of the blocking agent on the environment can be controlled.
Description
Technical field
The invention belongs to water-base polyurethane material technical field, be specifically related to water-based polyurethane adhesive and preparation method thereof.
Background technology
Introduce according in " aqueous polyurethane and application " (Chemical Industry Press, version in 2015) book, water-based polyurethane adhesive can be divided into single component and dual-component aqueous polyurethane adhesive agent.Most of water-based polyurethane adhesive is single-component system, monocomponent waterborne polyurethane tackiness agent take waterborne polyurethane resin as base-material, add the formation such as auxiliary agent, filler, and take water as the tackiness agent of a class one-component of dispersion medium, mostly be linear thermoplastic's urethane or the cross-linked polyurethane of crosslinking degree low (general degree of crosslinking is less than 2%).Monocomponent waterborne polyurethane is easy to use, but many performances are as not good in water tolerance, solvent resistance, chemical-resistant, wear resistance, hardness etc., so simple monocomponent waterborne polyurethane tackiness agent can not meet the demand in market.Dual-component aqueous polyurethane adhesive agent researches and develops on the basis of monocomponent waterborne polyurethane tackiness agent, first component wherein in most of dual-component aqueous polyurethane adhesive agent is the component containing active hydrogen, second component is the crosslinker component containing active isocyanate, during use, two components are mixed, namely usually said hydroxyl and isocyanic ester aqueous dual-component system." adhesive for polyurethane--preparation, formula and application " (Chemical Industry Press, version in 2009), Chinese patent 201110289506, and the two-component polyurethane systems that China's " Chinese tackiness agent " (volume 10 phase 15-18 page October the 18th in 2009) is introduced adopts aziridines bicomponent system, Carbodiimides bicomponent system and epoxy double component system, namely second component introduces the polynary aziridine of response type, carbodiimide and epoxide group, then with the amido in first component, the group such as hydroxyl or carboxyl reacts, obtain a kind of crosslinking curing product.For monocomponent waterborne polyurethane system, dual-component aqueous polyurethane substantially increases the cross-linking density of product, has strong adhesion, wear resistance is good, hardness is large and the high-performance such as chemicals-resistant, good weatherability.Therefore, dual-component aqueous polyurethane adhesive agent is a kind of advantage both with traditional solvent-borne system, meets again the type material of environmental legislation.
The current research about dual-component aqueous polyurethane adhesive agent mainly concentrates on and makes use or solvent-borne type solidifying agent be second component, carry out before use measuring and mixing, then gluing uses, as Chinese patent 201010209084.1,201110268241.0 etc. introduce.But these methods all also also exist some problems.Such as, two components are all strict packing, prepare by a certain percentage before using, must matching while using, operation has certain time-bounded, and the glue of general preparation can not use more than 2-4 hour, easily bubble is produced when preparing the tackiness agent of viscosity higher, be difficult to eliminate very soon, second component needs special anhydrous and oxygen-free system to preserve, and cost is generally higher.And aziridines bicomponent system, Carbodiimides bicomponent system have very high toxicity, very major injury can be produced to human body; Speed of reaction is slow, and solvent-borne type solidifying agent is difficult to dissolve in water-based system, and preparing the tackiness agent obtained is two-phase system in fact, and waterborne curing agent self contains hydrophilic radical, and the water tolerance for material after introducing has certain influence.
China's volume 10 phase 21-24 page in " coatings industry " October the 42nd in 2012 reports and utilizes 3,5-is dimethyl pyrazole-blocked as encapsulant, obtain dead front type water-based isocyanate solidifying agent, post-heating deblocking is mixed with host during use or before using, then curing cross-linked, but oil soluble end-blocking solidifying agent (or claiming to close solidifying agent) still faces the inconsistent problem with water-based system, is difficult to the bond effect obtained.About the report of water-based end-blocking solidifying agent, as " preparation of dead front type aqueous polyisocyanate curing agent and the performance study thereof " of China's volume 12 phase 17-19 page in " coatings industry " December the 37th in 2007 report, methyl ethyl ketoxime and IPDI tripolymer reactive grafting methoxypolyethylene glycol is utilized to prepare dead front type aqueous polyisocyanate curing agent, although can directly mix with water-base resin, but because the introducing of water miscible poly glycol monomethyl ether can have a certain impact to materials water-resistant, this end-blocking solidifying agent synthesis technique is complicated, and deblocking temperature is high.
Summary of the invention
The object of this invention is to provide a kind of speed of reaction high, harmless, process long water-based polyurethane adhesive of easy to use, period of storage and preparation method thereof, to overcome the above-mentioned deficiency of prior art.
Water-based polyurethane adhesive of the present invention, containing two kinds of components, wherein a kind of component is base polyurethane prepolymer for use as containing hydrophilic chain extender or enclosed polyurethane performed polymer, referred to as first component, another kind of component is containing water-insoluble Blocked Isocyanate Curing Agents or non-aqueous soluble polyols amine, referred to as second component; It is characterized in that: this tackiness agent is that second component is the nucleocapsid structure milk-globule solution of core with first component for shell; Wherein the mass ratio of first component and second component is 2-20:1;
When described first component is the enclosed polyurethane performed polymer containing hydrophilic chain extender, second component with matching selects non-aqueous soluble polyols amine or water-insoluble Blocked Isocyanate Curing Agents;
When described first component is the base polyurethane prepolymer for use as containing hydrophilic chain extender, then second component with matching is water-insoluble Blocked Isocyanate Curing Agents.
