CN109852326A - A kind of polyurethane thermosol and preparation method thereof containing oxime urethane dynamic key - Google Patents
A kind of polyurethane thermosol and preparation method thereof containing oxime urethane dynamic key Download PDFInfo
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- CN109852326A CN109852326A CN201910107536.6A CN201910107536A CN109852326A CN 109852326 A CN109852326 A CN 109852326A CN 201910107536 A CN201910107536 A CN 201910107536A CN 109852326 A CN109852326 A CN 109852326A
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- polyurethane
- oxime
- diisocyanate
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Abstract
The present invention relates to a kind of polyurethane thermosol and preparation method thereof containing oxime urethane dynamic key, polymerized monomer includes: at least one polyisocyanates, at least one small molecule oxime, at least one polyalcohol.Dynamic covalent bond is introduced into the polyurethane hot melt system of crosslinking by the present invention, it can make thermosetting material that there is certain thermoplastic property using the introducing of dynamic key, obtain having both the hot melt adhesive of thermoplastic polyurethane Yu reaction type polyurethane hot-melt adhesive advantage, for the practical application of adhesive for polyurethane, there is very big practical significance.
Description
Technical field
The invention belongs to thermosol field, in particular to a kind of polyurethane-hot melt gluing containing oxime urethane dynamic key
Agent and preparation method thereof.
Background technique
Thermosol is a kind of adhesive of no-solvent type, is solid under room temperature, do not have caking property, heating melting with
After can flow, good wetting action occurs with surface, there is excellent adhesive property after cooling.With solvent type adhesive
It compares, thermosol (HMA) is expected to become next-generation Green adhesive, because its adhesive for solvent-free use can be to avoid volatilization
The discharge of property organic compound (VOCs).The adjustability of polyurethane performance is very strong, and polyurethane hot melt is a kind of important hot melt
Adhesive.Existing hot melt urethane adhesives are broadly divided into two classes, and one kind is thermoplastic polyurethane (TPU) adhesive,
It is flowable and fix while cooling when being heated to certain temperature.Another kind is reaction type polyurethane (PUR), when it is fully cured
With permanent cross-linked structure.Reaction type polyurethane (PUR) usually indicates there is the isocyanate-terminated linear of low molecular weight
Polyurethane, can further with the reaction of moisture from atmosphere and ultimately form permanent cross-linked structure.With thermoplastic polyurethane
(TPU) it compares, reaction type polyurethane PUR usually has higher adhesive strength due to its permanent cross-linked structure, preferably resistance to
Hot and excellent chemical resistance.However, since its molecular weight is lower, curing rate is slower, at the beginning of reaction type polyurethane (PUR)
Beginning adhesive strength is generally lower.If ambient enviroment relatively dry, reaction type polyurethane (PUR) can hardly form friendship
Networking network, even if it also always needs could sufficiently react with moisture for several days under relatively wet atmosphere.In addition to this, by
There are a large amount of active isocyanate groups in reaction type polyurethane, therefore reaction type polyurethane (PUR) is with relatively short
Storage period.Moreover, cross-linked structure once being formed, it can hardly be removed from substrate.On the other hand, thermoplastic polyurethane bonds
Agent has the performance of some complementations, such as relatively high initial adhesion strength, longer Storage period and reversible adhesiveness.
Dynamic key is that a series of chemical reversible reaction based on reversible balances is formed by chemical bond, they can be certain
Under external condition (such as heat, pH value, light and catalyst) stimulation, reversible " fracture " and " in conjunction with " can occur, thus
Realize intermolecular Dynamic Separation and recombination.Dynamic key is introduced into extensively in crosslinking polymer system in recent years, assigns material
Expect some self-healings, the performance processed again, such as CN2017100311502.But the material previously based on dynamic key preparation, mostly
Report only focuses on the ability of self-healing and reprocessing with material, is not also many for the adhesive report containing dynamic key.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of polyurethane thermosols containing oxime urethane dynamic key
And preparation method thereof, which has both thermoplastic polyurethane and reaction type polyurethane hot-melt adhesive advantage, has
Good adhesive property and reversible adhesiveness.
