CN104893644A - Solvent type polyurethane structure adhesive and preparation method thereof - Google Patents
Solvent type polyurethane structure adhesive and preparation method thereof Download PDFInfo
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- CN104893644A CN104893644A CN201510319900.7A CN201510319900A CN104893644A CN 104893644 A CN104893644 A CN 104893644A CN 201510319900 A CN201510319900 A CN 201510319900A CN 104893644 A CN104893644 A CN 104893644A
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Abstract
The invention discloses a method for preparing a solvent type polyurethane structure adhesive. The method is characterized in that an isocyanate solidifying agent sealed by a sealing agent and a polyurethane prepolymer at the sealed end of hydroxyl group are mixed to obtain a polyurethane adhesive, or the polyurethane prepolymer sealed by the sealing agent and a trihydroxy compound are mixed, or the polyurethane prepolymer sealed by the sealing agent and the isocyanate solidifying agent sealed by the sealing agent are mixed to be added into an adsorbing filling material to obtain the polyurethane adhesive. When in use, the adhesive is heated and unsealed to obtain the isocyanate solidifying agent or polyurethane prepolymer containing NCO, and reacts with polyurethane prepolymer or the trihydroxy compound to obtain cross-linked and cured polyurethane. The adhesive can be stably stored at the room temperature, can be heated to obtain reaction type bi-component when in construction, and is different from the conventional bi-component solvent type polyurethane which wastes time in the processes of metering, mixing and the like, the construction process is simple, the performance adjustment of the single component polyurethane system is realized, and the unsealed unsealing agent cannot overflow.
Description
Technical field
The invention belongs to polyurethane material technical field, be specifically related to masked isocyanate and solvent borne polyurethane sqtructural adhesive and preparation method thereof.
Background technology
Introduce according in " adhesive for polyurethane--preparation, formula and application " (Chemical Industry Press, version in 2009) book, solvent borne polyurethane tackiness agent is mainly divided into one-component solvent borne tackiness agent and two part solvent type tackiness agent.One-component solvent borne tackiness agent is the class tackiness agent adding the one-component that solidifying agent, auxiliary agent, filler etc. are formed in the base polyurethane prepolymer for use as of synthesis, be divided into curing, hot-melting type, dead front type, radiation-curing type etc. several, there is the advantages such as processing is easy to use, period of storage is long.As, monocomponent moisture cure type polyurethane adhesive is applied more in monocomponent adhesive, the base polyurethane prepolymer for use as of monocomponent moisture cure urethanes adhesive to be isocyanate groups be end group, utilize air or use water contained in material to be cross-linked, reach the object of bonding, but also exist that solidification is slow, have the shortcoming that bubble, intensity are low in glue-line.
It is adjustable that bi-component polyurethane adhesive has performance, the advantage that bonding scope is wide.Compare monocomponent adhesive, two component adhesive adhesive property is better.Solvent-type double-component polyurethane adhesive is made up of first, second two components, and two components are packed separately, prepare by a certain percentage before using.First component is commonly referred to as host, mostly is hydroxy component; Second component is commonly referred to as solidifying agent, mostly is the component containing free isocyanate groups group.Also the host had is the base polyurethane prepolymer for use as of terminal isocyanate group, and solidifying agent is low molecular weight polyols or polyamine, and first component and second component mix generation urethane resin by a certain percentage.Owing to there is crosslinking reaction after two component mixing of reactive adhesive, produce cured product, there is the advantages such as performance is adjustable, bond strength is large, bonding scope is wide, become a most important large class in polyurethane adhesive, in tackiness agent, purposes is wide, and consumption is large.But solvent-type double-component polyurethane adhesive needs strict packing, use forward slip value and measurement process to expend man-hour, the operating time is restricted.At present; single component, two part solvent type polyurethane adhesive all contain active terminal group (isocyanate groups); storage, traffic requirements height enclosed system or nitrogen protection, cost is significantly increased, and the free isocyanate in system has very large toxicity.