The preparation method of water-based polyurethane adhesive of the present invention, obtains base polyurethane prepolymer for use as by macromolecule dihydric alcohol, vulcabond, hydrophilic chain extender, glycol chain extender by prepolymerization reaction, adds neutralizing agent neutralization; Or, after obtaining base polyurethane prepolymer for use as, add the base polyurethane prepolymer for use as that encapsulant phenol (PHE) is obtained by reacting blocking agent NCO end group again, add neutralizing agent neutralization; It is characterized in that: it is core that water-insoluble Blocked Isocyanate Curing Agents and base polyurethane prepolymer for use as mixing and emulsifying are obtained water-insoluble Blocked Isocyanate Curing Agents, and base polyurethane prepolymer for use as is the water-based polyurethane adhesive of shell; Or, it is core that the enclosed polyurethane performed polymer of blocking agent NCO end group and water-insoluble Blocked Isocyanate Curing Agents mixing and emulsifying are obtained water-insoluble Blocked Isocyanate Curing Agents, and the enclosed polyurethane performed polymer of blocking agent NCO end group is the water-based polyurethane adhesive of shell; Or it is core that the dead front type performed polymer of blocking agent NCO end group and water-insoluble polyamine mixing and emulsifying are obtained water-insoluble polyamine, the water-based polyurethane adhesive that the enclosed polyurethane performed polymer of blocking agent NCO end group is;
It is described that water-insoluble Blocked Isocyanate Curing Agents and base polyurethane prepolymer for use as to be mixed to get water-insoluble Blocked Isocyanate Curing Agents be core, base polyurethane prepolymer for use as is that the concrete operation step of the water-based polyurethane adhesive of shell is as follows: with the quality of non-aqueous and non-solvent component in aqueous polyurethane for benchmark, by the macromolecule dihydric alcohol by this Reference mass 30-70% at 110-120 DEG C of dehydration 0.5-1.5 hour, the vulcabond of 15-50% is added again by this Reference mass, the hydrophilic chain extender of 4-8% is added after 2-4 hour 70-100 DEG C of reaction, the glycol chain extender of 1.5-11%, the dibutyl tin laurate (DBTDL) of 0.01-0.08% and 20-50% acetone or butanone, within 1-4 hour, base polyurethane prepolymer for use as is obtained 60-90 DEG C of reaction, the preparation manipulation of described water-insoluble Blocked Isocyanate Curing Agents is as follows: vulcabond is dissolved in acetone or butanone that to be mixed with mass percent concentration be 10-30%, 60-80 DEG C is warming up under magnetic agitation, slow interpolation trihydric compounds, add in 2 hours, insulation reaction 2-4 hour under 60-80 DEG C of condition, obtain homemade isocyanate curing agent, wherein vulcabond is 3-3.2:1 with the ratio of the amount of substance of trihydric compounds, with the quality of non-solvent component in system for benchmark, this homemade isocyanate curing agent is added the acetone of 80-150% or butanone as solvent, the dibutyl tin laurate of 0.1-0.8%, as catalyzer, adds encapsulant phenol under agitation condition, 80-100 DEG C of reaction 2-6 hour, wherein isocyanate curing agent is 1:3-5 with the ratio of encapsulant amount of substance, after reaction terminates, the performed polymer of product with above-mentioned preparation is mixed, wherein, the mass ratio of base polyurethane prepolymer for use as and Blocked Isocyanate Curing Agents is 2-20:1, then under the condition of high speed shear and 0-40 DEG C, add the triethylamine of 3-6%, react the water adding 200-300% after 1-5 minute and stir 5-30 minute, by reaction product 40-50 DEG C, slough acetone or butanone under 0.01MPa vacuum condition, finally add the defoamer of the wetting agent of 0-1%, the thickening material of 0-1%, the antioxidant of 0-0.5%, the uv-absorbing agent of 0-0.5% and 0-0.5%, add the filler of 0-10% again, namely obtain water-based polyurethane adhesive,
It is described that the enclosed polyurethane performed polymer of blocking agent NCO end group and water-insoluble polyamine mixing and emulsifying are obtained water-insoluble polyamine is core, the enclosed polyurethane performed polymer of blocking agent NCO end group is that the concrete operation step of the water-based polyurethane adhesive of shell is as follows: with the quality of non-aqueous in aqueous polyurethane and non-solvent component for benchmark, by the macromolecule dihydric alcohol by this Reference mass 30-70% at 110-120 DEG C of dehydration 0.5-1.5 hour, the vulcabond of 15-50% is added again by this Reference mass, the hydrophilic chain extender of 4-8% is added after 2-4 hour 70-100 DEG C of reaction, the glycol chain extender of 1.5-11%, the dibutyl tin laurate of 0.01-0.08% and 20-50% acetone or butanone, the encapsulant phenol adding 1-4% 60-90 DEG C of reaction after 1-4 hour obtains the enclosed polyurethane performed polymer of blocking agent NCO end group for 1-5 hour 70-90 DEG C of reaction, the described operation steps by the enclosed polyurethane performed polymer of blocking agent NCO end group and water-insoluble Blocked Isocyanate Curing Agents mixing and emulsifying is as follows: by the water-insoluble polyamine of 1-4%, with the mass ratio of the enclosed polyurethane performed polymer of blocking agent NCO end group and water-insoluble polyamine for 2-20:1, under the condition of high speed shear and 0-40 DEG C, the triethylamine of 3-6% is added after stirring, react the water adding 200-300% after 1-5 minute, stir 5-30 minute, by reaction product at 40-50 DEG C, acetone or butanone is sloughed under 0.01MPa vacuum condition, finally add the wetting agent of 0-1%, the thickening material of 0-1%, the antioxidant of 0-0.5%, the uv-absorbing agent of 0-0.5% and the defoamer of 0-0.5%, add the filler of 0-10% again, namely water-based polyurethane adhesive is obtained,
