CN109749692A - A kind of heat resistant type wet-solidifying single-component polyurethane adhesive and its preparation method and application - Google Patents
A kind of heat resistant type wet-solidifying single-component polyurethane adhesive and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of heat resistant type wet-solidifying single-component polyurethane adhesive and its preparation method and application, pass through esterification using castor oil, phthalic anhydride and dihydric alcohol first, it is 2.0~2.5, the castor oil modified polyester polyol containing phenyl ring aromatic structure and longer fatty acid molecule segment that degree of functionality, which is prepared, when part substitution polyvalent alcohol is used for polyurethane-modified, rigid phenyl ring can be introduced into soft segment, control the crystallite distribution in soft segment structure, enhance glue-line flexibility, cohesive strength increases, and improves heat resistance；Meanwhile the degree of cross linking of polymer can be effectively controlled in castor oil polyester polyol after modified, prevents the excessive sharply decline or the generation of gel for leading to Adhensive performance of the degree of cross linking.Using castor oil modified polyester polyol to polyurethane-modified, it is remarkably improved the adhesive property and heat resistance of adhesive.The bonding problem to crack at bonding wood when the high temperature roasting procedure such as solving the drying of wood in timber process, do bent plate.
Description
Technical field
The invention belongs to polymer material technical field of modification, and in particular to a kind of heat resistant type wet-solidifying single-component polyurethane
Adhesive and its preparation method and application.Polyurethane adhesive cohesive strength of the invention is high, adhesive property is strong and heat-resist,
The bonding that can be used for wood processing field uses.
Background technique
Polyurethane adhesive is the high polymer being polymerized by polyisocyanates and polyvalent alcohol, is widely used in timber row
The bonding of industry.In the curing process, wet-solidifying single-component polyurethane adhesive is mainly with group active on strand, such as-
Active hydrogen compounds and moisture in NCO, with timber or the moisture in air are cured reaction, make to play bonding
With.
Single monocomponent moisture cure urethanes adhesive is also unable to satisfy the bonding demand of timber, is mainly manifested in cohesion
The problems such as intensity is low, adhesive property is weak, heat resistance is poor, heat resisting temperature is usually at 80 DEG C hereinafter, when temperature reaches 110 DEG C or more
When, hard segment structure starts to decompose, and the bonding requirements when high temperature roasting procedures such as bonding wood part is dry, does bent plate are not achieved.Cause
And heat-resisting type polyurethane adhesive has become research hotspot in recent years, often passes through the rigidity or crystallization of increase polymer at present
Structure adds the means such as nano inorganic material and additional antioxidant, the heat resistance of Lai Tigao adhesive.
However, simultaneously by the pure and mild silanization nano silica of castor oil modified polyester polyols be used for the modification of polyurethane with
Improve polymer heat resistant type not yet studies have reported that.Non-modified castor oil contains there are three the above activity hydroxy functional group,
The use of direct part substitution polyvalent alcohol can lead to the decline of polymer performance because the degree of cross linking is excessive, can not embody castor-oil plant
The excellent properties advantage of oil.And the nano silica of non-silylating reagent for it is polyurethane-modified when cause because compatibility is bad
Agglomeration is serious, and modified effect is bad.
Summary of the invention
In order to solve the deficiencies in the prior art, the method comprises the steps of firstly, preparing the pure and mild silanizations of castor oil modified polyester polyols to receive
Rice silica, is used further to the modification of polyurethane, which can be effectively by castor oil modified polyurethane polyalcohol and silane
The performance advantage for changing nano silica combines with the performance of polyurethane adhesive, and prepared adhesive has cohesion strong
The feature that degree is high, adhesive property is strong, heat resistance is good, heat resisting temperature can meet in timber process up to 160 DEG C or more
High temperature resistant bonding requirements when the drying of wood, the high temperature roasting procedure such as do bent plate.
The object of the present invention is to provide a kind of heat resistant type wet-solidifying single-component polyurethane adhesive and preparation method thereof and use
On the way, the heat resisting temperature of the polyurethane adhesive is up to 160 DEG C or more.
In order to achieve the above objectives, this invention takes following technical solutions:
A kind of heat resistant type wet-solidifying single-component polyurethane adhesive, which is characterized in that prepare the raw material group of the adhesive
Divide and its content includes:
Preferably, each component including following percentage composition:
According to the present invention, the polyvalent alcohol is selected from least one of polyester polyol or polyether polyol.
In the present invention, the polyvalent alcohol is unmodified polyvalent alcohol.
According to the present invention, the number-average molecular weight of the polyvalent alcohol is 1000~3000g/mol.
According to the present invention, the polyester polyol is selected from polyethylene glycol adipate glycol, one contracting diethyl of polyadipate
At least one of glycol esterdiol or polyadipate -1,4- butyl glycol ester diol.
