CN109762131A - A kind of wet double solidification polyurethane contact adhesives of the light of siloxane blocking agent and its preparation method and application the end-capping reagent - Google Patents
A kind of wet double solidification polyurethane contact adhesives of the light of siloxane blocking agent and its preparation method and application the end-capping reagent Download PDFInfo
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- CN109762131A CN109762131A CN201811646319.6A CN201811646319A CN109762131A CN 109762131 A CN109762131 A CN 109762131A CN 201811646319 A CN201811646319 A CN 201811646319A CN 109762131 A CN109762131 A CN 109762131A
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- blocking agent
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- contact adhesive
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Abstract
The present invention provides a kind of wet double solidification polyurethane contact adhesives of light of siloxane blocking agent and its preparation method and application the end-capping reagent, prepare the siloxane blocking agent of the polyurethane containing siloxane group and vinyl groups bifunctionality, and the polyurethane contact adhesive for capableing of the wet dual cure of light is obtained using the siloxane blocking agent, reduce traditional pressure sensitive glue toxic solvent volatilization bring environment to frustrate, it solves polyurethane moisturecuring and is easy to produce air bubble problem in the process, while the polyurethane contact adhesive that choosing is prepared in this way has excellent bonding property.
Description
Technical field
The invention belongs to polyurethane contact adhesive fields, in particular to a kind of siloxane blocking agent and preparation method thereof and answer
With the wet double solidification polyurethane contact adhesives of the light of the end-capping reagent.
Background technique
Pressure sensitive adhesive is a kind of viscoelastic body of the resilient nature of adhesion properties for being provided simultaneously with liquid and solid, is answered extensively
For packing, the fields such as coating, electric appliance and pressure sensitive adhesive tape.It is pressure-sensitive that current pressure sensitive adhesive is mainly partial to solvent-type acrylic type
Glue, due to the volatilization of solvent, a large amount of toxic and harmful gas can be caused damage and be injured to environmental and biological materials, as people are to ring
The attention further of border problem, solvent pressure-sensitive adhesive are gradually abandoned.Polyurethane has excellent physical and mechanical property, is commonly used for
The fields such as coating, leather and adhesive, and the moisture hair in common moisture cure urethanes adhesive utilization-NCO group and air
Raw cross-linking reaction solidification, but because CO can be generated in reaction process2Gas cause in resin matrix there are a large amount of aerations its
Mechanical property.Therefore, it is necessary to which polyurethane contact adhesive and its condition of cure are further improved.
Summary of the invention
The purpose of the present invention is to provide a kind of light of siloxane blocking agent and its preparation method and application the end-capping reagent is wet
Double solidification polyurethane contact adhesives are occurred using the monomer containing vinyl and amino with containing the monomer of epoxy group and siloxane group
Epoxy ring opening reaction obtains the siloxane blocking agent of trifunctional by reaction.Polyurethane contact adhesive be by diisocyanate with
Macromolecule dihydric alcohol polycondensation forms the performed polymer of band-NCO group, then the novel end-capping reagent by preparing is blocked, and has excellent
The wet dual cure characteristic of light.The method that the present invention uses the wet dual cure of light, the shortcomings that effectively preventing in the prior art, from
And it is prepared for a kind of polyurethane contact adhesive of function admirable.
The technical solution adopted by the present invention to solve the technical problems first is that:
A kind of siloxane blocking agent, the siloxane blocking agent are shown below:
The technical solution adopted by the present invention to solve the technical problems second is that:
A kind of preparation method of above-mentioned siloxane blocking agent, diallylamine monomer is dissolved in the first organic solvent, drop
Add 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, the diallylamine monomer and 3- (2,3- the third oxygen of epoxy) propyl front three
The molar ratio of oxysilane is 1:0.8~1.0；Under protective gas protection, 4~6h is reacted under the conditions of 60~80 DEG C, decompression is steamed
It evaporates to obtain the siloxane blocking agent.
In one embodiment: first organic solvent is ethyl alcohol or chloroform.
The reaction route is shown below:
The technical solution adopted by the present invention to solve the technical problems third is that:
A kind of polyurethane contact adhesive using above-mentioned siloxane blocking agent.
The technical solution adopted by the present invention to solve the technical problems fourth is that:
Macromolecule dihydric alcohol is placed under protective gas protection by a kind of preparation method of above-mentioned polyurethane contact adhesive,
Diisocyanate, the second organic solvent and organotin catalysts are added in 105~115 DEG C of 1~3h of dehydration, react 3 at 50~80 DEG C
~4h, obtains base polyurethane prepolymer for use as, and the siloxane blocking agent is added, and in 45~60 DEG C of 1~2h of reaction, vacuum distillation is obtained
The polyurethane contact adhesive.
