CN101880372A - Active prepolymer, preparation method thereof and polyurea adhesive and epoxy resin adhesive containing the same - Google Patents
Active prepolymer, preparation method thereof and polyurea adhesive and epoxy resin adhesive containing the same Download PDFInfo
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- CN101880372A CN101880372A CN 201010211655 CN201010211655A CN101880372A CN 101880372 A CN101880372 A CN 101880372A CN 201010211655 CN201010211655 CN 201010211655 CN 201010211655 A CN201010211655 A CN 201010211655A CN 101880372 A CN101880372 A CN 101880372A
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- epoxy
- resins
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- polyisocyanates
- polyether
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 32
- 239000000853 adhesive Substances 0.000 title claims abstract description 29
- 229920002396 Polyurea Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 16
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 16
- 239000004840 adhesive resin Substances 0.000 title 1
- 229920006223 adhesive resin Polymers 0.000 title 1
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 33
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 18
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims description 52
- 229920005989 resin Polymers 0.000 claims description 52
- 239000011347 resin Substances 0.000 claims description 52
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 32
- 229920000570 polyether Polymers 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 108010064470 polyaspartate Proteins 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 238000006276 transfer reaction Methods 0.000 abstract description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 29
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002924 oxiranes Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an active prepolymer, a preparation method thereof and a polyurea adhesive and an epoxy resin adhesive containing the same. In the invention, an active prepolymer which contains an isocyanate group and an epoxide group simultaneously is prepared by utilizing the hydrogen transfer reaction of a hydroxyl group and polyisocyanate in the molecular structure of epoxy resin, wherein the molar feeding ratio of the epoxy resin to the polyisocyanate is calculated according to the ratio of (0.9 to 1.0):(1.0 to 1.1) of the mole number of the hydroxyl group to the mole number of the polyisocyanate in 1 mole of epoxy resin. The active prepolymer provided by the invention can be used as a modifier of the polyurea or epoxy resin adhesive, and the modified adhesive has superior comprehensive mechanical property, filler filling resistance and environmental resistance. Meanwhile, the invention has the characteristics of quick surface drying, convenient construction and the like and can be applied to functional coating materials.
Description
Technical field
The present invention relates to the active performed polymer of a kind of Resins, epoxy grafting polyisocyanates, its preparation method, and the polyurea adhesive and the epoxyn that utilize this activity performed polymer to obtain as properties-correcting agent.
Background technology
Polyurea adhesive is the ep-type material that a kind of curing molding that grew up in recent years is fast, be convenient to construct.Its with the tensile strength height, snappiness is good and good performance such as waterproof, protection against corrosion, wear-resisting, anti-slippery, heat shock resistance, frost resistance and good decorative property, be subjected to people and more and more favor, showing unique characteristics aspect the big area ready coating of corrosion protection coating and abrasion-resistant coating material etc.The part but polyurea adhesive also comes with some shortcomings.Because the gel time of polyurea adhesive is very short, provides the polar group NH of bonding force very easily to form intermolecular hydrogen bonding, cause the internal cohesive energy of polyurea adhesive big, poor to the wetting property of ground, bonding strength is low.As to the sticking power of metal base, about 8MPa, be difficult to satisfy the requirement that some domain engineering are used.Epoxyn has characteristics such as excellent adhesiveproperties, wear-resisting, resistance to chemical attack, but common epoxyn enbrittles greatly, poor toughness, cracking are answered defectives such as step-down, and this has seriously hindered its further application and development.Adding active modifier in adhesive system is the effective way of improving the tackiness agent over-all properties.
Summary of the invention
For solving the problems of the technologies described above, the present invention proposes a kind of Resins, epoxy grafting polyisocyanates that utilizes and produces active performed polymer, its preparation method, and the polyurea adhesive and the epoxyn that utilize this activity performed polymer to obtain as properties-correcting agent.
The present invention is in conjunction with characteristics such as the snappiness of the adhesiveproperties of epoxyn excellence and polyurea adhesive, room temperature fast-curing, environmental protection, adopt the chemical graft reaction to provide a kind of Resins, epoxy grafting polyisocyanates active performed polymer, its preparation method, and utilize this activity performed polymer as properties-correcting agent, the polyurea adhesive of acquisition and epoxyn.