According to the present invention, the polyether polyol is selected from polyoxypropyleneglycol, polytetrahydrofuran ether glycol or tetrahydro
At least one of furans-propylene oxide copolymer glycols.
According to the present invention, it is 2.0~2.5 that the castor oil modified polyester polyol, which is selected from degree of functionality, number-average molecular weight
For 1900 to 4000g/mol castor oil modified polyester polyol.
According to the present invention, the castor oil modified polyester polyol is prepared via a method which to obtain:
Castor oil, phthalic anhydride, chain extender and catalyst are mixed, vacuum dehydration reaction is carried out, continues to heat, is made
It is standby to obtain castor oil modified polyester polyol.
According to the present invention, in the preparation method of above-mentioned castor oil modified polyester polyol, preferably in inert gas shielding item
It carries out under part, such as is carried out under nitrogen gas, argon gas, helium atmosphere protective condition.
Preferably, the mass percent of castor oil, phthalic anhydride, chain extender and catalyst is (15-25): (15-
35):(18-30):(0.03-0.08)。
According to the present invention, in the preparation method of above-mentioned castor oil modified polyester polyol, the vacuum dehydration reaction
Temperature is 150~160 DEG C, and the time of vacuum dehydration reaction is 2~3h.Vacuum dehydration reaction process preferably uses other solvents (such as
Toluene liquid) fluid-tight, make the water generated and polyester polyol separation.
According to the present invention, in the preparation method of above-mentioned castor oil modified polyester polyol, continue to heat and keep and evaporate head temperature
Degree is not less than 100 DEG C, reacts 4~5h.
According to the present invention, above-mentioned castor oil modified polyester polyol obtains in preparation method, further includes drying process, described dry
Dry process preferably carries out in 50 DEG C of vacuum ovens.
According to the present invention, the diisocyanate is selected from toluene di-isocyanate(TDI), hexamethylene diisocyanate, different Buddhist
That at least one of ketone diisocyanate or diphenyl methane -4,4 '-diisocyanate.
According to the present invention, the catalyst is selected from least one of dibutyl tin dilaurate, stannous octoate.
According to the present invention, the chain extender is selected from small molecule dihydric alcohol, and the small molecule dihydric alcohol is selected from C2-6Binary
Alcohol, such as at least one in ethylene glycol, 1,4-butanediol, diglycol, dipropylene glycol, 1,6- hexylene glycol
Kind.
According to the present invention, the silanization nano silica is prepared via a method which to obtain:
By nano silica and N-Methyl pyrrolidone ultrasonic disperse, gamma-aminopropyl-triethoxy-silane is then added,
Surface grafting reaction obtains silanization nano silica.
According to the present invention, in the preparation method of above-mentioned silanization nano silica, the nano silica, N- methyl
The mass percent of pyrrolidones and gamma-aminopropyl-triethoxy-silane is (10-15): (10-30): (1-5).
According to the present invention, in the preparation method of above-mentioned silanization nano silica, the time of ultrasonic disperse is 1~2h.
According to the present invention, in the preparation method of above-mentioned silanization nano silica, the temperature of Surface grafting reaction is 35
~45 DEG C, the time of Surface grafting reaction is 4~6h.Surface grafting reaction preferably carries out under agitation.
Preferably, cooling, centrifugation is carried out after Surface grafting reaction, is washed repeatedly with dehydrated alcohol, very
Sky is dried.
According to the present invention, the antioxidant is selected from 2,6-di-tert-butyl p-cresol (such as antioxidant 264), 4,4 '-
Two t-octyls-diphenylamines (such as antioxidant 5570), tetramethylene β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid Ji Wusi
Alcohol ester (such as antioxidant 1010).
According to the present invention, the solvent is selected from least one of acetone, butanone, ethyl acetate, butyl acetate.
According to the present invention, up to 160 DEG C or more, the polyurethane adhesive exists the heat resisting temperature of the polyurethane adhesive
160 DEG C of heat drying cracking time >=6 hours.
According to the present invention, the polyurethane adhesive storage period reaches >=6 months, resistance to boiling water boiling time >=6 hour, compression
Shear strength >=10.0MPa, tensile shear strength >=5.0MPa.
According to the present invention, heat resistant type wet-solidifying single-component polyurethane adhesive can be prepared by the following method, packet
It includes: castor oil modified polyester polyol, polyvalent alcohol, diisocyanate and catalyst is mixed, carry out pre-reaction, chain extension is added
Agent carries out chain extending reaction, obtains base polyurethane prepolymer for use as；Silanization nano silica is added to change base polyurethane prepolymer for use as
Property reaction, be added solvent be diluted, add antioxidant, obtain heat resistant type wet-solidifying single-component polyurethane adhesive.
