CN109749690A - Epoxy resin modified aqueous polyurethane adhesive for building and preparation method thereof - Google Patents
Epoxy resin modified aqueous polyurethane adhesive for building and preparation method thereof Download PDFInfo
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- CN109749690A CN109749690A CN201811438844.9A CN201811438844A CN109749690A CN 109749690 A CN109749690 A CN 109749690A CN 201811438844 A CN201811438844 A CN 201811438844A CN 109749690 A CN109749690 A CN 109749690A
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- epoxy resin
- aqueous polyurethane
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Abstract
The invention belongs to adhesive for polyurethane technical fields, and in particular to a kind of epoxy resin modified aqueous polyurethane adhesive for building and preparation method thereof.Aqueous Polyurethane Adhesives of the present invention include polyether polyol, isocyanates, crosslinking agent, hydroxyl epoxy resin, hydrophilic chain extender, triethylamine, solvent, amine chain extender and water；The polyether polyol relative molecular mass is 500~750, and degree of functionality is 1.5~2.5；The hydroxyl epoxy resin is reacted by bisphenol A type epoxy resin and diethanol amine to be made；The present invention also provides preparation methods.The Aqueous Polyurethane Adhesives of preparation method preparation of the present invention, improve the water resistance, heat resistance and mechanical property of Aqueous Polyurethane Adhesives, have high adhesion strength in the compound tense for construction material.
Description
Technical field
The invention belongs to adhesive for polyurethane technical fields, and in particular to a kind of epoxy resin modified aqueous poly- ammonia for building
Ester adhesive and preparation method thereof.
Background technique
Adhesive for polyurethane has many advantages, such as that hardness is adjustable, low temperature resistant, flexibility is good, adhesive strength is big, can be bonded
The multiple materials such as metal, nonmetallic, it is viscous in automobile inner ornament bonding, kitchen article manufacture, laminated film manufacture, sole upper of a shoe
It connects, clothes processing, building trade etc. are applied.
Aqueous Polyurethane Adhesives refer to polyurethane is dissolved in water or be dispersed in water and the adhesive that is formed, with solvent type
It is easily blended with other polymers especially emulsion polymer by force compared to solvent-free, pollution-free, good film-forming property, bonding force
Be conducive to the advantages that modified.With the reinforcement of the safety and environmental consciousness of people, the research of Aqueous Polyurethane Adhesives is able to fast
Speed development.But simple aqueous poly- propylhomoserin adhesive is not met by the demand of people in some performances, such as glue film mechanics
Performance is bad, and chemical resistance, water-fast, heat resistance is bad etc., needs to improve its function by various modifications.
Patent CN108641663A discloses a kind of environment-friendly water-based polyurethane adhesive, and epoxy resin, organosilicon is added
Solvent, fluoroalkyl polymer emulsion are modified product, and product is made to have good water resistance, chemical-resistant, pollution resistance
And biocompatibility, but its fluoroalkyl polymer emulsion number being added is more, influences the mechanical property of product, it is difficult to be used for
Building trade；Patent CN103013423A discloses a kind of preparation method of high temperature-resistanwaterborne waterborne polyurethane adhesive, and epoxy is added
Resin, nano silica are modified product, keep product high temperature resistant, water resistance superior, do not mention the mechanical property of product
Energy.Above scheme is to react to be grafted to aqueous polyurethane strand with isocyanates using the secondary hydroxyl in epoxy resin
In, but epoxy molecule is located at aqueous polyurethane molecule chain end, cannot increase substantially the mechanical strength of aqueous polyurethane.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of epoxy resin modified aqueous polyurethanes for building
Adhesive improves the water resistance, heat resistance and mechanical property of Aqueous Polyurethane Adhesives, in the compound tense for construction material
With high adhesion strength；The present invention also provides preparation methods.
Epoxy resin modified aqueous polyurethane adhesive for building of the present invention, the original including following mass fraction
Material:
The polyether polyol is that relative molecular mass is 500~750, the polyether polyol that degree of functionality is 1.5~2.5,
Preferably polyether polyol DDL-600, the federal chemical Industrial Co., Ltd's production of Zibo moral letter.
The hydroxyl epoxy resin is reacted by bisphenol A type epoxy resin and diethanol amine to be made, wherein bisphenol type epoxy tree
The molar ratio of rouge and diethanol amine is 1:0.8-1.2.