It is described that the enclosed polyurethane performed polymer of blocking agent NCO end group and water-insoluble Blocked Isocyanate Curing Agents mixing and emulsifying are obtained water-insoluble Blocked Isocyanate Curing Agents is core, the enclosed polyurethane performed polymer of blocking agent NCO end group is that the concrete operation step of the water-based polyurethane adhesive of shell is as follows: with the quality of non-aqueous in aqueous polyurethane and non-solvent component for benchmark, by the macromolecule dihydric alcohol by this Reference mass 30-70% at 110-120 DEG C of dehydration 0.5-1.5 hour, the vulcabond of 15-50% is added again by this Reference mass, the hydrophilic chain extender of 4-8% is added after 2-4 hour 70-100 DEG C of reaction, the glycol chain extender of 1.5-11%, the dibutyl tin laurate of 0.01-0.08% and 20-50% acetone or butanone, the encapsulant phenol of 1-4% is added after 1-4 hour at 70-90 DEG C of reaction 1-5 hour 60-90 DEG C of reaction, obtain the enclosed polyurethane performed polymer of blocking agent NCO end group, the preparation manipulation step of described water-insoluble Blocked Isocyanate Curing Agents is as follows: be dissolved in by vulcabond in acetone or butanone, being mixed with mass percent concentration is that 10-30% joins in system, 60-80 DEG C is warming up under magnetic agitation, slow interpolation trihydric compounds, add in 2 hours, within insulation reaction 2-4 hour under 60-80 DEG C of condition, obtain making isocyanate curing agent by oneself, wherein vulcabond is 3-3.2:1 with the ratio of the amount of substance of trihydric compounds, with the quality of non-solvent component in system for benchmark, isocyanate curing agent is added the acetone of 80-150% or butanone as solvent, the dibutyl tin laurate of 0.1-0.8%, as catalyzer, adds encapsulant phenol under agitation condition, 80-100 DEG C of reaction 2-6 hour, wherein, isocyanate curing agent is 1:3-5 with the ratio of encapsulant amount of substance, after reaction terminates, product is added the enclosed polyurethane performed polymer mixing of the blocking agent NCO end group of above-mentioned preparation, wherein the performed polymer of blocking agent NCO end group and the mass ratio of isocyanate curing agent are 2-20:1, then under the condition of high speed shear and 0-40 DEG C, add the triethylamine of 3-6%, react the water adding 200-300% after 1-5 minute and stir 5-30 minute, by reaction product 40-50 DEG C, slough acetone or butanone under 0.01MPa vacuum condition, finally add the defoamer of the wetting agent of 0-1%, the thickening material of 0-1%, the antioxidant of 0-0.5%, the uv-absorbing agent of 0-0.5% and 0-0.5%, add the filler of 0-10% again, namely obtain water-based polyurethane adhesive.
Described high speed shear refers to 2000-5000 rev/min.
Described macromolecule dihydric alcohol is selected from poly-hexanodioic acid-BDO ester dibasic alcohol (PBA), polyethylene glycol adipate dibasic alcohol (PEA), polycaprolactone diols (PCL), poly (propylene carbonate) dibasic alcohol (PPC) or PCDL (PCDL);
Described vulcabond is selected from tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI) or hexamethylene diisocyanate (HDI);
Described hydrophilic chain extender is selected from dimethylol propionic acid (DMPA) or dimethylolpropionic acid (DMBA);
Described glycol chain extender is selected from ethylene glycol (EG), BDO (BDO), 1,6-hexylene glycol (HDO) or glycol ether (DEG);
Described water-insoluble polyamine is selected from trimeric cyanamide (MA), diethyl toluene diamine (DETDA) or dimethythiotoluene diamine (DMTDA);
Described isocyanate curing agent is selected from hexamethylene diisocyanate trimer (HDIT) or toluene diisocyanate trimer (TDIT);
Described coupling agent is selected from γ-aminopropyl triethoxysilane (KH550) or γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560);
Described filler is selected from calcium carbonate, sodium hydroxide, talcum powder or nano silicon, or wherein two kinds and two or more mixtures;
Described antioxidant is selected from 2,6 ditertiary butyl p cresol, pentanoic, Ursol D or dihydroquinoline;
Described uv-absorbing agent is selected from 2,4 dihydroxyl benzophenone or ESCALOL 567;
Described thickening material is Xylo-Mucine, Natvosol, methyl hydroxyethylcellulose, Type 3U or methylhydroxypropylcellulose;
Described defoamer adopts (preferred German Bi Ke Company) silicone antifoaming agent BYK-141.