The present invention provides a kind of polyurethane thermosol containing oxime urethane dynamic key: polymerized monomer includes: at least
A kind of polyisocyanates, at least one small molecule oxime, at least one polyalcohol.
Further, it is different to be selected from toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, naphthalene two for the polyisocyanates
Oneself is two different by cyanate, paraphenylene diisocyanate, dimethyl diphenyl diisocyanate, polymethylene multi-phenenyl isocyanate, 1,6-
Cyanate, trimethyl -1,6- hexamethylene diisocyanate, phenylenedimethylidyne isocyanates, tetramethyl m-phenylenedimethylim- two
Isocyanates, isophorone diisocyanate, 1,4- cyclohexane diisocyanate, cyclohexanedimethyleterephthalate diisocyanate, drop
At least one of bornylane diisocyanate.
Further, the small molecule oxime is selected from dimethylglyoxime (dimethyl acetaldoxime), pyroracemic aldehyde dioxime, Isosorbide-5-Nitrae-benzoquinones two
Oxime, terephthalaldehyde dioxime, 1,3,5- benzene front three aldoxime, 4- amino benzyl amidoxime, 2- propoxybenzaldehyde oxime, 2- amino benzyl ammonia
At least one of oxime, cyclopropane -1- carboxamidoxime, furans -2- carboxamidoxime, 2,3- 4-dihydroxy benzaldehyde oxime.
Further, the polyalcohol is selected from glycerol, trimethylolpropane, pentaerythrite, sorbierite, castor oil, poly- four
Hydrogen furans glycol, polyoxypropyleneglycol, tetrahydrofuran-propylene oxide copolymer glycols, polyethylene glycol adipate, polyadipate
Butanediol ester, polyphenyl dioctyl phthalate diol ester, polyadipate-hexylene glycol ester, polyneopentyl glycol adipate, in poly- caprolactone
It is at least one
Preferably, the general structure of the polyurethane thermosol is as follows:
Wherein, the range of m is 2~150；The range of n is 2~600；R1For R2ForR3For Length be 50~700.
The present invention also provides a kind of preparation methods of polyurethane thermosol containing oxime urethane dynamic key, comprising:
At least one polyalcohol, at least one small molecule oxime are dissolved in organic solvent, are completely dissolved to small molecule dioxime,
Add at least one polyisocyanates and catalyst, at 50~60 DEG C react 12~for 24 hours, then heating removal it is organic molten
Agent to get.
Further, the organic solvent is acetone, in tetrahydrofuran, dimethylformamide, methylene chloride, cyclohexanone
It is a kind of.
Further, the catalyst is dibutyl tin dilaurate, stannous octoate, triethylamine, N, N- dimethyleyelohexane
One of amine, triethanolamine
Beneficial effect
Dynamic covalent bond is introduced into the polyurethane hot melt system of crosslinking by the present invention, can be made using the introducing of dynamic key
Thermosetting material has certain thermoplastic property, obtains having both thermoplastic polyurethane and reaction type polyurethane hot-melt adhesive advantage
Hot melt adhesive, initial bond strength with higher and final adhesion strength, have good solvent resistant at faster curing rate
Property, adhesive can remove and may be reused, and have longer storage period, for the practical application of adhesive for polyurethane
For, there is very big practical significance.