The crosslinking agent is silane coupling agent KH-151, KH-540, KH-550, KH-560, KH-570, KH-602, KH-
One or more of 792 mixture, preferably silane coupling agent KH-151.
The solvent is acetone, butanone or ethyl acetate, preferably acetone.
The hydrophilic chain extender is dihydromethyl propionic acid or dimethylolpropionic acid.
The amine chain extender is one or more of ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine
Mixture, preferably ethylenediamine.
The isocyanates is that isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride two are different
Cyanate or toluene di-isocyanate(TDI), preferably toluene di-isocyanate(TDI).
The preparation method of epoxy resin modified aqueous polyurethane adhesive for building of the present invention, including following step
It is rapid:
(1) by bisphenol A type epoxy resin, it is heated to 70-90 DEG C, stirs 20-30min, then diethanol amine is slowly added dropwise,
0.5-1h is dripped, and reacts 5-6h at a temperature of 100-110 DEG C, obtains hydroxyl epoxy resin；
(2) it after polyether polyols dehydration of alcohols, will be cooled to 70-80 DEG C, isocyanates is added, is reacted at a temperature of 85-90 DEG C
3-5h, then it is cooled to 70-80 DEG C, hydrophilic chain extender is added, reacts 3-5h at a temperature of 85-90 DEG C；It is cooled to after reaction
50-60 DEG C, hydroxyl epoxy resin made from solvent, crosslinking agent and step (1) is added, 1-2h is reacted at a temperature of 85-90 DEG C, then
It is cooled to 50-60 DEG C, obtains base polyurethane prepolymer for use as, NCO mass content is 3.0-4.0%；
(3) triethylamine and water, high speed dispersion are added in the base polyurethane prepolymer for use as made from step (2), adds amine expansion
1-2h is reacted in chain agent at a temperature of 85-90 DEG C, and finally decompression steams solvent, obtains epoxy resin modified aqueous polyurethane glue
Glutinous agent.
Wherein in step (2)-NCO content uses di-n-butylamine titration measuring.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) epoxy resin is carried out pre- open loop processing, secondary amino group and bisphenol A type epoxy resin in diethanol amine by the present invention
In an epoxy group react and generate 3 hydroxyls, the secondary hydroxyl of these hydroxyls and epoxy resin band itself together with
Isocyanates reaction, and is connected to epoxy resin in polyurethane molecular chain, and the remaining epoxy group of epoxy resin open loop can be with
It is crosslinked again in water phase with chain extender, so that aqueous polyurethane is showed a kind of cross-linked state of complexity, substantially increase product
Mechanical property and heat resistance, and epoxy resin itself has hydrophobicity, introduces epoxy resin in aqueous polyurethane strand,
Enhance the water resistance of product；
(2) silane coupling agent is added in the present invention in Aqueous Polyurethane Adhesives preparation process, and silane coupling agent contains work
Property Amino End Group, be introduced into aqueous polyurethane strand, form reticular structure, the crosslinking for further improving glue film is close
Degree enhances product cohesive force, while also enhancing the heat resistance, water resistance and mechanical performance of adhesive；
(3) present invention uses multistep polymerization in preparation method, first makes the pure and mild isocyanate polymeric of polyether polyols, then will be close
Water chain extender is introduced into strand, and hydroxyl epoxy resin is then added and crosslinking agent carries out further chain extension, is eventually adding amine
Chain extender carries out final chain extension；The segmentation of different types of chain extender is introduced into polyurethane molecular chain, the friendship of polyurethane molecular is made
Connection degree is more diversified, to enhance the mechanical performance and caking property of product.