How in conjunction with the high-performance of two component adhesive and the easy construction of monocomponent adhesive, can see at present report (as University Of Xiangtan's master thesis " Synthesis and application of aqueous polyurethane oximes encapsulant " in 2008, China's volume 10 phase 15-18 page in " Chinese tackiness agent " October 18 in 2009 " development of low-temperature plasticizing PVC colloidal sol blocked polyurethane ") thermofixation monocomponent adhesive system has good adhesive property and construction technology, general containing two kinds of components in thermofixation monocomponent adhesive system, this tackiness agent is closed or passivation by major constituent and solidifying agent active group one or both of physics or chemical process, thus there is not curing reaction under normal temperature, but the deblocking reaction of active group can be there is when being heated to proper temperature, or there is physical condition change elimination passive state, then there is curing reaction.Mainly contain closed solidifying agent and polyurethane prepolymer objects system, but close in solidifying agent and polyurethane prepolymer objects system and close solidifying agent deblocking and can discharge poisonous deblocking agent.
At present, sqtructural adhesive is used for the bonding of engineering structure part, is that a class can bear many ambient stress effects and destroyed tackiness agent within time rating, has chemicals-resistant and other media, the characteristic such as ageing-resistant.Current sqtructural adhesive is main mainly with two part solvent type.
Summary of the invention
The object of the invention is to propose a kind of solvent borne polyurethane sqtructural adhesive and preparation method thereof, with provide speed of reaction high, harmless, process easy to use, that adhesive property is excellent solvent borne polyurethane sqtructural adhesive, overcome the above-mentioned deficiency of prior art.
Solvent borne polyurethane sqtructural adhesive of the present invention, containing two kinds of components, wherein a kind of component is hydroxy-end capped base polyurethane prepolymer for use as or enclosed polyurethane performed polymer, referred to as first component, another kind of component is trihydric compounds or Blocked Isocyanate Curing Agents, referred to as second component; It is characterized in that: wherein first component and second components in mass portion are than being 2-20:1, and with mass percent be the filler of 0-30%, the solvent borne polyurethane sqtructural adhesive that mixes of the flow agent of the antioxidant of the coupling agent of 0-3%, 0-1%, the neutralizing agent of 0-20%, the uv-absorbing agent of 0-1% and 0-3%;
When described first component is hydroxy-end capped base polyurethane prepolymer for use as, second component with matching is Blocked Isocyanate Curing Agents;
When described first component is enclosed polyurethane performed polymer, then second component with matching can select trihydric compounds or Blocked Isocyanate Curing Agents;
Described filler is selected from calcium carbonate, sodium hydroxide, talcum powder or nano silicon, or wherein two kinds and two or more mixtures;
Described coupling agent is selected from γ-aminopropyl triethoxysilane (KH550) or γ-glycidyl ether oxygen propyl trimethoxy silicane (KH560);
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 flow agent preferably adopts the polyether-modified polydimethylsiloxane of German Bi Ke Products (BYK-333) or polyether-modified polydimethylsiloxane (BYK-306).
The preparation method of solvent borne polyurethane sqtructural adhesive of the present invention, obtains hydroxy-end capped base polyurethane prepolymer for use as by macromolecule dihydric alcohol, vulcabond, glycol chain extender by prepolymerization reaction; Or regulate reaction ratio obtain isocyanate-terminated base polyurethane prepolymer for use as after add encapsulant phenol (PHE) again and be obtained by reacting enclosed polyurethane performed polymer; It is characterized in that: trihydric compounds and enclosed polyurethane performed polymer are mixed to get solvent borne polyurethane sqtructural adhesive; Or, Blocked Isocyanate Curing Agents and hydroxy-end capped base polyurethane prepolymer for use as are mixed to get solvent borne polyurethane sqtructural adhesive; Or, Blocked Isocyanate Curing Agents is mixed to get solvent borne polyurethane sqtructural adhesive with enclosed polyurethane performed polymer;