In one embodiment: the molar ratio of the macromolecule dihydric alcohol, diisocyanate and siloxane blocking agent is 1:1
~3:0.1~0.3；The additional amount of the organotin catalysts is 0.05~0.15% (to account for macromolecular two for organotin catalysts
The mass percent of both first alcohol and diisocyanate total amount).
In one embodiment: the macromolecule dihydric alcohol is polytetramethylene glycol, polyethers 2000 or polytetrahydrofuran；Two isocyanide
Acid esters is toluene di-isocyanate(TDI), isophorone diisocyanate or methyl diphenylene diisocyanate；It is described organotin catalyzed
Agent is dibutyl tin dilaurate.
In one embodiment: second organic solvent is acetone or butanone.
In one embodiment: further include: photoinitiator is added in obtained polyurethane contact adhesive, the photoinitiator adds
Dosage is 2~5wt% of polyurethane contact adhesive, is uniformly mixed, is kept in dark place.
In one embodiment: the photoinitiator is photoinitiator 2959.
Further, the polyurethane contact adhesive after addition photoinitiator is uniformly coated on poly (methyl methacrylate) plate, certainly to it
Right moisturecuring, then with ultraviolet light irradiation two minutes of certain wavelength, carry out peel test force.
The invention has the benefit that obtained polyurethane contact adhesive has vinyl and siloxanes difunctional, ethylene
Base can be used for the crosslinking degree of photopolymerization enhancing polymer film, and it is anti-that hydrolytic condensation can occur during moisturecuring for siloxane group
It answers, forms siloxane network structure, and siloxane group and organic or inorganic material surface have excellent bonding property.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is fourier transform infrared spectroscopy (FT-IR) spectrum of the silicone coupling agents of 1 first step of embodiment synthesis
Figure.
Fig. 2 is fourier transform infrared spectroscopy (FT-IR) spectrogram for the polyurethane contact adhesive that embodiment 1 obtains.
Specific embodiment
The contents of the present invention are illustrated below by embodiment:
Embodiment 1
The first step；The synthesis of siloxane blocking agent
The diallylamine monomer of 10.00mL is dissolved in 20mL ethyl alcohol, is added in three-necked flask, the 3- of 17.70mL is added dropwise
(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, is passed through nitrogen protection, and 6h is reacted under the conditions of 80 DEG C, and vacuum distillation obtains silicon
Oxygen alkane end-capping reagent.
Step 2: the preparation of polyurethane contact adhesive
6.5g polytetramethylene glycol (Mn=650) is added in the three-necked flask for having nitrogen protection, is dehydrated under the conditions of 110 DEG C
4.44g isophorone diisocyanate is added in 2h, and the dibutyltin dilaurate catalyst of 5mL acetone and 0.1% is added,
4h is reacted under the conditions of 60 DEG C, obtains base polyurethane prepolymer for use as, the siloxane blocking agent 0.5g that the first step is reacted is added, at 50 DEG C
Under the conditions of reaction 2h blocked；Polyurethane contact adhesive is obtained by vacuum distillation, polyurethane is added in the photoinitiator of 3wt%
In pressure sensitive adhesive, progress ultrasonic mixing is uniform, is kept in dark place.
Step 3: the pressure sensitive adhesive that second step is obtained is uniformly coated on poly (methyl methacrylate) plate, to its natural moisturecuring, then use
Wavelength is 365nm 40W ultraviolet lamp prolonged exposure several minutes, carries out peel test force.
Embodiment 2
The first step；The synthesis of siloxane blocking agent
The diallylamine monomer of 10.00mL is dissolved in 20mL ethyl alcohol, is added in three-necked flask, be added dropwise 17.70mL 3- (2,
The third oxygen of 3- epoxy) propyl trimethoxy silicane, it is passed through nitrogen protection, 6h is reacted under the conditions of 80 DEG C, vacuum distillation obtains silicon oxygen
Alkane end-capping reagent.
Step 2: the preparation of polyurethane contact adhesive
10g polytetramethylene glycol (Mn=1000) is added in the three-necked flask for having nitrogen protection, is dehydrated under the conditions of 110 DEG C
4.44g isophorone diisocyanate is added in 2h, and the dibutyltin dilaurate catalyst of 5mL acetone and 0.1% is added,
4h is reacted under the conditions of 60 DEG C, obtains base polyurethane prepolymer for use as, the siloxane blocking agent 0.5g that the first step is reacted is added, at 50 DEG C
Under the conditions of reaction 2h blocked；Polyurethane contact adhesive is obtained by vacuum distillation, polyurethane is added in the photoinitiator of 3wt%
In pressure sensitive adhesive, progress ultrasonic mixing is uniform, is kept in dark place.