According to the present invention, in the preparation method of above-mentioned polyurethane adhesive, the temperature of pre-reaction is 70~90 DEG C, pre-reaction
Time be 2~3h.
According to the present invention, in the preparation method of above-mentioned polyurethane adhesive, the temperature of chain extending reaction is 70~90 DEG C, chain extension
The time of reaction is 1~2h.
According to the present invention, in the preparation method of above-mentioned polyurethane adhesive, the temperature of modified-reaction is 70~90 DEG C, modified
The time of reaction is 2~3h.Preferably, after solvent being added, 35~40 DEG C is cooled to, antioxidant is added.
According to the present invention, in the preparation method of above-mentioned polyurethane adhesive, castor oil modified polyester polyol, gather it is polynary
The mass percent of alcohol, diisocyanate and catalyst is (10-15): (30-50): (15-35): (0.01-0.1).
According to the present invention, in the preparation method of above-mentioned polyurethane adhesive, castor oil modified polyester polyol, polyvalent alcohol
After pretreatment, mixed；The pretreatment for example can be vacuum dehydration.
The present invention also provides the preparation methods of above-mentioned heat resistant type wet-solidifying single-component polyurethane adhesive, including following step
It is rapid:
Castor oil modified polyester polyol, polyvalent alcohol, diisocyanate and catalyst are mixed, pre-reaction is carried out, adds
Enter chain extender, carries out chain extending reaction, obtain base polyurethane prepolymer for use as；Silanization nano silica is added to base polyurethane prepolymer for use as
It is modified reaction, solvent is added and is diluted, adds antioxidant, obtains heat resistant type wet-solidifying single-component polyurethane gluing
Agent.
According to the present invention, in the preparation method of above-mentioned polyurethane adhesive, the temperature of pre-reaction is 70~90 DEG C, pre-reaction
Time be 2~3h.
According to the present invention, in the preparation method of above-mentioned polyurethane adhesive, the temperature of chain extending reaction is 70~90 DEG C, chain extension
The time of reaction is 1~2h.
According to the present invention, in the preparation method of above-mentioned polyurethane adhesive, the temperature of modified-reaction is 70~90 DEG C, modified
The time of reaction is 2~3h.Preferably, after solvent being added, 35~40 DEG C is cooled to, antioxidant is added.
According to the present invention, in the preparation method of above-mentioned polyurethane adhesive, castor oil modified polyester polyol, gather it is polynary
The mass percent of alcohol, diisocyanate and catalyst is (10-15): (30-50): (15-35): (0.01-0.1).
According to the present invention, in the preparation method of above-mentioned polyurethane adhesive, castor oil modified polyester polyol, polyvalent alcohol
After pretreatment, mixed；The pretreatment for example can be vacuum dehydration.
The present invention also provides the purposes of above-mentioned heat resistant type wet-solidifying single-component polyurethane adhesive, are used for timber processing neck
The bonding in domain uses.
The invention has the following beneficial effects:
Castor oil modified polyester polyol can draw rigid phenyl ring when part substitution polyvalent alcohol is used for polyurethane-modified
Enter into soft segment, controls the crystallite distribution in soft segment structure, enhance glue-line flexibility, cohesive strength increases, and improves heat resistance
Energy；Meanwhile the degree of functionality of castor oil polyester polyol institute hydroxyl after modified is 2.0~2.5, and polymer can be effectively controlled
The degree of cross linking, prevent the degree of cross linking it is excessive cause Adhensive performance sharply decline or gel generation.Therefore, changed using castor oil
Property polyester polyol is remarkably improved the adhesive property and heat resistance of adhesive to polyurethane-modified.
Surface silanization is carried out to nano silica using gamma-aminopropyl-triethoxy-silane to be modified, and is improved and is gathered
Compatibility between urethane, meanwhile, silanization nano-silicon dioxide particle surface grafting has end-NH2Organic molecule chain, can be with
End-NCO base in polyurethane molecular chain reacts, and nano silica and polyurethane are further enhanced in the form of chemical bond
Compatibility.Using the nano-silicon dioxide modified polyurethane adhesive of silanization, the heat-resisting of polyurethane adhesive can be significantly improved
Property.
The present invention is modified to polyurethane double using the pure and mild silanization nano silica of castor oil modified polyester polyols, right
It improves adhesive strength, the heat resistance of polyurethane adhesive etc. performance and plays synergistic effect, performance is significantly improved.