Described operation steps trihydric compounds and enclosed polyurethane performed polymer being mixed to get solvent borne polyurethane sqtructural adhesive is: by mass parts by the macromolecule dihydric alcohol of 100 parts 110-120 DEG C dehydration 0.5-1.5 hour, add the vulcabond of 5-60 part again, the glycol chain extender of 0-30 part is added after 2-4 hour 70-100 DEG C of reaction, the dibutyl tin laurate (DBTDL) of 0.01-0.08% and the solvent of 20-50%, the encapsulant phenol of 10-50 part is added after 1-4 hour 60-90 DEG C of reaction, 70-100 DEG C of reaction 3-6 hour, obtain enclosed polyurethane performed polymer, press mass parts again by the enclosed polyurethane performed polymer of 100 parts of above-mentioned preparations, mix with 2-50 part trihydric compounds, 0-3 part coupling agent, 0-30 part filler, 0-1 part antioxidant, 0-1 part uv-absorbing agent, 0-3 part flow agent and 0-20 part neutralizing agent, namely obtain solvent borne polyurethane sqtructural adhesive,
The operation steps of described PU Structural Adhesives Blocked Isocyanate Curing Agents and hydroxy-end capped base polyurethane prepolymer for use as are mixed to get is: by mass parts by the macromolecule dihydric alcohol of 100 parts at the 110-120 DEG C of 0.5-1.5 hour that dewaters, add 5-60 part vulcabond again, add the glycol chain extender of 0-30 part, the dibutyl tin laurate of 0.05-0.5 part and 50-200 part solvent 70-100 DEG C of reaction after 2-4 hour, within 1-4 hour, obtain hydroxy-end capped base polyurethane prepolymer for use as 60-90 DEG C of reaction; 100 parts of vulcabond are dissolved in solvent, are mixed with the solution that mass percent concentration is 10-30%, are warming up to 60-80 DEG C under magnetic agitation, slowly add trihydric compounds; Wherein the mol ratio of vulcabond and trihydric compounds is 3:1; Add in 2 hours, within 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; By above-mentioned homemade isocyanate curing agent, add the solvent of 80-200 part, the dibutyl tin laurate of 0.05-0.5 part, as catalyzer, adds encapsulant phenol under agitation condition, reacts and obtain Blocked Isocyanate Curing Agents in 2-6 hour at 70-100 DEG C; Wherein isocyanate curing agent is 1:3-5 with the ratio of encapsulant amount of substance; By the base polyurethane prepolymer for use as of 2-50 part Blocked Isocyanate Curing Agents, 100 parts of above-mentioned preparations after reaction terminates, mix with 0-3 part coupling agent, 0-30 part filler, 0-1 part antioxidant, 0-1 part uv-absorbing agent, 0-3 part flow agent and 0-20 part neutralizing agent, namely obtain solvent borne polyurethane sqtructural adhesive;
Described operation steps Blocked Isocyanate Curing Agents and enclosed polyurethane performed polymer being mixed to get solvent borne polyurethane sqtructural adhesive is: by mass parts by the macromolecule dihydric alcohol of 100 parts at the 110-120 DEG C of 0.5-1.5 hour that dewaters, add the vulcabond of 5-60 part again, the glycol chain extender of 0-30 part is added after 2-4 hour 70-100 DEG C of reaction, the dibutyl tin laurate of 0.01-0.08% and the solvent of 20-50%, the phenol of 10-50 part is added after 1-4 hour 60-90 DEG C of reaction, 70-100 DEG C of reaction 3-6 hour, obtain enclosed polyurethane performed polymer, 100 parts of vulcabond are dissolved in solvent, are mixed with the solution that mass percent concentration is 10-30%, are warming up to 60-80 DEG C under magnetic agitation, slowly add trihydric compounds, wherein the mol ratio of vulcabond and trihydric compounds is 3:1, 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, by above-mentioned homemade isocyanate curing agent, add the solvent of 80-200 part, the dibutyl tin laurate of 0.05-0.5 part, as catalyzer, adds encapsulant phenol under agitation condition, and 70-100 DEG C of reaction 2-6 hour, obtains Blocked Isocyanate Curing Agents, wherein isocyanate curing agent is 1:3-5 with the ratio of encapsulant amount of substance, by the enclosed polyurethane performed polymer of 2-50 part Blocked Isocyanate Curing Agents, 100 parts of above-mentioned preparations after reaction terminates, mix with 0-3 part coupling agent, 0-30 part filler, 0-1 part antioxidant, 0-1 part uv-absorbing agent, 0-3 part flow agent and 0-20 part neutralizing agent, namely obtain solvent borne polyurethane sqtructural adhesive.
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 glycol chain extender is selected from ethylene glycol (EG), BDO (BDO), 1,6-hexylene glycol (HDO) or glycol ether (DEG);
Described isocyanate curing agent is selected from hexamethylene diisocyanate trimer (HDIT) or toluene diisocyanate trimer (TDIT);
Described trihydric compounds is selected from TriMethylolPropane(TMP) (TMP), glycerine (GE) or Viscotrol C (CO), or wherein two kinds and two or more mixtures;
Described solvent selected from acetone, butanone, ethyl acetate, butylacetate or DMF, or wherein two kinds and two or more mixtures;
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 flow agent preferably adopts the polyether-modified polydimethylsiloxane of German Bi Ke Products (BYK-333) or polyether-modified polydimethylsiloxane (BYK-306).