Specific embodiment
Embodiment 1
(1) by 10mol bisphenol A type epoxy resin, it is heated to 70-90 DEG C, stirs 20-30min, then 8mol bis- is slowly added dropwise
Ethanol amine, 0.5h are dripped, and are reacted 5h at a temperature of 110 DEG C, are obtained hydroxyl epoxy resin；
(2) by after 100 parts of polyether polyols dehydration of alcohols, 70 DEG C is cooled to, 50 parts of toluene di-isocyanate(TDI)s are added, in 90 DEG C of temperature
Degree is lower to react 3h, then is cooled to 80 DEG C, and 9 parts of dihydromethyl propionic acids are added, react 3.5h at a temperature of 90 DEG C；It drops after reaction
To 50 DEG C hydroxyl epoxy resin made from 60 parts of acetone, 5 parts of silane coupling agent KH-151 and 11 parts of steps (1) is added, 90 in temperature
2h is reacted at a temperature of DEG C, then is cooled to 50 DEG C, obtains base polyurethane prepolymer for use as, and NCO mass content is 3.0%；
(3) 11 parts of triethylamines of addition and 100 parts of water in the base polyurethane prepolymer for use as made from step (2), high speed dispersion, then plus
Enter 15 parts of ethylenediamines, react 1h at a temperature of 90 DEG C, finally decompression steams acetone, obtains epoxy resin modified aqueous polyurethane
Adhesive.
Embodiment 2
(1) by 10mol bisphenol A type epoxy resin, it is heated to 70-90 DEG C, stirs 20-30min, then 8mol bis- is slowly added dropwise
Ethanol amine, 0.5h are dripped, and are reacted 5h at a temperature of 110 DEG C, are obtained hydroxyl epoxy resin；
(2) by after 90 parts of polyether polyols dehydration of alcohols, 70 DEG C is cooled to, 40 parts of toluene di-isocyanate(TDI)s are added, in 85 DEG C of temperature
Degree is lower to react 3h, then is cooled to 80 DEG C, and 7 parts of dimethylolpropionic acids are added, react 3.5h at a temperature of 85 DEG C；It drops after reaction
50 parts of butanone, 2 parts of silane coupling agent KH-602,4 parts of silane resin acceptor kh-550s and 14 parts of step (1) systems are added to 50 DEG C in temperature
The hydroxyl epoxy resin obtained, reacts 1h at a temperature of 85 DEG C, then be cooled to 50 DEG C, obtains base polyurethane prepolymer for use as, NCO mass content
It is 4.0%；
(3) 12 parts of triethylamines and 250 parts of water, high speed dispersion are added to add in the base polyurethane prepolymer for use as made from step (2)
10 parts of ethylenediamines and 8 parts of hexamethylene diamines, react 1h at a temperature of 85 DEG C, and finally decompression steams butanone, obtain epoxy resin modification
Aqueous Polyurethane Adhesives.
Embodiment 3
(1) by 10mol bisphenol A type epoxy resin, it is heated to 70-90 DEG C, stirs 20-30min, then 8mol bis- is slowly added dropwise
Ethanol amine, 0.5h are dripped, and are reacted 5h at a temperature of 110 DEG C, are obtained hydroxyl epoxy resin；
(2) by after 110 parts of polyether polyols dehydration of alcohols, 80 DEG C is cooled to, 60 parts of isophorone diisocyanate are added, 90
3h is reacted at a temperature of DEG C, then is cooled to 80 DEG C, 10 parts of dihydromethyl propionic acids are added, and reacts 4h at a temperature of 90 DEG C；Reaction terminates
After be cooled to 60 DEG C, add hydroxyl asphalt mixtures modified by epoxy resin made from 90 parts of ethyl acetate, 7 parts of silane coupling agent KH-792 and 15 parts of steps (1)
Rouge reacts 2h at a temperature of 90 DEG C, then is cooled to 60 DEG C, obtains base polyurethane prepolymer for use as, and NCO mass content is 3.0%；
(3) 13 parts of triethylamines of addition and 180 parts of water in the base polyurethane prepolymer for use as made from step (2), high speed dispersion, then plus
Enter 20 parts of diethylenetriamines, react 1h at a temperature of 90 DEG C, finally decompression steams ethyl acetate, obtains epoxy resin modification water
Property adhesive for polyurethane.
Comparative example 1
(1) by after 100 parts of polyether polyols dehydration of alcohols, 70 DEG C is cooled to, 50 parts of toluene di-isocyanate(TDI)s are added, in 90 DEG C of temperature
Degree is lower to react 3h, then is cooled to 80 DEG C, and 9 parts of dihydromethyl propionic acids are added, react 3.5hj at a temperature of 90 DEG C；After reaction
50 DEG C are cooled to, 60 parts of acetone, 5 parts of silane coupling agent KH-151 and 11 parts of bisphenol A type epoxy resins are added, at a temperature of 90 DEG C
2h is reacted, then is cooled to 50 DEG C, obtains base polyurethane prepolymer for use as, NCO mass content is 3.0%；
(2) 11 parts of triethylamines of addition and 220 parts of water in the base polyurethane prepolymer for use as made from step (2), high speed dispersion, then plus
Enter 15 parts of ethylenediamines, react 1h at a temperature of 90 DEG C, finally decompression steams acetone, obtains Aqueous Polyurethane Adhesives.