Polyurethane adhesive of the present invention through castor oil modified polyester polyol, the dual modified preparation of silanization nano silica, tool
There are excellent adhesive property, heat resistance, it is dry to solve timber in timber process up to 160 DEG C or more for heat resisting temperature
The bonding problem to crack at bonding wood when dry, the high temperature roasting procedure such as do bent plate.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read documented content of the invention, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within limited range of the present invention.
Embodiment 1
A kind of heat resistant type wet-solidifying single-component polyurethane adhesive and preparation method thereof, mainly comprises the steps that
(1) synthesis of castor oil modified polyester polyol
Be added in the reaction kettle of logical nitrogen 15g castor oil, 25g phthalic anhydride, 30g diglycol and
0.05g catalyst methanesulfonic acid separates the water generated and polyester polyol with toluene, and vacuum is esterified dehydration at 160 DEG C
After 2.5h, 220 DEG C are warming up to, holding evaporates a temperature not less than 100 DEG C of reaction 5h, and it is dry that cooling is placed on 50 DEG C of vacuum ovens
It is dry, obtain castor oil modified polyester polyol；
(2) silylating reagent of nano silica
11g nano silica and 14g solvent N-methyl pyrilidone is taken to mix, at room temperature after ultrasonic disperse 1.5h,
Be heated to 35 DEG C, 2g gamma-aminopropyl-triethoxy-silane be added into reaction system, after reacting 4.5h, carry out it is cooling, be centrifuged it is heavy
It forms sediment, is washed repeatedly with dehydrated alcohol, silanization nano silica is obtained after vacuum drying；
(3) preparation of modified polyurethane adhesive
Take the polyadipate -1,4- butanediol ester of castor oil modified polyester polyol made from 10g, 30g molecular weight 2000
Two pure and mild 30g toluene di-isocyanate(TDI)s are added in reaction kettle, and 0.02g catalyst dibutyltin dilaurylate is added at 85 DEG C
2h is reacted, base polyurethane prepolymer for use as is obtained；75 DEG C are cooled to, 5g1 is added, 4- butanediol reacts 2h, adds 5g silanization and receive
Rice silica is to base polyurethane prepolymer for use as modified-reaction 2h；Then after addition 20g solvent butanone is diluted, is cooled to 40 DEG C,
0.01g antioxidant 264 is added, obtains heat resistant type wet-solidifying single-component polyurethane adhesive after mixing evenly.
Each feature of polyurethane adhesive through the dual modified preparation of the pure and mild epoxy resin of castor oil modified polyester polyols
See Table 1 for details for parameter.
Embodiment 2
A kind of polyurethane adhesive and preparation method thereof of difficult bonding hardwood, mainly comprises the steps that
(1) preparation of castor oil modified polyalcohol
25g castor oil, 35g phthalic anhydride, 22g ethylene glycol and 0.08g catalysis are added in the reaction kettle of logical nitrogen
Agent methanesulfonic acid separates the water generated and polyester polyol with toluene, at 150 DEG C after vacuum esterification dehydration 3h, heating
To 200 DEG C, holding evaporates a temperature not less than 100 DEG C of reaction 5h, and cooling is placed on 60 DEG C of vacuum ovens dryings, obtains castor-oil plant
Oily modified poly ester polyalcohol；
(2) silylating reagent of nano silica
It takes 12g nano silica and 16g solvent N-methyl pyrilidone to mix, at room temperature after ultrasonic disperse 2h, adds
2.5g gamma-aminopropyl-triethoxy-silane is added into reaction system to 35 DEG C for heat, after reacting 4h, carry out it is cooling, be centrifuged it is heavy
It forms sediment, is washed repeatedly with dehydrated alcohol, silanization nano silica is obtained after vacuum drying；
(3) preparation of modified polyurethane adhesive
Take castor oil modified polyester polyol made from 7.5g, the polytetrahydrofuran ether glycol of 40g molecular weight 1000 and
Diphenyl methane -4 27.5g, 4 '-diisocyanate are added in reaction kettle, and 0.03g octoate catalyst stannous is added at 80 DEG C
3h is reacted, base polyurethane prepolymer for use as is obtained；70 DEG C are cooled to, 6g dipropylene glycol reaction 2h is added, adds 4g silanization
Nano silica is to base polyurethane prepolymer for use as modified-reaction 1h；Then 15g solvent butanone is added to be diluted, be cooled to 35 DEG C
Afterwards, 0.02g antioxidant 1010 is added, obtains heat resistant type wet-solidifying single-component polyurethane adhesive after mixing evenly.
Each feature of polyurethane adhesive through the dual modified preparation of the pure and mild epoxy resin of castor oil modified polyester polyols
See Table 1 for details for parameter.