Due to the preparation method of solvent borne polyurethane sqtructural adhesive of the present invention, use adds enclosed polyurethane performed polymer or masked isocyanate as active ingredient, or use enclosed polyurethane performed polymer and masked isocyanate as active ingredient simultaneously, play dual cure effect, masked isocyanate or enclosed polyurethane performed polymer, as active ingredient post-heating deblocking, play the effect of curing cross-linked.Owing to adding excessive basic filler, urethane is alkaline system, and the encapsulant phenol that deblocking goes out carries out acid-base reaction salify with it, can not discharge work the mischief to human body and environment from system.Solve in current polyurethane adhesive and discharge harmful compound, process the problem using inconvenience, period of storage short.
Preparation method of the present invention compared with prior art has the following advantages:
1. adopt polyurethane adhesive prepared by the inventive method, the application accessibility of existing single component has again the high strength of high curing speed and response type glue, is applicable to large-duty automatic production line requirement;
2. the polyurethane adhesive adopting the inventive method to prepare can obtain solvent resistance, the contour performance of thermotolerance of reactive polyurethane adhesive, and by regulating Blocked Isocyanate Curing Agents at the content of system, the performance achieving single-component system is adjustable;
3. adopt polyurethane adhesive prepared by the inventive method, simply, processing property is good, and during construction, deblocking temperature is low, energy efficient for production, bonding process, can avoid the infringement to bonding consumptive material;
4. adopt the polyurethane adhesive prepared of the inventive method, can preserve for a long time, under normal temperature for water, containing the reactionless activity of active hydrogen substance;
5. the polyurethane adhesive adopting the inventive method to prepare, the problems such as the toxicity that can reduce to greatest extent to cause because of free isocyanate is large.
6. the preparation method of solvent borne polyurethane sqtructural 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 serial glued membrane (PU-A1, PU-A2, PU-A3 and PU-A4) the thermogravimetric curve figure prepared in Application Example of the present invention;
Fig. 2 prepares the DSC graphic representation that glued membrane (PU-A2) recorded by differential scanning calorimeter in Application Example of the present invention;
The deblocking graphic representation that Fig. 3 is recorded by differential scanning calorimeter for the Blocked Isocyanate Curing Agents PU-CA prepared in Application Example of the present invention.
Embodiment
Embodiment 1:
By 50.00 grams of PCL (M
n=2000) join in the there-necked flask of 500mL, after dewatering 1 hour at 115 DEG C, be cooled to 60 DEG C.Get 0.04 gram of DBTDL, 18 grams of TDI and 30 gram butanone add in there-necked flask, add 12 grams of PHE after 2 hours in 80 DEG C of stirring reactions and react at 80 DEG C and within 5 hours, obtain enclosed polyurethane performed polymer (first component).
Then 3 grams of TMP, 3.3 grams of CO are obtained second component after mixing with 10 grams of ethyl acetate, solvent borne polyurethane sqtructural adhesive is obtained after being uniformly mixed again with 0.1 gram of 2,6 ditertiary butyl p cresol, 0.5 gram of KH560,7 grams of nano silicons, above-mentioned enclosed polyurethane performed polymers.
According to practice of construction needs, also the ratio of adjustable first component, second component obtains the tackiness agent of different cohesive strength, thermomechanical property.
Embodiment 2:
By 80.00 grams of PEA (M
n=2000) join in the there-necked flask of 500mL, after dewatering 1 hour at 115 DEG C, be cooled to 60 DEG C.Get 0.04 gram of DBTDL, 10 grams of MDI and 70 gram butanone add in there-necked flask, add 0.95 gram of DEG in 70 DEG C of stirring reactions after 2 hours, at 60 DEG C, reaction obtains hydroxy-end capped base polyurethane prepolymer for use as in 5 hours.
Then by 6.25 grams of HDIT, 1.40 gram PHE, 0.02 gram of DBTDL and 10 gram butylacetate joins in 50mL there-necked flask, the lower 85 DEG C of reactions of agitation condition obtain Blocked Isocyanate Curing Agents in 3 hours, obtain solvent borne polyurethane sqtructural adhesive after being then uniformly mixed with above-mentioned base polyurethane prepolymer for use as.
According to practice of construction needs, also the ratio of adjustable two components obtains the tackiness agent of different cohesive strength, thermomechanical property.
If other condition of the present embodiment is constant, and DEG is changed into BDO, HDO or EG, also polyurethane adhesive can be obtained.