Because the preparation method of water-based polyurethane adhesive of the present invention is in self-emulsifying technique, introducing water-insoluble solidifying agent is the inside of second component to aqueous polyurethane double electrical layers, define with the base polyurethane prepolymer for use as containing hydrophilic chain extender or enclosed polyurethane performed polymer as shell, non-water-soluble second component is core, stablize, have the water-based polyurethane adhesive of nucleocapsid structure under normal temperature, achieve the unitary package of two-pack, easy to use, shelf-stable.Because aqueous polyurethane is alkaline system, then add excessive basic filler, the encapsulants such as the phenol that deblocking goes out carry out acid-base reaction salify with it, can not discharge work the mischief to human body and environment from system.Solve in current water-based polyurethane adhesive use water soluble solid agent to obtain tackiness agent poor water resistance, discharge harmful compound, processing uses inconvenient, that period of storage is short problem.
Water-based polyurethane adhesive product of the present invention and preparation method thereof compared with prior art has the following advantages:
1. adopt water-based polyurethane adhesive prepared by the inventive method, two-pack Absorbable organic halogens storage in the hybrid case under normal temperature, construction technology is simple, be different from two part solvent type polyurethane and expend man-hour because of operations such as metering and mixing, direct gluing use can be carried out by the glue-applying technique of monocomponent adhesive;
2. the water-based polyurethane adhesive adopting the inventive method to prepare can obtain solvent resistance, thermotolerance, the water tolerance of two-part reaction type polyurethane adhesive, also can obtain the mechanical properties such as higher breaking tenacity, elongation at break;
3. the water-based polyurethane adhesive adopting the inventive method to prepare can control curing speed or working life by change formula and Heating temperature, thus can adapt to the requirement of automatization bonding line of production technology;
4. adopt the inventive method to prepare water-based polyurethane adhesive, solidifying agent is easy to get, and cost is low, and production technique is simple, to human body and environment without harm.
5. the preparation method of water-based polyurethane adhesive of the present invention, technique is simple, and reaction conditions is gentle, can control the add-on of filler, avoids encapsulant to discharge environment.
Accompanying drawing explanation
Fig. 1 is the stress-strain curve that the water-based polyurethane adhesive emulsion (raw sample) prepared in the embodiment of the present invention 2 forms glued membrane;
Fig. 2 be in the embodiment of the present invention 2 preparation water-based polyurethane adhesive emulsion (raw sample) and standard aqueous polyurethane adhesive emulsion (comparative sample) formed glued membrane thermogravimetric curve figure.
Embodiment
Embodiment 1:
By 100.00 grams of PEA (M
n=3000) join in the there-necked flask of 500mL, after dewatering 1 hour at 115 DEG C, be cooled to 60 DEG C.Getting 29.70 grams of IPDI adds in there-necked flask, 0.05 gram of DBTDL is added after 2 hours in 90 DEG C of stirring reactions, 6.23 grams of hydrophilic chain extender DMPA, 4.53 grams of HDO and 90.00 gram butanone, constant temperature adds 3.03 grams of DCP at 75 DEG C of stirring reactions after 4 hours, react 3 hours at 80 DEG C, then 2.76 grams of DETDA are added, after being uniformly mixed, reaction product is proceeded to high speed shear dispersion machine, 4.77 grams of TEA are added under the condition of 3000 revs/min, react and add 325 grams of water after 5 minutes, stir, after 5 minutes, reaction product is proceeded to Rotary Evaporators, at 50 DEG C, butanone is sloughed under 0.01MPa vacuum condition, obtain water-based polyurethane adhesive emulsion.
Embodiment 2:
By 50.00 grams of PBA (M
n=3200) join in the there-necked flask of 500mL, after dewatering 1 hour at 110 DEG C, be cooled to 50 DEG C.Getting 11.00 grams of TDI adds in there-necked flask, 0.03 gram of DBTDL is added after 2 hours in 80 DEG C of stirring reactions, 3.00 grams of hydrophilic chain extender DMPA, 0.94 gram of BDO and 55.00 gram butanone, constant temperature adds 1.63 grams of PHE at 70 DEG C of stirring reactions after 4 hours, react 3 hours at 80 DEG C, then 1.2 grams of DCP are added, after being uniformly mixed, reaction product is proceeded to high speed shear dispersion machine, 2.27 grams of TEA are added under the condition of 3000 revs/min, react and add 155 grams of water after 5 minutes, stir, after 5 minutes, reaction product is proceeded to Rotary Evaporators, at 50 DEG C, butanone is sloughed under 0.01MPa vacuum condition, obtain water-based polyurethane adhesive emulsion (raw sample).
Make a contrast sample, reactions steps is as follows simultaneously: by 50.00 grams of PBA (M
n=3200) join in the there-necked flask of 500mL, after dewatering 1 hour at 110 DEG C, be cooled to 50 DEG C.Getting 11.00 grams of TDI adds in there-necked flask, 0.03 gram of DBTDL, 3.00 grams of hydrophilic chain extender DMPA, 1.32 grams of BDO and 55.00 gram butanone are added after 2 hours in 80 DEG C of stirring reactions, reaction product is proceeded to high speed shear dispersion machine at 70 DEG C of stirring reactions after 4 hours by constant temperature, 2.27 grams of TEA are added under the condition of 3000 revs/min, react and add 155 grams of water after 5 minutes, stir, after 5 minutes, reaction product is proceeded to Rotary Evaporators, 50 DEG C, slough butanone under 0.01MPa vacuum condition, obtain standard aqueous polyurethane adhesive emulsion (comparative sample).