Comparative example 2
(1) by 10mol bisphenol A type epoxy resin, it is heated to 70-90 DEG C, stirs 20-30min, then 8mol bis- is slowly added dropwise
Ethanol amine, 0.5h are dripped, and are reacted 5h at a temperature of 110 DEG C, are obtained hydroxyl epoxy resin；
(2) by after 100 parts of polyether polyols dehydration of alcohols, 70 DEG C is cooled to, 50 parts of toluene di-isocyanate(TDI)s are added, in 90 DEG C of temperature
Degree is lower to react 3h, then is cooled to 80 DEG C, and 9 parts of dihydromethyl propionic acids are added, react 3.5h at a temperature of 90 DEG C；It drops after reaction
Temperature is added hydroxyl epoxy resin made from 60 parts of acetone, 11 parts of steps (1), reacts 2h at a temperature of 90 DEG C, then cool down to 50 DEG C
To 50 DEG C, base polyurethane prepolymer for use as is obtained, NCO mass content is 3.0%；
(3) 11 parts of triethylamines of addition and 250 parts of water in the base polyurethane prepolymer for use as made from step (2), high speed dispersion, then plus
Enter 15 parts of ethylenediamines, react 1h at a temperature of 90 DEG C, finally decompression steams acetone, obtains Aqueous Polyurethane Adhesives.
The embodiment 1-3 and comparative example 1-2 Aqueous Polyurethane Adhesives prepared are tested for the property, test method is such as
Under:
(1) glue film tensile strength is tested: using GB/T528-1998；
(2) peel strength test: GB/T2791-1995 is used；
(3) glue film water absorption rate test: preparing glue film with equi-volume process, and the glue film after vacuum drying is cut into 60mm × 60mm
× 1mm small cube, its quality are referred to as m0, impregnate into the water for 24 hours, the liquid on surface blotted after taking-up, its quality is referred to as m1,
Water absorption rate the W=[(m of glue film in water1-m0)/m0] × l00%；
(4) heat resisting temperature is tested: using synchronous solving, nitrogen protection, 20-600 DEG C of temperature test range, heating speed
Rate 10 DEG C/min, sample quality 10mg.
Test result is as shown in table 1:
The performance test table of the Aqueous Polyurethane Adhesives of table 1 embodiment 1-3 and comparative example 1-2 preparation
Wherein, hydroxyl epoxy resin is not added in comparative example 1, is changed to that bisphenol A type epoxy resin, remaining condition and embodiment is added
1 is identical；Silane coupling agent is not added in comparative example 2, remaining condition is same as Example 1.
As can be seen from the table, be added epoxy resin and it is silane coupler modified or only be added hydroxyl epoxy resin modification
Result it is unsatisfactory；And be added hydroxyl epoxy resin and it is silane coupler modified after, the power of Aqueous Polyurethane Adhesives product
Performance, water resistance and heat resistance is learned to be significantly improved.
Claims (10)
1. a kind of epoxy resin modified aqueous polyurethane adhesive for building, it is characterised in that: including following raw material: polyether polyols
Alcohol, isocyanates, crosslinking agent, hydroxyl epoxy resin, hydrophilic chain extender, triethylamine, solvent, amine chain extender and water；
The polyether polyol relative molecular mass is 500~750, and degree of functionality is 1.5~2.5；
The hydroxyl epoxy resin is reacted by bisphenol A type epoxy resin and diethanol amine to be made.
2. epoxy resin modified aqueous polyurethane adhesive for building according to claim 1, it is characterised in that: bisphenol-A
The molar ratio of type epoxy resin and diethanol amine is 1:0.8-1.4.
3. epoxy resin modified aqueous polyurethane adhesive for building according to claim 1, it is characterised in that: including with
The raw material of lower mass fraction:
4. epoxy resin modified aqueous polyurethane adhesive for building according to claim 1, it is characterised in that: crosslinking agent
For one or both of silane coupling agent KH-151, KH-540, KH-550, KH-560, KH-570, KH-602, KH-792 with
On mixture.