If other condition of the present embodiment is constant, and MDI is changed into HDI or IPDI, all polyurethane adhesive can be obtained.
Embodiment 3:
By 50.00 grams of PBA (M
n=3200) join in the there-necked flask of 500mL, after dewatering 1 hour at 115 DEG C, be cooled to 60 DEG C.Get 0.02 gram of DBTDL, 2.72 grams of TDI and 55 gram butanone add in there-necked flask, obtain hydroxy-end capped base polyurethane prepolymer for use as PU-CA after 2 hours in 80 DEG C of stirring reactions.
Then, getting 80 grams of TDI and 230mL butanone joins in the there-necked flask of 500mL, be warming up to 65 DEG C, stir lower interpolation and add 20.5 grams of TMP, add in 2 hours, at 70 DEG C, be incubated 2 hours, then add 51.9 grams of PHE, react 4 hours at 80 DEG C, be cooled to room temperature and obtain Blocked Isocyanate Curing Agents PU-CA.
Finally according to construction needs, after a certain proportion of Blocked Isocyanate Curing Agents and above-mentioned base polyurethane prepolymer for use as being uniformly mixed, obtain solvent borne polyurethane sqtructural adhesive.
Embodiment 4:
By 50.00 grams of PCL (M
n=2000) join in the there-necked flask of 500mL, after dewatering 1 hour at 115 DEG C, be cooled to 60 DEG C.Get 0.04 gram of DBTDL, 18 grams of TDI and 30 gram butanone add in there-necked flask, add 12 grams of PHE after 2 hours in 80 DEG C of stirring reactions and react at 80 DEG C and within 5 hours, obtain enclosed polyurethane performed polymer (first component).
Then, getting 8 grams of TDI and 100mL butanone joins in the there-necked flask of 500mL, be warming up to 65 DEG C, stir lower interpolation and add 2.05 grams of TMP, add in 2 hours, at 70 DEG C, be incubated 2 hours, then add 5.2 grams of PHE, react 4 hours at 80 DEG C, be cooled to room temperature and obtain Blocked Isocyanate Curing Agents PU-CA2.
Finally according to construction needs, after a certain proportion of Blocked Isocyanate Curing Agents and above-mentioned base polyurethane prepolymer for use as being uniformly mixed, obtain solvent borne polyurethane sqtructural adhesive.
Application Example:
According to different ratio in table 1, the hydroxy-end capped base polyurethane prepolymer for use as PU-CA of synthesis in embodiment 3 and Blocked Isocyanate Curing Agents PU-CA is deployed into the solvent borne polyurethane sqtructural adhesive of different ratios.With reference to National Standard of the People's Republic of China's soft composite plastics material peel test method, the Average peel force utilizing polyvinyl chloride (PVC) leatheroid to record tackiness agent PU-A2 is 40.16N.Acetone, butanone is insoluble to after adhesive solidification.120 DEG C time, set time is 5 minutes, shows higher curing speed.
Table 1
After solvent is removed in above prepared tackiness agent drying, at 120 DEG C of formation glued membranes that are heating and curing, thermogravimetric curve is adopted to weigh the resistance toheat of glued membrane, Shimadzu (Shimadzu TGA-50H) thermogravimetric analyzer is used to test the thermogravimetric curve of film, the testing sample taking 6-10mg puts into crucible, heat flow rate is 10 DEG C/min under nitrogen atmosphere, Range of measuring temp 50 DEG C-700 DEG C.Fig. 1 prepares serial glued membrane (PU-A1 in this Application Example, PU-A2, PU-A3 and PU-A4) thermogravimetric curve figure, as can be seen from the figure the thermal degradation process of urethane can be divided into two stages: the first stage is from about 128 DEG C, the degraded of what this one-phase was corresponding is hard section ammonia ester bond, this stage, thermal degradation temperature reduced along with the increase of Blocked Isocyanate Curing Agents; Subordinate phase from about 400 DEG C, the degraded of flexible polyurethane section that corresponding is.Fig. 1 also shows, along with the increase of Blocked Isocyanate Curing Agents content, sample carryover Mass lost, illustrates the different ratios of change two component, and the thermomechanical property that can realize monocomponent polyurethane adhesive is adjustable.
Fig. 2 is the DSC graphic representation being recorded PU-A2 by differential scanning calorimeter.Under nitrogen protection, nitrogen rate is 100mL/min, and temperature rise rate is under 10 DEG C/min condition in experiment, measures second-order transition temperature to polyurethane adhesive PU-A2 in embodiment 3.As seen from the figure, the second-order transition temperature of PU-A2 is-32.08 DEG C.Fig. 2 illustrates that this polyurethane adhesive has good resistance to low temperature.