The active performed polymer that the present invention proposes, contain epoxide group and isocyanate group simultaneously, form by Resins, epoxy and polyisocyanates scion grafting reaction, contain hydroxyl in the described Resins, epoxy molecular structure, Resins, epoxy for E series or its modification, the hydroxyl in the Resins, epoxy and the mol ratio of polyisocyanates are (0.9-1.0): (1.0-1.1), the best is 1: 1.The present invention proposes a kind of preparation method of above-mentioned active performed polymer; comprise the following steps: under the anhydrous atmosphere protection; the liquid-state epoxy resin and the polyisocyanates that will contain hydroxyl mix; at 30-80 ℃ of following stirring reaction 0.5-8h; wherein; the feed ratio of Resins, epoxy and polyisocyanates is pressed the mol ratio (0.9～1.0) of hydroxyl and polyisocyanates in the Resins, epoxy: (1.0～1.1), optimum mole ratio are to determine at 1: 1.
Its average functionality of described polyisocyanates 〉=2 are liquid during room temperature.Described its average functionality of liquid-state epoxy resin 〉=1 of containing hydroxyl.
The present invention proposes a kind of polyurea adhesive, comprising: A component, active performed polymer that Resins, epoxy grafting polyisocyanates obtains and the trimerical blend of HDI; The B component, steric hindrance type amino-polyether; The add-on of Resins, epoxy grafting polyisocyanates accounts for the 10%-30% of A component molar content in the A component, and the blend ratio of A, B component is by amino kind decision in the content of the isocyano of A component and epoxy group(ing) and the B component.
The present invention also proposes a kind of epoxyn, comprising: A component, the active performed polymer that Resins, epoxy grafting polyisocyanates produces and the blend of Resins, epoxy; The B component, steric hindrance type amino-polyether, the add-on of Resins, epoxy grafting polyisocyanates accounts for the 10%-30% of A component molar content in the A component, and the blend ratio of A, B component is by amino kind decision in the content of the isocyano of A component and epoxy group(ing) and the B component.
The present invention proposes to prepare a kind of active prepolymer that contains isocyanate group and epoxide group simultaneously with hydroxyl in the Resins, epoxy molecular structure and the hydrogen transfer reactions between polyisocyanates.This activity performed polymer can be used as the properties-correcting agent of polyurea adhesive and epoxyn, give good comprehensive mechanical property, anti-filler fillibility and the environmental resistance of tackiness agent after the modification, have characteristics such as surface drying is fast, easy construction is pollution-free simultaneously, can be applied to the functional coating material.
Embodiment
At first, produce active performed polymer with Resins, epoxy grafting polyisocyanates, contain hydroxyl in the described Resins, epoxy molecular structure, be the Resins, epoxy of E series or its modification, the mol ratio of hydroxyl and polyisocyanates is 1: 1 in the Resins, epoxy.Its average functionality of described polyisocyanates 〉=2 are liquid during room temperature.Described its average functionality of liquid-state epoxy resin 〉=1 of containing hydroxyl.
Further set forth the preparation method of active performed polymer below in conjunction with embodiment.
Embodiment 1,0.2mol E-44 and 0.08mol HDI (hexamethylene diisocyanate) tripolymer joined in the 100ml there-necked flask, and under anhydrous atmosphere, as inflated with nitrogen protection, warming while stirring to 40 ℃, reaction 6h promptly can obtain.
Embodiment 2,0.2mol E-44 and 0.08mol TDI (tolylene diisocyanate) tripolymer joined in the 100ml there-necked flask, and under anhydrous atmosphere protection, warming while stirring to 60 ℃, reaction 4h can prepare.
Embodiment 3,0.2mol E-51 and 0.036mol HDI tripolymer joined in the 100ml there-necked flask, and inflated with nitrogen protection, warming while stirring to 65 ℃, reaction 3h can prepare.
Embodiment 4,0.2mol E-51 and 0.036mol HDI tripolymer joined in the 100ml there-necked flask, and inflated with nitrogen protection, warming while stirring to 50 ℃, reaction 3.5h can prepare.