Detailed description of the invention
Fig. 1 is the synthetic route of 1 product of embodiment (DMG-CPU)；
Fig. 2 is the structure variation with temperature schematic diagram of 1 product of embodiment (DMG-CPU)；
Fig. 3 is the infrared absorpting light spectra that 1 product of embodiment (DMG-CPU) varies with temperature；
Fig. 4 is 1 product of embodiment (DMG-CPU), commercially available thermoplastic polyurethane hot melt adhesive (TPU), commercially available response type
Polyurethane hot melt (Henkel Loctite 3542,3M2665) bonds the lap shear strength comparison of stainless steel different time；
Fig. 5 is 1 product of embodiment (DMG-CPU), commercially available thermoplastic polyurethane hot melt adhesive (TPU) bonds the first of stainless steel
Adhesive strength after impregnating 18h in beginning adhesive strength and acetone solvent compares；
Fig. 6 is 1 product of embodiment (DMG-CPU), commercially available thermoplastic polyurethane hot melt adhesive (TPU), commercially available response type
Polyurethane hot melt (Henkel Loctite 3542,3M2665) bonds stainless steel, aluminium, pine, phenolic resin, epoxy resin, glass and increases
The lap shear strength comparison of strong epoxy resin；
Fig. 7 is pulling force-displacement of 1 product of embodiment (DMG-CPU), initial adhesion stainless steel and second of bonding stainless steel
Curve
Fig. 8 is the synthetic route of product of the present invention.
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.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
(1) experimental raw
Polytetrahydrofuran diol (PTMG, Mn=~1000g mol-1, Aladdin), methyl diphenylene diisocyanate
(MDI, 99%, Aladdin) and dibutyl tin dilaurate (DBTDL, 95%, Aladdin)；Dimethylglyoxime (DMG, 98%,
Chinese medicines group) and glycerine (99%, Chinese medicines group).Acetone (99.8%, forever Cheng Huaxue).
(2) preparation method
First by the above raw material according to the mol ratio feeding drafted, for example, take polytetrahydrofuran diol (PTMG,
0.575g, 1 molfraction), dimethylglyoxime (DMG, 0.200g, 3 molfraction), glycerine (GLY, 0.026g, 0.5 molar part
Number) it is dissolved in 5ml acetone；It is completely dissolved to dimethylglyoxime, and after forming colourless transparent liquid, it is different that diphenyl methane two is added
Cyanate (MDI, 0.682g, 4.75 molfraction) and dibutyl tin dilaurate (DBTDL, 0.015g, 1wt%)；Mixing is equal
After even, liquid mixture is transferred in tetrafluoro mold, and the tetrafluoro mold for filling liquid mixture is put into 50 DEG C of baking oven
Middle 12h reacts mixture sufficiently, then heats to 70 DEG C of remaining solvents of removal, finally takes out from baking oven, can be four
A transparent polyurethane-hot melt glue film is obtained in fluorine mold, is denoted as DMG-CPU, structural formula are as follows:
Wherein, 52, m:n=1:3 x.
(3) dynamic of oxime ammonia ester bond proves
Oxime ammonia ester bond has stability at normal temperature, at a higher temperature can be reversible dissociate isocyanate groups
With the group of oxime.Due to this property of oxime ammonia ester bond, oximes small molecule is a kind of important in reaction type polyurethane hot-melt adhesive
End-capping reagent, using more stable oxime ammonia ester bond is formed at room temperature, to avoid isocyanate groups and the moisture in air anti-
It answers, extends the service life of reaction type polyurethane hot-melt adhesive；Isocyanate groups can be dissociateed again at a higher temperature, are reached
To the purpose with moisture-curable enhancing adhesive property.
Small molecule dioxime is introduced into the polyurethane system of crosslinking by the present invention, makes to contain reversible oxime ammonia in molecular backbone
Ester dynamic key has preferable stability at room temperature, keeps cross-linked structure, the dissociation that oxime ammonia ester bond can be reversible at high temperature
Isocyanate groups out destroy cross-linked structure, and polyurethane has certain mobility at a higher temperature, so as to so that
This hot melt adhesive film can soak substrate surface enough at high temperature, can re-form crosslinking knot after being cooled to room temperature again
Structure.Using in polyurethane system, there are more hydrogen bond action and the chemical structures of possessed crosslinking, can be with substrate shape
At preferable adhesive property.