Fig. 3 is the deblocking graphic representation being recorded Blocked Isocyanate Curing Agents PU-CA by differential scanning calorimeter.Experiment condition is: nitrogen atmosphere, and nitrogen rate is 100mL/min, and temperature rise rate is 10 DEG C/min.As can be seen from the figure the deblocking temperature of PU-CA is between 90-110 DEG C.Fig. 3 illustrates that this polyurethane adhesive has lower deblocking temperature, can reach convenient construction, energy efficient, avoids effects such as the destructions of matrix material using.
Claims (10)
1. a solvent borne polyurethane sqtructural adhesive, containing two kinds of components, wherein a kind of component is hydroxy-end capped base polyurethane prepolymer for use as or enclosed polyurethane performed polymer, referred to as first component, another kind of component is trihydric compounds or Blocked Isocyanate Curing Agents, referred to as second component; It is characterized in that: wherein first component and second components in mass portion are than being 2-20:1, and with mass percent be the filler of 0-30%, the solvent borne polyurethane sqtructural adhesive that mixes of the flow agent of the antioxidant of the coupling agent of 0-3%, 0-1%, the neutralizing agent of 0-20%, the uv-absorbing agent of 0-1% and 0-3%;
When described first component is hydroxy-end capped base polyurethane prepolymer for use as, second component with matching is Blocked Isocyanate Curing Agents;
When described first component is enclosed polyurethane performed polymer, then second component with matching selects trihydric compounds or Blocked Isocyanate Curing Agents;
Described filler is selected from calcium carbonate, sodium hydroxide, talcum powder or nano silicon, or wherein two kinds and two or more mixtures;
Described coupling agent is selected from γ-aminopropyl triethoxysilane or γ-glycidyl ether oxygen propyl trimethoxy silicane;
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 flow agent adopts polyether-modified polydimethylsiloxane or polyether-modified polydimethylsiloxane.
2. the preparation method of solvent borne polyurethane sqtructural adhesive described in claim 1, obtains hydroxy-end capped base polyurethane prepolymer for use as by macromolecule dihydric alcohol, vulcabond, glycol chain extender by prepolymerization reaction; Or regulate reaction ratio obtain isocyanate-terminated base polyurethane prepolymer for use as after add encapsulant phenol reactant again and obtain enclosed polyurethane performed polymer; It is characterized in that: trihydric compounds and enclosed polyurethane performed polymer are mixed to get solvent borne polyurethane sqtructural adhesive; Or, Blocked Isocyanate Curing Agents and hydroxy-end capped base polyurethane prepolymer for use as are mixed to get solvent borne polyurethane sqtructural adhesive; Or, Blocked Isocyanate Curing Agents is mixed to get solvent borne polyurethane sqtructural adhesive with enclosed polyurethane performed polymer;
Described operation steps trihydric compounds and enclosed polyurethane performed polymer being mixed to get solvent borne polyurethane sqtructural adhesive is: by mass parts by the macromolecule dihydric alcohol of 100 parts 110-120 DEG C dehydration 0.5-1.5 hour, add the vulcabond of 5-60 part again, the glycol chain extender of 0-30 part is added after 2-4 hour 70-100 DEG C of reaction, the dibutyl tin laurate of 0.01-0.08% and the solvent of 20-50%, the encapsulant phenol of 10-50 part is added after 1-4 hour 60-90 DEG C of reaction, 70-100 DEG C of reaction 3-6 hour, obtain enclosed polyurethane performed polymer, press mass parts again by the enclosed polyurethane performed polymer of 100 parts of above-mentioned preparations, mix with 2-50 part trihydric compounds, 0-3 part coupling agent, 0-30 part filler, 0-1 part antioxidant, 0-1 part uv-absorbing agent, 0-3 part flow agent and 0-20 part neutralizing agent, namely obtain solvent borne polyurethane sqtructural adhesive,