Embodiment 5,0.1mol E-44 and 0.04mol HDI monomer joined in the 100ml there-necked flask, and inflated with nitrogen protection, warming while stirring to 50 ℃, reaction 3h promptly can prepare.
Second step was to adopt the active performed polymer of Resins, epoxy grafting polyisocyanates to make tackiness agent as properties-correcting agent.
The preparation of polyurea adhesive:
Embodiment 1, component A:E-51 Resins, epoxy grafting HDI tripolymer and the trimerical blend of HDI; B component: aromatic amino-terminated polyether.
Preparation: 0.1mol epoxy resin modification HDI tripolymer and 0.9mol HDI tripolymer are mixed, add the 0.775mol aromatic amino-terminated polyether and continue to mix the composition polyurea adhesive in mixture, the room temperature surface drying time of tackiness agent is 21min.
According to the GB test, following mechanical property is arranged after the polyurea adhesive self-vulcanizing:
Snappiness:＜1mm; Sticking power: 18MPa; Stripping strength: 140N/cm; Tensile strength 18MPa; Elongation: 28%; Impact resistance:＞50kgcm.
Embodiment 2, component A:E-51 Resins, epoxy grafting HDI tripolymer and the trimerical blend of HDI (hexamethylene diisocyanate); B component: aromatic amino-terminated polyether.
Preparation: 0.2mol Resins, epoxy grafting HDI tripolymer and 0.8mol HDI tripolymer are mixed, add the 0.7mol aromatic amino-terminated polyether and continue to mix the composition polyurea adhesive in mixture, the room temperature surface drying time of tackiness agent is 18min.
According to the GB test, following mechanical property is arranged after the polyurea adhesive self-vulcanizing:
Snappiness:＜1mm; Sticking power: 18.5MPa; Stripping strength: 155N/cm; Tensile strength: 32MPa; Elongation: 22.36%; Impact resistance:＞50kgcm.
Embodiment 3, component A:E-51 Resins, epoxy grafting HDI tripolymer and TDI tripolymer blend; B component: poly-aspartic-acid ester polyether.
Preparation: 0.15mol Resins, epoxy grafting HDI tripolymer and 0.85mol TDI are mixed, add 0.7125mol end poly-aspartic-acid ester polyether and continue to mix the composition polyurea adhesive in mixture, the room temperature surface drying time of tackiness agent is 19min.
According to the GB test, following mechanical property is arranged after the polyurea adhesive self-vulcanizing:
Snappiness:＜1mm; Sticking power: 19.6MPa; Stripping strength: 145.8N/cm; Tensile strength: 38.05MPa; Elongation: 40.05%; Impact resistance:＞50kgcm.
Embodiment 4, component A:E-51 Resins, epoxy grafting HDI tripolymer and HDI tripolymer blend; B component: aromatic amino-terminated polyether.
Preparation: 0.3mol Resins, epoxy grafting HDI tripolymer and 0.7mol HDI tripolymer mixed be configured to the A component, the 0.675mol aromatic amino-terminated polyether is configured to the B component, A, B component mix the back and form polyurea adhesive, and the room temperature surface drying time of tackiness agent is 18min.
According to the GB test, following mechanical property is arranged after the polyurea adhesive self-vulcanizing:
Snappiness:＜1mm; Sticking power: 17.40MPa; Stripping strength: 148N/cm; Tensile strength: 28MPa; Elongation: 35%; Impact resistance:＞50kgcm.
The blend ratio of A, B component is by amino kind decision in the content of the isocyano of A component and epoxy group(ing) and the B component in the above polyurea adhesive.
The preparation of epoxyn:
Embodiment 1, the blend of component A:E-51 Resins, epoxy grafting HDI tripolymer and epoxy resin E-44; B component: aromatic amino-terminated polyether.
Preparation: 0.1mol Resins, epoxy grafting HDI tripolymer and 0.9mol Resins, epoxy mixed be configured to the A component, the aromatic amino-terminated polyether of 0.52mol is configured to the B component, A, B component mixed be prepared into epoxyn, surface drying time 30min under the room temperature.