Embodiment 3:
By 2 kilograms of PCL (M
n=2000) join in reactor, after dewatering 1 hour at 110 DEG C, be cooled to 50 DEG C.Getting 700.7 grams of TDI adds in there-necked flask, 0.03 gram of DBTDL is added after 2 hours in 80 DEG C of stirring reactions, 139.47 gram hydrophilic chain extender DMBA, 150.53 grams of DEG and 0.9L acetone, constant temperature adds 75 grams of PHE at 70 DEG C of stirring reactions after 4 hours, react 3 hours at 80 DEG C, then 142.6 grams of DMTDA are added, after being uniformly mixed, reaction product is proceeded to high speed shear dispersion machine, 96 grams of TEA are added under the condition of 3000 revs/min, react and add 7L water after 5 minutes, stir, after 5 minutes, reaction product is proceeded to Rotary Evaporators, at 40 DEG C, acetone is sloughed under 0.01MPa vacuum condition, obtain water-based polyurethane adhesive emulsion.
If other condition of the present embodiment is constant, and DEG is changed into EG, also water-based polyurethane adhesive emulsion can be obtained.
If other condition of the present embodiment is constant, and TDI is changed into HDI or MDI, all water-based polyurethane adhesive emulsion can be obtained.
Embodiment 4:
By 100 grams of PCDL (M
n=2000) join in reactor, after dewatering 1 hour at 110 DEG C, be cooled to 50 DEG C.Getting 22 grams of TDI adds in there-necked flask, 0.03 gram of DBTDL, 5.86 grams of hydrophilic chain extender DMPA, 2.2 grams of DEG and 80 gram acetone are added after 2 hours in 80 DEG C of stirring reactions, constant temperature adds 75 grams at 70 DEG C of stirring reactions after 4 hours, and at 80 DEG C, reaction obtains base polyurethane prepolymer for use as in 3 hours;
Then by 2.5 grams of HDIT, 1.7 grams of DMP, 0.02 gram of DBTDL and 5 gram butylacetate joins in 50mL there-necked flask, the lower 85 DEG C of reactions of agitation condition 3 hours, underpressure distillation is removed solvent and is obtained isocyanate curing agent closing compound, high speed shear dispersion machine will be proceeded to after this closing compound and base polyurethane prepolymer for use as being uniformly mixed, 4.43 grams of TEA are added under the condition of 3000 revs/min, react and add 280 grams of water after 5 minutes, stir, after 5 minutes, reaction product is proceeded to Rotary Evaporators, at 40 DEG C, acetone is sloughed under 0.01MPa vacuum condition, obtain water-based polyurethane adhesive emulsion.
In sum, in the preparation method of the embodiment of the present invention, by by the performed polymer of blocking agent NCO end group and non-aqueous soluble polyols amine mixing and emulsifying, or after water-insoluble closed isocyanate curing agent mixed with base polyurethane prepolymer for use as emulsification obtain a kind of two-pack in the hybrid case Absorbable organic halogens store (under normal temperature) and obtain a kind of water-based polyurethane adhesive, under certain storing temperature, the isocyanic ester generation deblocking reaction closed, again NCO group is discharged, with the reactive hydrogen generation crosslinking reaction in system, system is made to produce 3 D cross-linked reticulated structure, improve the over-all properties of material.Not only combine dual-component aqueous polyurethane safety and environmental protection, energy consumption is low, the advantage that performance is good, more combines the list packaging not available for standard aqueous bi-component polyurethane adhesive, the advantages such as construction technology is simple.
The above; be only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Embodiment 5:
By 50.00 grams of PBA (M
n=3200) join in the there-necked flask of 500mL, after dewatering 1 hour at 110 DEG C, be cooled to 50 DEG C.Getting 11.00 grams of TDI adds in there-necked flask, 0.03 gram of DBTDL, 3.00 grams of hydrophilic chain extender DMPA, 0.94 gram of BDO and 55.00 gram butanone are added after 2 hours in 80 DEG C of stirring reactions, constant temperature adds 1.63 grams of PHE at 70 DEG C of stirring reactions after 4 hours, at 80 DEG C, reaction obtains the base polyurethane prepolymer for use as of blocking agent NCO end group for 3 hours.
Then by 0.25 gram of HDIT, 0.17 gram of DMP, 0.02 gram of DBTDL and 5 gram butylacetate joins in 50mL there-necked flask, the lower 85 DEG C of reactions of agitation condition 3 hours, underpressure distillation is removed solvent and is obtained isocyanate curing agent closing compound, high speed shear dispersion machine is proceeded to after this closing compound and NCO enclosed polyurethane performed polymer being uniformly mixed, 2.3 grams of TEA are added under the condition of 3000 revs/min, react and add 155 grams of water after 5 minutes, stir, after 5 minutes, reaction product is proceeded to Rotary Evaporators, at 40 DEG C, acetone is sloughed under 0.01MPa vacuum condition, obtain water-based polyurethane adhesive emulsion.