Using reversible change of the heating infrared spectrum analysis oxime ammonia ester bond in situ during varying with temperature, by heating up
Infrared spectrogram in journey can be seen that (Fig. 3), at 100 DEG C hereinafter, 2275cm-1Locate the suction without there is apparent isocyanates
Receive peak, after temperature is more than 110 DEG C, 2275cm-1Place isocyanates absorption peak intensity gradually increasing, illustrate be more than in temperature
The rate that oxime ammonia ester bond dissociates isocyanates after 110 DEG C becomes larger.But temperature it is excessively high more than 140 DEG C after, 2275cm-1
The absorption peak of place's isocyanates is becoming smaller, this is because side reaction has occurred in isocyanate groups at a higher temperature.
(4) the adhesive property test of polyurethane thermosol
In order to prove the adhesive property of the polyurethane thermosol containing oxime urethane dynamic key, commercially available heat is tested respectively
Plastic polyurethane hot melt adhesive (TPU), commercially available reaction type polyurethane hot-melt adhesive (Henkel Loctite 3542,3M2665) and contain oxime urethane
The lap shear strength of adhesive for polyurethane (DMG-CPU) the bonding stainless steel of dynamic key.As shown in figure 4, dynamic containing oxime urethane
Polyurethane thermosol (DMG-CPU) initial bond strength with higher of state key, 5min just has 3MPa left after sizing
Right adhesion strength, and adhesive can be fully cured substantially after sizing 1 day, and the bonding with 6MPa or so is strong
Degree.And the initial bond strength that reaction type polyurethane hot-melt adhesive sticks agent is relatively low, the adhesion strength after sizing in 30min exists
0.5MPa is hereinafter, this is because this kind of reaction type polyurethane hot-melt adhesive is by isocyanate-terminated polyurethane prepolymer, molecule
It measures relatively low, reacts to form cross-linked structure with the moisture in air by isocyanates, test result shows that curing rate compares
Slowly, the adhesion strength after sizing after 14 days can achieve 6MPa or so, with the polyurethane hot melt containing oxime urethane dynamic key
Adhesion strength after sizing after 1 day is suitable.The curing rate of thermoplastic polyurethane adhesive is relatively fast, and sizing has after one day
The adhesive strength of 4MPa or so can achieve the adhesion strength of 5MPa or so after solidifying 7 days.Adhesive phase with cross-linked structure
More some higher than thermoplastic adhesive bonds intensity, cross-linked structure can also make adhesive have certain solvent resistance.
As shown in figure 5, found after impregnating 18h in acetone with commercially available TPU hot melt adhesive stainless steel Nian Jie with DMG-CPU,
Fallen off with the two panels stainless steel that TPU hot melt adhesive bonds, do not have an adhesion strength, and it is same under the conditions of, DMG-CPU is bonded not
Rust steel still has the nearly adhesion strength of 3MPa or so after impregnating 18h in acetone.This explanation contains oxime urethane dynamic key
Polyurethane hot melt initial bond strength with higher, faster curing rate, it is stronger final adhesion strength, certain
Chemical reagent resistance.
In order to illustrate the practicability of the polyurethane thermosol containing oxime urethane dynamic key, it is viscous to be also tested for DMG-CPU
The feasibility of different substrate materials, including metal, timber, plastics, composite material are tied, and glutinous with commercially available thermoplastic polyurethane hot melt adhesive
Agent is compared with reaction type hot-fusible gluing agent.Since response type adhesive curing rate is slower, reaction type polyurethane heat is tested
Melten gel solidifies the adhesion strength after 7 days, and TPU and DMG-CPU are the adhesion strengths after being glued one day.Such as Fig. 6, test result table
Show, DMG-CPU has preferable bonding to stainless steel, aluminium, pine, phenolic resin, epoxy resin, glass fiber reinforced epoxy resin
Property.It may be speculated that there is very big relationship with cross-linked structure in this excellent adhesive property and adhesive for polyurethane, and
Oxime ammonia ester bond can dissociate isocyanate groups at a higher temperature, if substrate surface is containing can be with isocyanate group
The active hydrogen of group's reaction further enhances adhesion strength then can form covalently key connection between adhesive and substrate.