After the epoxyn self-vulcanizing,, following mechanical property is arranged according to the GB test:
Snappiness:＜2mm; Sticking power: 40MPa; Stripping strength: 180N/cm; Tensile strength: 58MPa; Elongation: 8%; Impact strength:＞50kgcm.
Case study on implementation 2, the blend of component A:E-51 Resins, epoxy grafting HDI tripolymer and epoxy resin E-44; B component: aromatic amino-terminated polyether.
Preparation: 0.2mol Resins, epoxy grafting HDI tripolymer and 0.8mol Resins, epoxy mixed be configured to the A component, the aromatic amino-terminated polyether of 0.54mol is configured to the B component, A, B component mixed be prepared into epoxyn, surface drying time 28min under the room temperature.
Behind the epoxyn intermediate temperature setting,, following mechanical property is arranged according to the GB test:
Snappiness:＜2mm; Sticking power: 43MPa; Stripping strength: 190N/cm; Tensile strength: 60MPa; Elongation: 10%; Impact strength:＞50kgcm.
Case study on implementation 3, the blend of component A:E-51 Resins, epoxy grafting HDI tripolymer and epoxy resin E-44; B component: aromatic amino-terminated polyether.
Preparation: 0.3mol Resins, epoxy grafting HDI tripolymer and 0.7mol Resins, epoxy mixed be configured to the A component, the aromatic amino-terminated polyether of 0.56mol is configured to the B component, A, B component mixed be prepared into epoxyn, surface drying time 26min under the room temperature.
After the epoxyn self-vulcanizing,, following mechanical property is arranged according to the GB test:
Snappiness:＜2mm; Sticking power: 46MPa; Stripping strength: 203N/cm; Tensile strength: 64MPa; Elongation: 12%; Impact strength:＞50kgcm.
Case study on implementation 4, the blend of component A:E-51 Resins, epoxy grafting HDI tripolymer and epoxy resin E-44; B component: poly-aspartic-acid ester polyether.
Preparation: 0.4mol Resins, epoxy grafting HDI tripolymer and 0.6mol Resins, epoxy mixed be configured to the A component, the poly-aspartic-acid ester polyether of 1.16mol is configured to the B component, A, B component mixed be prepared into epoxyn, surface drying time 26min under the room temperature.
After the epoxyn self-vulcanizing,, following mechanical property is arranged according to the GB test:
Snappiness:＜2mm; Sticking power: 50MPa; Stripping strength: 210N/cm; Tensile strength: 68MPa; Elongation: 14%; Impact strength:＞50kgcm.
The middle A of above epoxyn, the blend ratio of B component are by amino kind decision in the content of the isocyano of A component and epoxy group(ing) and the B component.
Aromatic amino-terminated polyether is the compound with general formula (1) expression in the above case study on implementation:
In the general formula (1): m, x are integer, and 10 〉=m 〉=2,6 〉=x 〉=0; N is the repeating unit of polyether segment, its value between the molecular weight that makes polyether segment between 200 to 10000; Substituting group on the phenyl ring lays respectively at ortho position, a position, the contraposition on the phenyl ring, or is positioned at ortho position, a position, contraposition on the phenyl ring simultaneously.
The poly aspartic acid ester polyether is the compound with general formula (2) expression in the above case study on implementation:
In the general formula (2): R, R ' are respectively aromatic series alkyl or aliphatic alkyl; N is the repeating unit of polyether segment, its value between the molecular weight that makes polyether segment between 200 to 10000; y
1, y
2, y
3And y
4Be integer, and 4 〉=y
1, y
2, y
3And y
4〉=1; X
1, X
2, X
3And X
4Be H or OH, and hydroxyl can not be primary hydroxyl.
Add functional stuffing in the tackiness agent after modification, the functional coating material that fields such as electromagnetic shielding, microwave be stealthy, antistatic have important use can be used as, the requirement that functional paint improves day by day to tackiness agent filmogen mechanical property, curing performance and workability can be satisfied.
Claims (10)
1. active performed polymer, it is characterized in that: contain epoxide group and isocyanate group simultaneously in the described active performed polymer, form by Resins, epoxy and polyisocyanates scion grafting reaction, contain hydroxyl in the described Resins, epoxy molecular structure, Resins, epoxy for E series or its modification, the mol ratio of hydroxyl and polyisocyanates is (0.9-1.0) in the Resins, epoxy: (1.0-1.1), the best is 1: 1.