It is 365nm to its natural moisturecuring, then with wavelength step 3: pressure sensitive adhesive is uniformly coated on poly (methyl methacrylate) plate
40W ultraviolet lamp prolonged exposure several minutes carry out peel test force.
Embodiment 3
The first step；The synthesis of siloxane blocking agent
The diallylamine monomer of 10.00mL is dissolved in 20mL ethyl alcohol, is added in three-necked flask, be added dropwise 17.70mL 3- (2,
The third oxygen of 3- epoxy) propyl trimethoxy silicane, it is passed through nitrogen protection, 6h is reacted under the conditions of 80 DEG C, vacuum distillation obtains silicon oxygen
Alkane end-capping reagent.
Step 2: the preparation of polyurethane contact adhesive
14g polytetramethylene glycol (Mn=1400) is added in the three-necked flask for having nitrogen protection, is dehydrated under the conditions of 110 DEG C
4.44g isophorone diisocyanate is added in 2h, and the dibutyltin dilaurate catalyst of 5mL acetone and 0.1% is added,
4h is reacted under the conditions of 60 DEG C, obtains base polyurethane prepolymer for use as, the siloxane blocking agent 0.5g that the first step is reacted is added, at 50 DEG C
Under the conditions of reaction 2h blocked；Polyurethane contact adhesive is obtained by vacuum distillation, polyurethane is added in the photoinitiator of 3wt%
In pressure sensitive adhesive, progress ultrasonic mixing is uniform, is kept in dark place.
It is 365nm to its natural moisturecuring, then with wavelength step 3: pressure sensitive adhesive is uniformly coated on poly (methyl methacrylate) plate
40W ultraviolet lamp prolonged exposure several minutes carry out peel test force.
Embodiment 4
The first step；The synthesis of siloxane blocking agent
The diallylamine monomer of 10.00mL is dissolved in 20mL ethyl alcohol, is added in three-necked flask, be added dropwise 17.70mL 3- (2,
The third oxygen of 3- epoxy) propyl trimethoxy silicane, it is passed through nitrogen protection, 6h is reacted under the conditions of 80 DEG C, vacuum distillation obtains silicon oxygen
Alkane end-capping reagent.
Step 2: the preparation of polyurethane contact adhesive
18g polytetramethylene glycol (Mn=1800) is added in the three-necked flask for having nitrogen protection, is dehydrated under the conditions of 110 DEG C
4.44g isophorone diisocyanate is added in 2h, and the dibutyltin dilaurate catalyst of 5mL acetone and 0.1% is added,
4h is reacted under the conditions of 60 DEG C, obtains base polyurethane prepolymer for use as, the siloxane blocking agent 0.5g that the first step is reacted is added, at 50 DEG C
Under the conditions of reaction 2h blocked；Polyurethane contact adhesive is obtained by vacuum distillation, polyurethane is added in the photoinitiator of 3wt%
In pressure sensitive adhesive, progress ultrasonic mixing is uniform, is kept in dark place.
It is 365nm to its natural moisturecuring, then with wavelength step 3: pressure sensitive adhesive is uniformly coated on poly (methyl methacrylate) plate
40W ultraviolet lamp prolonged exposure several minutes carry out peel test force.
Embodiment 5
The first step；The synthesis of siloxane blocking agent
The diallylamine monomer of 10.00mL is dissolved in 20mL ethyl alcohol, is added in three-necked flask, be added dropwise 17.70mL 3- (2,
The third oxygen of 3- epoxy) propyl trimethoxy silicane, it is passed through nitrogen protection, 6h is reacted under the conditions of 80 DEG C, vacuum distillation obtains silicon oxygen
Alkane end-capping reagent.
Step 2: the preparation of polyurethane contact adhesive
20g polytetramethylene glycol (Mn=2000) is added in the three-necked flask for having nitrogen protection, is dehydrated under the conditions of 110 DEG C
4.44g isophorone diisocyanate is added in 2h, and the dibutyltin dilaurate catalyst of 5mL acetone and 0.1% is added,
4h is reacted under the conditions of 60 DEG C, obtains base polyurethane prepolymer for use as, the siloxane blocking agent 0.5g that the first step is reacted is added, at 50 DEG C
Under the conditions of reaction 2h blocked；Polyurethane contact adhesive is obtained by vacuum distillation, second step is added in the photoinitiator of 3wt%
In obtained polyurethane contact adhesive, progress ultrasonic mixing is uniform, is kept in dark place.
It is 365nm to its natural moisturecuring, then with wavelength step 3: pressure sensitive adhesive is uniformly coated on poly (methyl methacrylate) plate
40W ultraviolet lamp prolonged exposure several minutes carry out peel test force.