Embodiment 3
A kind of polyurethane adhesive and preparation method thereof of difficult bonding hardwood, mainly comprises the steps that
(1) preparation of castor oil modified polyalcohol
20g castor oil, 15g phthalic anhydride, 18g neopentyl glycol and 0.05g is added in the reaction kettle of logical nitrogen to urge
Agent methanesulfonic acid separates the water generated and polyester polyol with butyl acetate, and vacuum is esterified dehydration 2h at 150 DEG C
Afterwards, 200 DEG C are warming up to, holding evaporates a temperature not less than 100 DEG C of reaction 4h, and cooling is placed on 40 DEG C of vacuum ovens dryings, i.e.,
Castor oil modified polyester polyol is made；
(2) silylating reagent of nano silica
It takes 13g nano silica and 15g solvent N-methyl pyrilidone to mix, at room temperature after ultrasonic disperse 1h, adds
2g gamma-aminopropyl-triethoxy-silane is added into reaction system to 35 DEG C for heat, after reacting 4h, carries out cooling, centrifugation,
It is washed repeatedly with dehydrated alcohol, silanization nano silica is obtained after vacuum drying.
(3) preparation of modified polyurethane adhesive
Take the polyadipate -1,4- butanediol ester of castor oil modified polyester polyol made from 15g, 35g molecular weight 2000
Two pure and mild 30g hexamethylene diisocyanates are added in reaction kettle, and 0.01g catalyst dibutyltin dilaurylate is added 90
2h is reacted at DEG C, obtains base polyurethane prepolymer for use as；75 DEG C are cooled to, 4g1 is added, 4- butanediol reacts 1h, adds 6g silane
Change nano silica to base polyurethane prepolymer for use as modified-reaction 3h；Then 10g solvent acetone is added to be diluted, be cooled to 40 DEG C
Afterwards, 0.05g antioxidant 5570 is added, obtains heat resistant type wet-solidifying single-component polyurethane adhesive after mixing evenly.
Each feature of polyurethane adhesive through the dual modified preparation of the pure and mild epoxy resin of castor oil modified polyester polyols
See Table 1 for details for parameter.
Embodiment 4
A kind of polyurethane adhesive and preparation method thereof of difficult bonding hardwood, mainly comprises the steps that
(1) preparation of castor oil modified polyalcohol
25g castor oil, 25g phthalic anhydride, 20g neopentyl glycol and 0.03 catalysis are added in the reaction kettle of logical nitrogen
Agent methanesulfonic acid separates the water generated and polyester polyol with toluene, at 150 DEG C after vacuum esterification dehydration 3h, then
It is warming up to 170 DEG C the reaction was continued 4h, cooling to be placed on 50 DEG C of vacuum ovens dry, obtains castor oil modified polyester polyols
Alcohol；
(2) silylating reagent of nano silica
It takes 10g nano silica and 12g solvent N-methyl pyrilidone to mix, at room temperature after ultrasonic disperse 1h, adds
3g gamma-aminopropyl-triethoxy-silane is added into reaction system to 35 DEG C for heat, after reacting 5h, carries out cooling, centrifugation,
It is washed repeatedly with dehydrated alcohol, silanization nano silica is obtained after vacuum drying.
(3) preparation of modified polyurethane adhesive
Take castor oil modified polyester polyol made from 5g, the polyoxypropyleneglycol of 50g molecular weight 2000 and 20g toluene
Diisocyanate is added in reaction kettle, and 0.01g catalyst dibutyltin dilaurylate is added and reacts 3h at 85 DEG C, is gathered
Urethane performed polymer；80 DEG C are cooled to, 8g diglycol reaction 2h is added, adds 2g silanization nano silica pair
Base polyurethane prepolymer for use as modified-reaction 2h；Then after addition 15g solvent acetic acid ethyl ester is diluted, is cooled to 35 DEG C, 0.04g is added
Antioxidant 264 obtains heat resistant type wet-solidifying single-component polyurethane adhesive after mixing evenly.
Each feature of polyurethane adhesive through the dual modified preparation of the pure and mild epoxy resin of castor oil modified polyester polyols
See Table 1 for details for parameter.
Embodiment 5
A kind of polyurethane adhesive and preparation method thereof of difficult bonding hardwood, mainly comprises the steps that
(1) preparation of castor oil modified polyalcohol
18g castor oil, 21g phthalic anhydride, 25g propylene glycol and 0.06 catalyst is added in the reaction kettle of logical nitrogen
Methanesulfonic acid separates the water generated and polyester polyol with butyl acetate, at 160 DEG C after vacuum esterification dehydration 2h, rises
Temperature is to 210 DEG C, and holding evaporates a temperature not less than 100 DEG C of reaction 5h, and cooling is placed on 50 DEG C of vacuum ovens dryings, obtains castor
Sesame oil modified poly ester polyalcohol；
(2) silylating reagent of nano silica
It takes 14g nano silica and 11g solvent N-methyl pyrilidone to mix, at room temperature after ultrasonic disperse 1h, adds
5g gamma-aminopropyl-triethoxy-silane is added into reaction system to 35 DEG C for heat, after reacting 4h, carries out cooling, centrifugation,
It is washed repeatedly with dehydrated alcohol, silanization nano silica is obtained after vacuum drying.