Application Example:
Two emulsions embodiment 2 prepared are got equivalent and are poured on film forming on tetrafluoroethylene plate, place one week under 25 DEG C of conditions.After moisture slowly volatilizees, put into vacuum drying oven again at 60 DEG C dry 2 days, obtain the gluey film of urethane of thickness about 100 microns.This gluey film is measured according to the carrying out of National Standard of the People's Republic of China GB/T 11547-2008 to the water tolerance of material, tests by soak 72 hours in 25 DEG C of distilled water after.Acquired results is as shown in table 1:
Table 1
Can be seen by mass change contrast after the immersion of table 1, water-based polyurethane adhesive obtained in the present embodiment has reasonable water tolerance, and the water-based polyurethane adhesive water-intake rate of more conventional preparation reduces by 29%, and water tolerance increases greatly.
With reference to National Standard of the People's Republic of China's soft composite plastics material peel test method, PVC artificial leather is utilized to record the Average peel force of raw sample and comparative sample for 42.0N, 26.5N.
The sample of film forming is made dumbbell shaped rectangular, with reference to plastic tensile method for testing performance GB/T1040-92, stress-strain curve test is carried out to material.Fig. 1 is the stress-strain curve that the water-based polyurethane adhesive emulsion (raw sample) of synthesizing in the embodiment of the present invention 2 forms glued membrane.Acquired results is as shown in table 2:
Table 2
From the data of table 2, water-based polyurethane adhesive obtained in the present embodiment is relative to comparative sample, and its breaking tenacity, elongation at break increase all greatly, embody good mechanical property.If there is higher crosslinking degree due to conventional mono-component aqueous tackiness agent, can performed polymer molecular weight excessive, the emulsion instability forming emulsion difficulty or obtain, so do not have the mechanical property such as good elasticity, higher breaking tenacity after monocomponent adhesive emulsion film forming, and the inventive method can well solve conventional this problem of monocomponent waterborne polyurethane tackiness agent.
Second-order transition temperature and the deblocking temperature of raw sample is recorded by differential scanning calorimeter.Under nitrogen protection; nitrogen rate is 100mL/min; temperature rise rate is under 10 DEG C/min condition; the second-order transition temperature recording raw sample is-31.44 DEG C; illustrate that this polyurethane adhesive all has lower second-order transition temperature and good resistance to low temperature; the second-order transition temperature of comparative sample is-31.36 DEG C, and Comparatively speaking, the low temperature resistant of tackiness agent adopting invention method to prepare makes moderate progress.The deblocking temperature of raw sample is between 100-120 DEG C, illustrates that the tackiness agent adopting invention method to prepare has lower deblocking temperature, can reach energy efficient, easy construction, avoid the effect destroyed matrix material.
Thermogravimetric curve is adopted to weigh the resistance toheat of glued membrane, Shimadzu TGA-50H thermogravimetric analyzer is used to test the thermogravimetric curve of film, the testing sample taking 6-10mg puts into crucible, and heat flow rate is 10 DEG C/min under nitrogen atmosphere, Range of measuring temp 25 DEG C-700 DEG C.Fig. 2 is the thermogravimetric curve figure of raw sample and comparative sample, and as can be seen from the figure the thermal degradation process of urethane can be divided into two stages: the first stage from about 180 DEG C, the degraded of what this one-phase was corresponding is hard section ammonia ester bond; Subordinate phase from about 400 DEG C, the degraded of flexible polyurethane section that corresponding is.Fig. 2 also shows, two kinds of polyurethane materials, the degradation temperature of first stage and hard section ammonia ester bond is from 180 DEG C to 400 DEG C, the degraded difference of material is little, residual mass is substantially identical, but when temperature is increased to after 430 DEG C, comparative sample sustaining degradation, raw sample residual mass remains unchanged substantially, and the water-based polyurethane adhesive resistance toheat that application the inventive method obtains improves.
Claims (10)
1. a water-based polyurethane adhesive, containing two kinds of components, wherein a kind of component is base polyurethane prepolymer for use as containing hydrophilic chain extender or enclosed polyurethane performed polymer, referred to as first component, another kind of component is containing water-insoluble Blocked Isocyanate Curing Agents or non-aqueous soluble polyols amine, referred to as second component; It is characterized in that: this tackiness agent is that second component is the nucleocapsid structure milk-globule solution of core with first component for shell; Wherein the mass ratio of first component and second component is 2-20:1;
When described first component is the enclosed polyurethane performed polymer containing hydrophilic chain extender, second component with matching selects non-aqueous soluble polyols amine or water-insoluble Blocked Isocyanate Curing Agents;
When described first component is the base polyurethane prepolymer for use as containing hydrophilic chain extender, then second component with matching is water-insoluble Blocked Isocyanate Curing Agents.