The operation steps of described PU Structural Adhesives Blocked Isocyanate Curing Agents and hydroxy-end capped base polyurethane prepolymer for use as are mixed to get is: by mass parts by the macromolecule dihydric alcohol of 100 parts at the 110-120 DEG C of 0.5-1.5 hour that dewaters, add 5-60 part vulcabond again, add the glycol chain extender of 0-30 part, the dibutyl tin laurate of 0.05-0.5 part and 50-200 part solvent 70-100 DEG C of reaction after 2-4 hour, within 1-4 hour, obtain hydroxy-end capped base polyurethane prepolymer for use as 60-90 DEG C of reaction; 100 parts of vulcabond are dissolved in solvent, are mixed with the solution that mass percent concentration is 10-30%, are warming up to 60-80 DEG C under magnetic agitation, slowly add trihydric compounds; Wherein the mol ratio of vulcabond and trihydric compounds is 3:1; Add in 2 hours, within 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; By above-mentioned homemade isocyanate curing agent, add the solvent of 80-200 part, the dibutyl tin laurate of 0.05-0.5 part, as catalyzer, adds encapsulant phenol under agitation condition, reacts and obtain Blocked Isocyanate Curing Agents in 2-6 hour at 70-100 DEG C; Wherein isocyanate curing agent is 1:3-5 with the ratio of encapsulant amount of substance; By the base polyurethane prepolymer for use as of 2-50 part Blocked Isocyanate Curing Agents, 100 parts of above-mentioned preparations after reaction terminates, mix with 0-3 part coupling agent, 0-30 part filler, 0-1 part antioxidant, 0-1 part uv-absorbing agent, 0-3 part flow agent and 0-20 part neutralizing agent, namely obtain solvent borne polyurethane sqtructural adhesive;
Described operation steps Blocked Isocyanate Curing Agents and enclosed polyurethane performed polymer being mixed to get solvent borne polyurethane sqtructural adhesive is: by mass parts by the macromolecule dihydric alcohol of 100 parts at the 110-120 DEG C of 0.5-1.5 hour that dewaters, add the vulcabond of 5-60 part again, the glycol chain extender of 0-30 part is added after 2-4 hour 70-100 DEG C of reaction, the dibutyl tin laurate of 0.01-0.08% and the solvent of 20-50%, the phenol of 10-50 part is added after 1-4 hour 60-90 DEG C of reaction, 70-100 DEG C of reaction 3-6 hour, obtain enclosed polyurethane performed polymer, 100 parts of vulcabond are dissolved in solvent, are mixed with the solution that mass percent concentration is 10-30%, are warming up to 60-80 DEG C under magnetic agitation, slowly add trihydric compounds, wherein the mol ratio of vulcabond and trihydric compounds is 3:1, 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, by above-mentioned homemade isocyanate curing agent, add the solvent of 80-200 part, the dibutyl tin laurate of 0.05-0.5 part, as catalyzer, adds encapsulant phenol under agitation condition, and 70-100 DEG C of reaction 2-6 hour, obtains Blocked Isocyanate Curing Agents, wherein isocyanate curing agent is 1:3-5 with the ratio of encapsulant amount of substance, by the enclosed polyurethane performed polymer of 2-50 part Blocked Isocyanate Curing Agents, 100 parts of above-mentioned preparations after reaction terminates, mix with 0-3 part coupling agent, 0-30 part filler, 0-1 part antioxidant, 0-1 part uv-absorbing agent, 0-3 part flow agent and 0-20 part neutralizing agent, namely obtain solvent borne polyurethane sqtructural adhesive.
3. the preparation method of solvent borne polyurethane sqtructural 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 solvent borne polyurethane sqtructural 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 solvent borne polyurethane sqtructural 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.
6. the preparation method of solvent borne polyurethane sqtructural adhesive as claimed in claim 2, is characterised in that described isocyanate curing agent is selected from hexamethylene diisocyanate trimer or toluene diisocyanate trimer.
7. the preparation method of solvent borne polyurethane sqtructural adhesive as claimed in claim 2, is characterised in that described trihydric compounds is selected from TriMethylolPropane(TMP), glycerine or Viscotrol C, or wherein two kinds and two or more mixtures.
8. the preparation method of solvent borne polyurethane sqtructural adhesive as claimed in claim 2, is characterised in that described solvent selected from acetone, butanone, ethyl acetate, butylacetate or DMF, or wherein two kinds and two or more mixtures.
9. the preparation method of solvent borne polyurethane sqtructural 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 solvent borne polyurethane sqtructural 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 flow agent selects polyether-modified polydimethylsiloxane or polyether-modified polydimethylsiloxane.