(3) preparation of modified polyurethane adhesive
Take the polyethylene glycol adipate two of castor oil modified polyester polyol made from 15g, 30g molecular weight 3000 pure and mild
35g isophorone diisocyanate is added in reaction kettle, and 0.05g octoate catalyst stannous is added and reacts 2.5h at 80 DEG C,
Obtain base polyurethane prepolymer for use as；75 DEG C are cooled to, 7g1 is added, 6- hexylene glycol reacts 1.5h, adds 3g silanization nano-silica
SiClx is to base polyurethane prepolymer for use as modified-reaction 2h；Then after addition 10g solvent butyl acetate is diluted, is cooled to 40 DEG C, add
Enter 0.03g antioxidant 1010, obtains heat resistant type wet-solidifying single-component polyurethane adhesive after mixing evenly.
Each feature of polyurethane adhesive through the dual modified preparation of the pure and mild epoxy resin of castor oil modified polyester polyols
See Table 1 for details for parameter.
Comparative example 1
(1) preparation of castor oil modified polyester polyol
Castor oil, phthalic anhydride, ethylene glycol and catalyst methanesulfonic acid is added in the reaction kettle of logical nitrogen, uses toluene
Make the water generated and polyester polyol separation, at 150 DEG C after vacuum esterification dehydration 2.5h, is warming up to 210 DEG C, keeps evaporating
Head temperature is not less than 100 DEG C of reaction 4h, cooling to be placed on 50 DEG C of vacuum ovens dryings, obtains castor oil modified polyester polyols
Alcohol；
(2) preparation of modified polyurethane adhesive
Take castor oil modified polyester polyol made from 10g, the polyoxypropyleneglycol of 40g molecular weight 1000 and 30g first
Phenylene diisocyanate is added in reaction kettle, and 0.02g catalyst dibutyltin dilaurylate is added and reacts 2.5h at 88 DEG C, obtains
To base polyurethane prepolymer for use as；70 DEG C are cooled to, 8g diglycol is added the reaction was continued 2h；Then solvent acetic acid ethyl ester is added
After being diluted, being cooled to 40 DEG C, 0.03g antioxidant 264 is added, obtains heat resistant type mono component wet solidifying after mixing evenly
Polyurethane adhesive.
See Table 1 for details for each characteristic parameter of the modified polyurethane adhesive prepared through castor oil modified polyester polyol.
Comparative example 2
(1) silylating reagent of nano silica
It takes 15g nano silica and 12g solvent N-methyl pyrilidone to mix, at room temperature after ultrasonic disperse 1h, adds
4g gamma-aminopropyl-triethoxy-silane is added into reaction system to 35 DEG C for heat, after reacting 4h, carries out cooling, centrifugation,
It is washed repeatedly with dehydrated alcohol, silanization nano silica is obtained after vacuum drying.
(2) preparation of modified polyurethane adhesive
The polyoxypropyleneglycol and 30g toluene di-isocyanate(TDI) for taking 45g molecular weight 2000 are added in reaction kettle, are added
0.04g catalyst dibutyltin dilaurylate reacts 2.5h at 88 DEG C, obtains base polyurethane prepolymer for use as；It is cooled to 70 DEG C, then plus
Enter 8g diglycol reaction 2h, adds 5g silanization nano silica to base polyurethane prepolymer for use as modified-reaction 2h；So
After addition 12g solvent acetone is diluted, is cooled to 40 DEG C afterwards, 0.02g antioxidant 1010 is added, obtains after mixing evenly
Heat resistant type wet-solidifying single-component polyurethane adhesive.
See Table 1 for details for each characteristic parameter of polyurethane adhesive through the nano-silicon dioxide modified preparation of silanization.
The physical parameter of polyurethane adhesive described in 1 embodiment 1-5 of table
From the data of the embodiment 1-5 and comparative example 1-2 of table 1 it can be found that the present invention is more using castor oil modified polyester
The pure and mild silanization nano silica of member is modified to polyurethane double, to adhesive strength, the heat resistance for improving polyurethane adhesive
Etc. performance play synergistic effect, heat resistance is improved significantly.Polyurethane adhesive prepared by the present invention has excellent
Different adhesive property, heat resistance, heat resisting temperature solve the drying of wood in timber process, do up to 160 DEG C or more
The bonding problem to crack at bonding wood when the high temperature roasting procedure such as bent plate.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of heat resistant type wet-solidifying single-component polyurethane adhesive, which is characterized in that prepare the raw material components of the adhesive
And its content includes:
2. adhesive according to claim 1, which is characterized in that each component including following percentage composition:
3. adhesive according to claim 1 or 2, which is characterized in that the polyvalent alcohol be selected from polyester polyol or
At least one of polyether polyol.