2. the preparation method of water-based polyurethane adhesive described in claim 1, macromolecule dihydric alcohol, vulcabond, hydrophilic chain extender, glycol chain extender are obtained base polyurethane prepolymer for use as by prepolymerization reaction, adds neutralizing agent neutralization; Or, after obtaining base polyurethane prepolymer for use as, add the base polyurethane prepolymer for use as that encapsulant phenol reactant obtains blocking agent NCO end group again, add neutralizing agent neutralization; It is characterized in that: it is core that water-insoluble Blocked Isocyanate Curing Agents and base polyurethane prepolymer for use as mixing and emulsifying are obtained water-insoluble Blocked Isocyanate Curing Agents, and base polyurethane prepolymer for use as is the water-based polyurethane adhesive of shell; Or, it is core that the enclosed polyurethane performed polymer of blocking agent NCO end group and water-insoluble Blocked Isocyanate Curing Agents mixing and emulsifying are obtained water-insoluble Blocked Isocyanate Curing Agents, and the enclosed polyurethane performed polymer of blocking agent NCO end group is the water-based polyurethane adhesive of shell; Or it is core that the dead front type performed polymer of blocking agent NCO end group and water-insoluble polyamine mixing and emulsifying are obtained water-insoluble polyamine, the water-based polyurethane adhesive that the enclosed polyurethane performed polymer of blocking agent NCO end group is;
It is described that water-insoluble Blocked Isocyanate Curing Agents and base polyurethane prepolymer for use as to be mixed to get water-insoluble Blocked Isocyanate Curing Agents be core, base polyurethane prepolymer for use as is that the concrete operation step of the water-based polyurethane adhesive of shell is as follows: with the quality of non-aqueous and non-solvent component in aqueous polyurethane for benchmark, by the macromolecule dihydric alcohol by this Reference mass 30-70% at 110-120 DEG C of dehydration 0.5-1.5 hour, the vulcabond of 15-50% is added again by this Reference mass, the hydrophilic chain extender of 4-8% is added after 2-4 hour 70-100 DEG C of reaction, the glycol chain extender of 1.5-11%, the dibutyl tin laurate of 0.01-0.08% and 20-50% acetone or butanone, within 1-4 hour, base polyurethane prepolymer for use as is obtained 60-90 DEG C of reaction, the preparation manipulation of described water-insoluble Blocked Isocyanate Curing Agents is as follows: vulcabond is dissolved in acetone or butanone that to be mixed with mass percent concentration be 10-30%, 60-80 DEG C is warming up under magnetic agitation, slow interpolation trihydric compounds, add in 2 hours, insulation reaction 2-4 hour under 60-80 DEG C of condition, obtain homemade isocyanate curing agent, wherein vulcabond is 3-3.2:1 with the ratio of the amount of substance of trihydric compounds, with the quality of non-solvent component in system for benchmark, this homemade isocyanate curing agent is added the acetone of 80-150% or butanone as solvent, the dibutyl tin laurate of 0.1-0.8%, as catalyzer, adds encapsulant phenol under agitation condition, 80-100 DEG C of reaction 2-6 hour, wherein isocyanate curing agent is 1:3-5 with the ratio of encapsulant amount of substance, after reaction terminates, the performed polymer of product with above-mentioned preparation is mixed, wherein, the mass ratio of base polyurethane prepolymer for use as and Blocked Isocyanate Curing Agents is 2-20:1, then under the condition of high speed shear and 0-40 DEG C, add the triethylamine of 3-6%, react the water adding 200-300% after 1-5 minute and stir 5-30 minute, by reaction product 40-50 DEG C, slough acetone or butanone under 0.01MPa vacuum condition, finally add the defoamer of the wetting agent of 0-1%, the thickening material of 0-1%, the antioxidant of 0-0.5%, the uv-absorbing agent of 0-0.5% and 0-0.5%, add the filler of 0-10% again, namely obtain water-based polyurethane adhesive,
It is described that the enclosed polyurethane performed polymer of blocking agent NCO end group and water-insoluble polyamine mixing and emulsifying are obtained water-insoluble polyamine is core, the enclosed polyurethane performed polymer of blocking agent NCO end group is that the concrete operation step of the water-based polyurethane adhesive of shell is as follows: with the quality of non-aqueous in aqueous polyurethane and non-solvent component for benchmark, by the macromolecule dihydric alcohol by this Reference mass 30-70% at 110-120 DEG C of dehydration 0.5-1.5 hour, the vulcabond of 15-50% is added again by this Reference mass, the hydrophilic chain extender of 4-8% is added after 2-4 hour 70-100 DEG C of reaction, the glycol chain extender of 1.5-11%, the dibutyl tin laurate of 0.01-0.08% and 20-50% acetone or butanone, the encapsulant phenol adding 1-4% 60-90 DEG C of reaction after 1-4 hour obtains the enclosed polyurethane performed polymer of blocking agent NCO end group for 1-5 hour 70-90 DEG C of reaction, the described operation steps by the enclosed polyurethane performed polymer of blocking agent NCO end group and water-insoluble Blocked Isocyanate Curing Agents mixing and emulsifying is as follows: by the water-insoluble polyamine of 1-4%, with the mass ratio of the enclosed polyurethane performed polymer of blocking agent NCO end group and water-insoluble polyamine for 2-20:1, under the condition of high speed shear and 0-40 DEG C, the triethylamine of 3-6% is added after stirring, react the water adding 200-300% after 1-5 minute, stir 5-30 minute, by reaction product at 40-50 DEG C, acetone or butanone is sloughed under 0.01MPa vacuum condition, finally add the wetting agent of 0-1%, the thickening material of 0-1%, the antioxidant of 0-0.5%, the uv-absorbing agent of 0-0.5% and the defoamer of 0-0.5%, add the filler of 0-10% again, namely water-based polyurethane adhesive is obtained,