2. active performed polymer as claimed in claim 1 is characterized in that: described polyisocyanates is HDI tripolymer or monomer, or the TDI tripolymer.
3. the preparation method of the described active performed polymer of claim 1, it is characterized in that comprising the following steps: under anhydrous atmosphere, the liquid-state epoxy resin and the polyisocyanates that will contain hydroxyl mix, at 30～80 ℃ of following stirring reaction 0.5～8h, wherein, the mol ratio that the feed ratio of Resins, epoxy and polyisocyanates is pressed hydroxyl and polyisocyanates in the Resins, epoxy is (0.9-1.0): (1.0-1.1), the best is 1: 1.
4. preparation method as claimed in claim 3 is characterized in that: described Resins, epoxy is the Resins, epoxy of E series or its modification, and described polyisocyanates is HDI tripolymer or monomer, or the TDI tripolymer.
5. preparation method as claimed in claim 3 is characterized in that: its average functionality of described polyisocyanates 〉=2 are liquid during room temperature, described its average functionality of liquid-state epoxy resin 〉=1 of containing hydroxyl.
6. polyurea adhesive, it is characterized in that comprising: the A component, active performed polymer and the trimerical blend of HDI that Resins, epoxy grafting polyisocyanates produces, the B component, steric hindrance type amino-polyether, the add-on of Resins, epoxy grafting polyisocyanates accounts for 10%～30% of A component molar content in the A component.
7. polyurea adhesive as claimed in claim 7 is characterized in that: described steric hindrance type amino-polyether is aromatic amino-terminated polyether and/or poly aspartic acid ester polyether.
8. epoxyn, it is characterized in that comprising: the A component, the active performed polymer that Resins, epoxy grafting polyisocyanates produces and the blend of Resins, epoxy, the B component, steric hindrance type amino-polyether, the add-on of Resins, epoxy grafting polyisocyanates accounts for 10%～30% of A component molar content in the A component.
9. epoxyn as claimed in claim 8 is characterized in that: described steric hindrance type amino-polyether is Amino Terminated polyether(ATPE) and/or poly aspartic acid ester polyether.
10. as claim 6 or 8 described tackiness agent, it is characterized in that: the blend ratio of A, B component is by amino kind decision in the content of the isocyano of A component and epoxy group(ing) and the B component.
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| CN 201010211655 CN101880372B (en) | 2010-06-25 | 2010-06-25 | Active prepolymer, preparation method thereof and polyurea adhesive and epoxy resin adhesive containing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010211655 CN101880372B (en) | 2010-06-25 | 2010-06-25 | Active prepolymer, preparation method thereof and polyurea adhesive and epoxy resin adhesive containing the same |
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| CN101880372A true CN101880372A (en) | 2010-11-10 |
| CN101880372B CN101880372B (en) | 2013-02-13 |
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| CN102585752A (en) * | 2011-12-31 | 2012-07-18 | 济南大学 | Recovery polyethylene terephthalate (PET)-base adhesive, and preparation method and application thereof |
| CN104341580A (en) * | 2014-11-11 | 2015-02-11 | 李开成 | Spraying elastomer with high mechanical property |
| CN104371484A (en) * | 2013-08-13 | 2015-02-25 | 关西涂料株式会社 | Coating composition and coating construction method using the same |
| CN105238314A (en) * | 2015-11-13 | 2016-01-13 | 深圳先进技术研究院 | Dampness-heat-resistant high-reliability epoxy conductive silver adhesive as well as preparation method and application thereof |
| CN105838311A (en) * | 2016-04-08 | 2016-08-10 | 深圳科诺桥科技股份有限公司 | A polyurethane-epoxy resin hybrid electrically conductive adhesive, a preparing method thereof and an electrically conductive film |
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| CN105238314A (en) * | 2015-11-13 | 2016-01-13 | 深圳先进技术研究院 | Dampness-heat-resistant high-reliability epoxy conductive silver adhesive as well as preparation method and application thereof |
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