Preferably, the number-average molecular weight of the polyvalent alcohol is 1000~3000g/mol.
Preferably, the polyester polyol is selected from polyethylene glycol adipate glycol, polyadipate diglycol ester two
At least one of alcohol or polyadipate -1,4- butyl glycol ester diol.
Preferably, the polyether polyol is selected from polyoxypropyleneglycol, polytetrahydrofuran ether glycol or tetrahydrofuran-oxidation
At least one of propylene copolymer glycols.
Preferably, the castor oil modified polyester polyol be selected from degree of functionality be 2.0~2.5, number-average molecular weight be 1900 to
The castor oil modified polyester polyol of 4000g/mol.
Preferably, it is different to be selected from toluene di-isocyanate(TDI), hexamethylene diisocyanate, isophorone two for the diisocyanate
At least one of cyanate or diphenyl methane -4,4 '-diisocyanate.
Preferably, the catalyst is selected from least one of dibutyl tin dilaurate, stannous octoate.
Preferably, the chain extender is selected from small molecule dihydric alcohol, and the small molecule dihydric alcohol is selected from C2-6Dihydric alcohol, such as
Selected from least one of ethylene glycol, 1,4- butanediol, diglycol, dipropylene glycol, 1,6-HD.
Preferably, the antioxidant is selected from 2,6-di-tert-butyl p-cresol (such as antioxidant 264), 4,4 '-two t-octyls-
Diphenylamines (such as antioxidant 5570), tetramethylene β-(3,5- di-tert-butyl-hydroxy phenyl) propionate are (as resisted
Oxidant 1010).
Preferably, the solvent is selected from least one of acetone, butanone, ethyl acetate, butyl acetate.
4. adhesive according to any one of claim 1-3, which is characterized in that the castor oil modified polyester polyols
Alcohol is prepared via a method which to obtain:
Castor oil, phthalic anhydride, chain extender and catalyst are mixed, vacuum dehydration reaction is carried out, continues to heat, be prepared into
To castor oil modified polyester polyol.
Preferably, it is carried out under the conditions of inert gas shielding, such as in nitrogen gas, argon gas, helium atmosphere protective condition
Lower progress.
Preferably, the mass percent of castor oil, phthalic anhydride, chain extender and catalyst is (15-25): (15-35):
(18-30):(0.03-0.08)。
Preferably, the temperature of vacuum dehydration reaction is 150~160 DEG C, and the time of vacuum dehydration reaction is 2~3h.Very
Empty dehydration process preferably uses other solvent (such as toluene liquid) fluid-tights, makes the water generated and polyester polyol separation.
Preferably, continue to heat and keep and evaporate a temperature not less than 100 DEG C, react 4~5h.
It preferably, further include drying process, the drying process preferably carries out in 50 DEG C of vacuum ovens.
5. adhesive described in any one of -4 according to claim 1, which is characterized in that the silanization nano silica
It is prepared via a method which to obtain:
By nano silica and N-Methyl pyrrolidone ultrasonic disperse, gamma-aminopropyl-triethoxy-silane, surface is then added
Graft reaction obtains silanization nano silica.
Preferably, in the preparation method of above-mentioned silanization nano silica, the nano silica, N-Methyl pyrrolidone
Mass percent with gamma-aminopropyl-triethoxy-silane is (10-15): (10-30): (1-5).
Preferably, in the preparation method of above-mentioned silanization nano silica, the time of ultrasonic disperse is 1~2h.
Preferably, in the preparation method of above-mentioned silanization nano silica, the temperature of Surface grafting reaction is 35~45 DEG C, table
The time of face graft reaction is 4~6h.Surface grafting reaction preferably carries out under agitation.
Preferably, cooling, centrifugation is carried out after Surface grafting reaction, is washed repeatedly with dehydrated alcohol, and vacuum is dry
Dry processing.
6. adhesive according to any one of claims 1-5, which is characterized in that the heat-resisting temperature of the polyurethane adhesive
Degree is up to 160 DEG C or more, and the polyurethane adhesive is in 160 DEG C of heat drying cracking time >=6 hours.
Preferably, the polyurethane adhesive storage period reaches >=6 months, resistance to boiling water boiling time >=6 hour, compression shear strength
>=10.0MPa, tensile shear strength >=5.0MPa.