It is described that the enclosed polyurethane performed polymer of blocking agent NCO end group and water-insoluble Blocked Isocyanate Curing Agents mixing and emulsifying are obtained water-insoluble Blocked Isocyanate Curing Agents is core, the enclosed polyurethane performed polymer of blocking agent NCO end group is that the concrete operation step of the water-based polyurethane adhesive of shell is as follows: with the quality of non-aqueous in aqueous polyurethane and non-solvent component for benchmark, by the macromolecule dihydric alcohol by this Reference mass 30-70% at 110-120 DEG C of dehydration 0.5-1.5 hour, the vulcabond of 15-50% is added again by this Reference mass, the hydrophilic chain extender of 4-8% is added after 2-4 hour 70-100 DEG C of reaction, the glycol chain extender of 1.5-11%, the dibutyl tin laurate of 0.01-0.08% and 20-50% acetone or butanone, the encapsulant phenol of 1-4% is added after 1-4 hour at 70-90 DEG C of reaction 1-5 hour 60-90 DEG C of reaction, obtain the enclosed polyurethane performed polymer of blocking agent NCO end group, the preparation manipulation step of described water-insoluble Blocked Isocyanate Curing Agents is as follows: be dissolved in by vulcabond in acetone or butanone, being mixed with mass percent concentration is that 10-30% joins in system, 60-80 DEG C is warming up under magnetic agitation, slow interpolation trihydric compounds, add in 2 hours, within insulation reaction 2-4 hour under 60-80 DEG C of condition, obtain making isocyanate curing agent by oneself, wherein vulcabond is 3-3.2:1 with the ratio of the amount of substance of trihydric compounds, with the quality of non-solvent component in system for benchmark, isocyanate curing agent is added the acetone of 80-150% or butanone as solvent, the dibutyl tin laurate of 0.1-0.8%, as catalyzer, adds encapsulant phenol under agitation condition, 80-100 DEG C of reaction 2-6 hour, wherein, isocyanate curing agent is 1:3-5 with the ratio of encapsulant amount of substance, after reaction terminates, product is added the enclosed polyurethane performed polymer mixing of the blocking agent NCO end group of above-mentioned preparation, wherein the performed polymer of blocking agent NCO end group and the mass ratio of isocyanate curing agent are 2-20:1, then under the condition of high speed shear and 0-40 DEG C, add the triethylamine of 3-6%, react the water adding 200-300% after 1-5 minute and stir 5-30 minute, by reaction product 40-50 DEG C, slough acetone or butanone under 0.01MPa vacuum condition, finally add the defoamer of the wetting agent of 0-1%, the thickening material of 0-1%, the antioxidant of 0-0.5%, the uv-absorbing agent of 0-0.5% and 0-0.5%, add the filler of 0-10% again, namely obtain water-based polyurethane adhesive.
3. the preparation method of water-based polyurethane adhesive as claimed in claim 2, be characterised in that described macromolecule dihydric alcohol is selected from poly-hexanodioic acid-BDO ester dibasic alcohol, polyethylene glycol adipate dibasic alcohol, polycaprolactone diols, poly (propylene carbonate) dibasic alcohol or PCDL.
4. the preparation method of water-based polyurethane adhesive as claimed in claim 2, is characterised in that described vulcabond is selected from tolylene diisocyanate, diphenylmethanediisocyanate, isophorone diisocyanate or hexamethylene diisocyanate.
5. the preparation method of water-based polyurethane adhesive as claimed in claim 2, is characterised in that described hydrophilic chain extender is selected from dimethylol propionic acid or dimethylolpropionic acid.
6. the preparation method of water-based polyurethane adhesive as claimed in claim 2, is characterised in that described glycol chain extender is selected from ethylene glycol, BDO, 1,6-hexylene glycol or glycol ether.
7. the preparation method of water-based polyurethane adhesive as claimed in claim 2, is characterised in that described water-insoluble polyamine is selected from trimeric cyanamide, diethyl toluene diamine or dimethythiotoluene diamine.
8. the preparation method of water-based polyurethane adhesive as claimed in claim 2, is characterised in that described isocyanate curing agent is selected from hexamethylene diisocyanate trimer or toluene diisocyanate trimer.
9. the preparation method of water-based polyurethane adhesive as claimed in claim 2, is characterised in that described coupling agent is selected from γ-aminopropyl triethoxysilane or γ-glycidyl ether oxygen propyl trimethoxy silicane.
10. the preparation method of water-based polyurethane adhesive as claimed in claim 2, is characterised in that described filler is selected from calcium carbonate, sodium hydroxide, talcum powder or nano silicon, or wherein two kinds and two or more mixtures;
Described antioxidant is selected from 2,6 ditertiary butyl p cresol, pentanoic, Ursol D or dihydroquinoline;
Described uv-absorbing agent is selected from 2,4 dihydroxyl benzophenone or ESCALOL 567;
Described thickening material is Xylo-Mucine, Natvosol, methyl hydroxyethylcellulose, Type 3U or methylhydroxypropylcellulose;
Described defoamer adopts silicone antifoaming agent.
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