Disassembled type adhesive is also a kind of critically important adhesive, can satisfy the dismantling and recycling benefit of bonding component
With for the biggish mechanical force of component dismantling needs of cross-linking type adhesive bond, and it is possible to glued component can be destroyed,
Become difficult the recycling of component.Although the adhesive for polyurethane containing oxime urethane dynamic key has cross-linked structure, by
It can be dissociated at a higher temperature in oxime ammonia ester bond, therefore this kind of adhesive is also used as disassembled adhesive,
For heat-resisting component, being heated to the dissociation temperature of oxime ammonia ester bond or more just can be such that glued component easily tears open
Solution.The weight of 300g can be born by the DMG-CPU stainless steel being bonded at room temperature, after heating 30s with heat gun, adhesive is just
It is destroyed, the stainless steel bonded is easy for be disassembled.
This thermosol containing dynamic key also has the performance of repeatable bonding, as shown in fig. 7, it is viscous to test it
After the primary failure of knot, stainless steel is bonded according to original glue-applying technique again, discovery is in second of bonding stainless steel, basic energy
Enough keep first adhesion strength.It is this to repeat the performance recycled recycling with very big meaning for material
Justice.
Claims (8)
1. a kind of polyurethane thermosol containing oxime urethane dynamic key, it is characterised in that: polymerized monomer includes: at least one
Polyisocyanates, at least one small molecule oxime, at least one polyalcohol.
2. polyurethane thermosol according to claim 1, it is characterised in that: the polyisocyanates is selected from toluene two
Isocyanates, methyl diphenylene diisocyanate, naphthalene diisocyanate, paraphenylene diisocyanate, dimethyl diphenyl diisocyanate
Ester, polymethylene multi-phenenyl isocyanate, hexamethylene diisocyanate, trimethyl -1,6- hexamethylene diisocyanate, benzene two
Methylene based isocyanate, tetramethyl m-xylylene diisocyanate, isophorone diisocyanate, 1,4- hexamethylene two are different
At least one of cyanate, cyclohexanedimethyleterephthalate diisocyanate, norbornene alkyl diisocyanate.
3. polyurethane thermosol according to claim 1, it is characterised in that: the small molecule oxime is selected from diacetyl
Oxime, pyroracemic aldehyde dioxime, 1,4- benzoquinones dioxime, terephthalaldehyde dioxime, 1,3,5- benzene front three aldoxime, 4- amino benzyl amidoxime, 2- third
Oxygroup benzaldoxime, 2- amino benzyl amidoxime, cyclopropane -1- carboxamidoxime, furans -2- carboxamidoxime, in 2,3- 4-dihydroxy benzaldehyde oxime
At least one.
4. polyurethane thermosol according to claim 1, it is characterised in that: the polyalcohol is selected from glycerol, three hydroxyls
Methylpropane, pentaerythrite, sorbierite, castor oil, polytetrahydrofuran diol, polyoxypropyleneglycol, tetrahydrofuran-oxidation third
Alkene copolymer glycols, polyethylene glycol adipate, poly adipate succinic acid ester, polyphenyl dioctyl phthalate diol ester, polyadipate-hexylene glycol
At least one of ester, polyneopentyl glycol adipate, poly- caprolactone.
5. polyurethane thermosol according to claim 1, it is characterised in that: the knot of the polyurethane thermosol
Structure general formula is as follows:
Wherein, the range of m is 2~150；The range of n is 2~600；R1For R2ForR3For Length be 50~700.
6. a kind of preparation method of the polyurethane thermosol as described in claim 1 containing oxime urethane dynamic key, comprising:
At least one polyalcohol, at least one small molecule oxime are dissolved in organic solvent, is completely dissolved, adds to small molecule oxime
At least one polyisocyanates and catalyst, at 50~60 DEG C react 12~for 24 hours, then heating removal organic solvent to get.
7. preparation method according to claim 7, it is characterised in that: the organic solvent is acetone, tetrahydrofuran, diformazan
One of base formamide, methylene chloride, cyclohexanone.