Aptitude test
The peeling force for the polyurethane contact adhesive being prepared is tested, as a result as shown in the table:
The peeling force of the polyurethane contact adhesive of 1 Examples 1 to 5 of table synthesis
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Peeling force (N/25mm) | 14 | 12 | 9 | 9 | 8 |
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (10)
1. a kind of siloxane blocking agent, it is characterised in that: the siloxane blocking agent is shown below:
2. a kind of preparation method of siloxane blocking agent described in claim 1, it is characterised in that: diallylamine monomer to be dissolved in
In first organic solvent, 3- (2,3- the third oxygen of epoxy) propyl trimethoxy silicane, the diallylamine monomer and 3- (2,3- is added dropwise
The third oxygen of epoxy) propyl trimethoxy silicane molar ratio be 1:0.8~1.0, protective gas protection under, under the conditions of 60~80 DEG C
4~6h is reacted, vacuum distillation obtains the siloxane blocking agent.
3. the preparation method of siloxane blocking agent according to claim 2, it is characterised in that: first organic solvent is
Ethyl alcohol or chloroform.
4. a kind of polyurethane contact adhesive using siloxane blocking agent described in claim 1.
5. a kind of preparation method of polyurethane contact adhesive as claimed in claim 4, it is characterised in that: macromolecule dihydric alcohol to be placed in
Under protective gas protection, in 105~115 DEG C of 1~3h of dehydration, addition diisocyanate, the second organic solvent and organotin catalyzed
Agent obtains base polyurethane prepolymer for use as, the siloxane blocking agent is added in 50~80 DEG C of 3~4h of reaction, reacts 1 at 45~60 DEG C
~2h, vacuum distillation, obtains the polyurethane contact adhesive.
6. the preparation method of polyurethane contact adhesive according to claim 5, it is characterised in that: the macromolecule dihydric alcohol,
Diisocyanate and the molar ratio of siloxane blocking agent are 1:1~3:0.1~0.3；The addition of the organotin catalysts
Amount is 0.05~0.15%.
7. the preparation method of polyurethane contact adhesive according to claim 5, it is characterised in that: the macromolecule dihydric alcohol is
Polytetramethylene glycol, polyethers 2000 or polytetrahydrofuran；The diisocyanate is toluene di-isocyanate(TDI), isophorone diisocyanate
Ester or methyl diphenylene diisocyanate；The organotin catalysts are dibutyl tin dilaurate.
8. the preparation method of polyurethane contact adhesive according to claim 5, it is characterised in that: second organic solvent is
Acetone or butanone.
9. the preparation method of polyurethane contact adhesive according to claim 5, it is characterised in that: further include: it is poly- what is obtained
Photoinitiator is added in urethane pressure sensitive adhesive, the additive amount of the photoinitiator is 2~5wt% of polyurethane contact adhesive, and mixing is equal
It is even, it is kept in dark place.
10. the preparation method of polyurethane contact adhesive according to claim 9, it is characterised in that: the photoinitiator is
Photoinitiator 2959.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811646319.6A CN109762131B (en) | 2018-12-29 | 2018-12-29 | Siloxane end-capping agent, preparation method thereof and light-moisture dual-curing polyurethane pressure-sensitive adhesive applying end-capping agent |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811646319.6A CN109762131B (en) | 2018-12-29 | 2018-12-29 | Siloxane end-capping agent, preparation method thereof and light-moisture dual-curing polyurethane pressure-sensitive adhesive applying end-capping agent |
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| CN109762131A true CN109762131A (en) | 2019-05-17 |
| CN109762131B CN109762131B (en) | 2020-07-24 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467717A (en) * | 2019-07-09 | 2019-11-19 | 广东德美精细化工集团股份有限公司 | A kind of not fluorine-containing waterproof polymer intermediate and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269071A (en) * | 1995-03-31 | 1996-10-15 | Nitto Boseki Co Ltd | Silane coupling agent and its production |
| CN101631813A (en) * | 2007-01-12 | 2010-01-20 | 陶氏康宁公司 | Silicone-containing composition |
| CN103718110A (en) * | 2011-07-15 | 2014-04-09 | 株式会社Lg化学 | Photosensitive composition and compound used therein |
-
2018
- 2018-12-29 CN CN201811646319.6A patent/CN109762131B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08269071A (en) * | 1995-03-31 | 1996-10-15 | Nitto Boseki Co Ltd | Silane coupling agent and its production |
| CN101631813A (en) * | 2007-01-12 | 2010-01-20 | 陶氏康宁公司 | Silicone-containing composition |
| CN103718110A (en) * | 2011-07-15 | 2014-04-09 | 株式会社Lg化学 | Photosensitive composition and compound used therein |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467717A (en) * | 2019-07-09 | 2019-11-19 | 广东德美精细化工集团股份有限公司 | A kind of not fluorine-containing waterproof polymer intermediate and preparation method thereof |
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| CN109762131B (en) | 2020-07-24 |
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