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| CN201510319900.7A CN104893644A (en) | 2015-06-09 | 2015-06-09 | Solvent type polyurethane structure adhesive and preparation method thereof |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221654A (en) * | 2016-02-02 | 2016-12-14 | 北京理工大学 | A kind of flame retardant bicomponent adhesive for polyurethane and preparation method thereof |
| CN106833489A (en) * | 2015-12-04 | 2017-06-13 | 中国人民解放军军械工程学院 | A kind of double-component silicane-modified polyurethane fluid sealant |
| CN106905503A (en) * | 2015-12-21 | 2017-06-30 | Dic株式会社 | Polyurethane resin composition and synthetic leather |
| CN108250993A (en) * | 2018-01-23 | 2018-07-06 | 苏州世华新材料科技有限公司 | A kind of no base material low-temp reaction type Hot melt adhesive tape and its with glue and preparation method |
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| CN114276772A (en) * | 2021-12-07 | 2022-04-05 | 黎明化工研究设计院有限责任公司 | Flame-retardant polyurethane adhesive and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029203A (en) * | 2007-02-08 | 2007-09-05 | 常熟理工学院 | Production of cryogenic direct-welding polyurethane envelope without pinhole |
| US20080289761A1 (en) * | 2004-05-10 | 2008-11-27 | Bernhard Bosshard | Polyurethane Composition with High Early Strength |
| CN101469259A (en) * | 2007-12-27 | 2009-07-01 | 上海轻工业研究所有限公司 | Polyurethane reactive hot melt structure adhensive |
| CN102268217A (en) * | 2011-06-09 | 2011-12-07 | 常州虹波涂料有限公司 | Method for preparing polyurethane enamelled wire paint allowing for direct welding without weld slag |
-
2015
- 2015-06-09 CN CN201510319900.7A patent/CN104893644A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080289761A1 (en) * | 2004-05-10 | 2008-11-27 | Bernhard Bosshard | Polyurethane Composition with High Early Strength |
| CN101029203A (en) * | 2007-02-08 | 2007-09-05 | 常熟理工学院 | Production of cryogenic direct-welding polyurethane envelope without pinhole |
| CN101469259A (en) * | 2007-12-27 | 2009-07-01 | 上海轻工业研究所有限公司 | Polyurethane reactive hot melt structure adhensive |
| CN102268217A (en) * | 2011-06-09 | 2011-12-07 | 常州虹波涂料有限公司 | Method for preparing polyurethane enamelled wire paint allowing for direct welding without weld slag |
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| CN106221654B (en) * | 2016-02-02 | 2019-08-23 | 北京理工大学 | A kind of flame retardant bicomponent adhesive for polyurethane and preparation method thereof |
| CN106221654A (en) * | 2016-02-02 | 2016-12-14 | 北京理工大学 | A kind of flame retardant bicomponent adhesive for polyurethane and preparation method thereof |
| CN108250993A (en) * | 2018-01-23 | 2018-07-06 | 苏州世华新材料科技有限公司 | A kind of no base material low-temp reaction type Hot melt adhesive tape and its with glue and preparation method |
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| CN108997964A (en) * | 2018-09-05 | 2018-12-14 | 江苏科麦特科技发展有限公司 | One kind blocks water oxygen adhesive and preparation method and application method |
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| CN109796921B (en) * | 2019-01-30 | 2021-03-26 | 广东盈通新材料有限公司 | Modified polyurethane adhesive, composite waterproof strip comprising modified polyurethane adhesive, and preparation method and application of composite waterproof strip |
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| CN111690364A (en) * | 2020-07-22 | 2020-09-22 | 佛山市同骏环保科技有限公司 | Single-component high-temperature curing adhesive |
| CN111675993A (en) * | 2020-07-22 | 2020-09-18 | 佛山市同骏环保科技有限公司 | Novel bottle cap printing process |
| CN111675993B (en) * | 2020-07-22 | 2022-03-29 | 佛山市同骏环保科技有限公司 | Novel bottle cap printing process |
| CN111690364B (en) * | 2020-07-22 | 2022-05-06 | 佛山市同骏环保科技有限公司 | Single-component high-temperature curing adhesive |
| CN111978852A (en) * | 2020-09-01 | 2020-11-24 | 西北大学 | Cultural relic structure reinforcing material and preparation method and application thereof |
| CN111978852B (en) * | 2020-09-01 | 2021-10-22 | 西北大学 | Cultural relic structure reinforcing material and preparation method and application thereof |
| CN114276772A (en) * | 2021-12-07 | 2022-04-05 | 黎明化工研究设计院有限责任公司 | Flame-retardant polyurethane adhesive and preparation method thereof |
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