7. adhesive according to claim 1 to 6, which is characterized in that the heat resistant type mono component wet solidifying is poly-
Urethane adhesive can be prepared by the following method, comprising: by castor oil modified polyester polyol, polyvalent alcohol, two different
Cyanate and catalyst mixing, carry out pre-reaction, chain extender are added, carry out chain extending reaction, obtain base polyurethane prepolymer for use as；It adds
Silanization nano silica is modified reaction to base polyurethane prepolymer for use as, and solvent is added and is diluted, adds antioxidant,
Obtain heat resistant type wet-solidifying single-component polyurethane adhesive.
Preferably, the temperature of pre-reaction is 70~90 DEG C, and the time of pre-reaction is 2~3h.
Preferably, the temperature of chain extending reaction is 70~90 DEG C, and the time of chain extending reaction is 1~2h.
Preferably, the temperature of modified-reaction is 70~90 DEG C, and the time of modified-reaction is 2~3h.Preferably, after solvent being added,
35~40 DEG C are cooled to, antioxidant is added.
Preferably, the mass percent of castor oil modified polyester polyol, polyvalent alcohol, diisocyanate and catalyst is (10-
15):(30-50):(15-35):(0.01-0.1)。
Preferably, it after castor oil modified polyester polyol, polyvalent alcohol are preferably through pretreatment, is mixed；The pretreatment
Such as it can be vacuum dehydration.
8. the preparation method of heat resistant type wet-solidifying single-component polyurethane adhesive of any of claims 1-7, special
Sign is, the described method comprises the following steps:
Castor oil modified polyester polyol, polyvalent alcohol, diisocyanate and catalyst are mixed, pre-reaction is carried out, is added and expands
Chain agent carries out chain extending reaction, obtains base polyurethane prepolymer for use as；Silanization nano silica is added to carry out base polyurethane prepolymer for use as
Modified-reaction is added solvent and is diluted, adds antioxidant, obtain heat resistant type wet-solidifying single-component polyurethane adhesive.
9. preparation method according to claim 8, which is characterized in that the temperature of pre-reaction is 70~90 DEG C, pre-reaction
Time is 2~3h.
Preferably, the temperature of chain extending reaction is 70~90 DEG C, and the time of chain extending reaction is 1~2h.
Preferably, the temperature of modified-reaction is 70~90 DEG C, and the time of modified-reaction is 2~3h.
Preferably, after solvent being added, 35~40 DEG C is cooled to, antioxidant is added.
Preferably, the mass percent of castor oil modified polyester polyol, polyvalent alcohol, diisocyanate and catalyst is (10-
15):(30-50):(15-35):(0.01-0.1)。
Preferably, it after castor oil modified polyester polyol, polyvalent alcohol are preferably through pretreatment, is mixed；The pretreatment
Such as it can be vacuum dehydration.
10. the purposes of heat resistant type wet-solidifying single-component polyurethane adhesive of any of claims 1-7, is used for wood
The bonding of material manufacture field uses.
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| CN111394044A (en) * | 2020-04-16 | 2020-07-10 | 上海炼升化工股份有限公司 | Fast-curing high-temperature-resistant adhesive and preparation method thereof |
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| CN112358842A (en) * | 2020-09-29 | 2021-02-12 | 无锡市佳盛高新改性材料有限公司 | Preparation method of organic silicon polyurethane adhesive |
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| CN112557582A (en) * | 2020-12-17 | 2021-03-26 | 南通恒华粘合材料科技有限公司 | Method for measuring hydroxyl value of polyester polyol |
| CN112724916A (en) * | 2020-12-28 | 2021-04-30 | 上海华峰新材料研发科技有限公司 | Solvent-free adhesive for electrical insulation composite material and preparation method and application thereof |
| CN113105824B (en) * | 2021-04-13 | 2022-05-20 | 湖南福森竹木科技有限公司 | Anti-cracking wood board and preparation method thereof |
| CN113105824A (en) * | 2021-04-13 | 2021-07-13 | 湖南福森竹木科技有限公司 | Anti-cracking wood board and preparation method thereof |
| CN114456763A (en) * | 2022-02-28 | 2022-05-10 | 河南省海绵城市建设有限公司 | Single-component polyurethane adhesive and preparation method and application thereof |
| CN115109556A (en) * | 2022-06-29 | 2022-09-27 | 上海回天新材料有限公司 | High-temperature-cooking-resistant solvent-free two-component polyurethane adhesive and preparation method thereof |
| KR102506527B1 (en) * | 2022-08-17 | 2023-03-08 | 주식회사 그래핀 코어 | Manufacturing method of polyol pre-polymer comprising nano copper and Manufacturing method of antibacterial wood using thereof |
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