8. preparation method according to claim 7, it is characterised in that: the catalyst is dibutyl tin dilaurate, pungent
Sour stannous, triethylamine, N, one of N- dimethyl cyclohexyl amine, triethanolamine.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110066414A (en) * | 2019-04-09 | 2019-07-30 | 东华大学 | A kind of multi-functional multiple-protection material and preparation method thereof |
| CN112126036A (en) * | 2020-09-11 | 2020-12-25 | 常州大学 | Disulfide bond-based biodegradable cross-linked self-repairing polyurethane and preparation method thereof |
| CN112521574A (en) * | 2020-12-07 | 2021-03-19 | 西安交通大学 | Intrinsic black polyurethane with near-infrared thermal effect and preparation and application thereof |
| CN112778489A (en) * | 2020-12-31 | 2021-05-11 | 东华大学 | Reconfigurable driver based on self-healing elastomer and preparation method thereof |
| CN114149555A (en) * | 2021-11-11 | 2022-03-08 | 东华大学 | Self-healing polyurethane and preparation and application thereof |
| CN115028791A (en) * | 2022-05-11 | 2022-09-09 | 东华大学 | Liquid crystal polyurethane material with stress enhancement |
| CN115141353A (en) * | 2022-05-26 | 2022-10-04 | 中国海洋大学 | Self-repairing polyurethane composite material and preparation method and application thereof |
| WO2023168066A1 (en) | 2022-03-04 | 2023-09-07 | Conagen Inc. | Oxime-based hot melt adhesives for rework, repair and recycle |
| WO2023168077A1 (en) | 2022-03-04 | 2023-09-07 | Conagen Inc. | Phenol-based hot melt adhesives for rework, repair and recycle |
| WO2023168045A1 (en) | 2022-03-04 | 2023-09-07 | Conagen Inc. | Hydroxy/amino oxime-based hot melt adhesives for rework, repair and recycle |
| CN115028791B (en) * | 2022-05-11 | 2024-05-10 | 东华大学 | Liquid crystal polyoxime urethane material with stress enhancement |
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| CN110066414A (en) * | 2019-04-09 | 2019-07-30 | 东华大学 | A kind of multi-functional multiple-protection material and preparation method thereof |
| CN110066414B (en) * | 2019-04-09 | 2021-09-21 | 东华大学 | Multifunctional multiple protection material and preparation method thereof |
| CN112126036A (en) * | 2020-09-11 | 2020-12-25 | 常州大学 | Disulfide bond-based biodegradable cross-linked self-repairing polyurethane and preparation method thereof |
| CN112521574A (en) * | 2020-12-07 | 2021-03-19 | 西安交通大学 | Intrinsic black polyurethane with near-infrared thermal effect and preparation and application thereof |
| CN112778489A (en) * | 2020-12-31 | 2021-05-11 | 东华大学 | Reconfigurable driver based on self-healing elastomer and preparation method thereof |
| CN114149555A (en) * | 2021-11-11 | 2022-03-08 | 东华大学 | Self-healing polyurethane and preparation and application thereof |
| WO2023168077A1 (en) | 2022-03-04 | 2023-09-07 | Conagen Inc. | Phenol-based hot melt adhesives for rework, repair and recycle |
| WO2023168066A1 (en) | 2022-03-04 | 2023-09-07 | Conagen Inc. | Oxime-based hot melt adhesives for rework, repair and recycle |
| WO2023168045A1 (en) | 2022-03-04 | 2023-09-07 | Conagen Inc. | Hydroxy/amino oxime-based hot melt adhesives for rework, repair and recycle |
| CN115028791A (en) * | 2022-05-11 | 2022-09-09 | 东华大学 | Liquid crystal polyurethane material with stress enhancement |
| CN115028791B (en) * | 2022-05-11 | 2024-05-10 | 东华大学 | Liquid crystal polyoxime urethane material with stress enhancement |
| CN115141353A (en) * | 2022-05-26 | 2022-10-04 | 中国海洋大学 | Self-repairing polyurethane composite material and preparation method and application thereof |
| CN115141353B (en) * | 2022-05-26 | 2023-12-22 | 中国海洋大学 | Self-repairing polyurethane composite material and preparation method and application thereof |
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