5. epoxy resin modified aqueous polyurethane adhesive for building according to claim 1, it is characterised in that: solvent is
Acetone, butanone or ethyl acetate.
6. epoxy resin modified aqueous polyurethane adhesive for building according to claim 1, it is characterised in that: hydrophilic expansion
Chain agent is dihydromethyl propionic acid or dimethylolpropionic acid.
7. epoxy resin modified aqueous polyurethane adhesive for building according to claim 1, it is characterised in that: amine expands
Chain agent is the mixture of one or more of ethylenediamine, hexamethylene diamine, diethylenetriamine, triethylene tetramine.
8. epoxy resin modified aqueous polyurethane adhesive for building according to claim 1, it is characterised in that: isocyanic acid
Ester is isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate or toluene diisocyanate
Acid esters.
9. a kind of preparation side of the described in any item epoxy resin modified aqueous polyurethane adhesives for building of claim 1-8
Method, it is characterised in that: the following steps are included:
(1) bisphenol A type epoxy resin is heated to 70-90 DEG C, stirs 20-30min, then diethanol amine is added dropwise, 0.5-1h is added dropwise
It is complete, 5-6h is reacted at a temperature of 100-110 DEG C, obtains hydroxyl epoxy resin；
(2) it after polyether polyols dehydration of alcohols, will be cooled to 70-80 DEG C, isocyanates is added, reacts 3-5h at a temperature of 85-90 DEG C,
It is cooled to 70-80 DEG C again, hydrophilic chain extender is added, reacts 3-5h at a temperature of 85-90 DEG C；It is cooled to 50-60 after reaction
DEG C, hydroxyl epoxy resin made from addition solvent, crosslinking agent and step (1) reacts 1-2h, then cool down at a temperature of 85-90 DEG C
To 50-60 DEG C, base polyurethane prepolymer for use as is obtained；
(3) triethylamine and water are added in the base polyurethane prepolymer for use as made from step (2), dispersion adds amine chain extender,
1-2h is reacted at a temperature of 85-90 DEG C, finally decompression steams solvent, obtains epoxy resin modified aqueous polyurethane adhesive.
10. the preparation method of epoxy resin modified aqueous polyurethane adhesive for building according to claim 9, feature
Be :-NCO the mass content of base polyurethane prepolymer for use as is 3.0-4.0% in step (2).
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Cited By (8)
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| CN110129121A (en) * | 2019-05-31 | 2019-08-16 | 黄智翔 | Antirust corrosion-proof cutting fluid and preparation method thereof |
| CN111057213A (en) * | 2019-12-31 | 2020-04-24 | 北京市市政工程研究院 | Latent curing polyurethane material for maintaining hinge joint of fabricated concrete hollow slab bridge and preparation method thereof |
| CN112592455A (en) * | 2020-12-09 | 2021-04-02 | 湖南林特新材料科技有限责任公司 | Synthesis method of single-component water-based epoxy emulsion |
| CN112877020A (en) * | 2019-11-29 | 2021-06-01 | 昆山市冠宝化学有限公司 | Novel water-based polyurethane adhesive and preparation method thereof |
| CN114085638A (en) * | 2021-12-22 | 2022-02-25 | 南宝树脂（佛山）有限公司 | Water-based hydrolysis-resistant polyurethane adhesive for shoes and preparation method thereof |
| CN114133533A (en) * | 2021-12-17 | 2022-03-04 | 鹤山市金润纳新型材料有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
| CN115595035A (en) * | 2022-10-31 | 2023-01-13 | 浙江兴土桥梁专用装备制造有限公司（Cn） | Road surface anti-skid coating |
| CN116622326A (en) * | 2023-06-29 | 2023-08-22 | 东莞市艺辉胶粘剂有限公司 | Modified polyurethane adhesive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110129121A (en) * | 2019-05-31 | 2019-08-16 | 黄智翔 | Antirust corrosion-proof cutting fluid and preparation method thereof |
| CN110129121B (en) * | 2019-05-31 | 2022-04-05 | 黄智翔 | Antirust corrosion-resistant cutting fluid and preparation method thereof |
| CN112877020A (en) * | 2019-11-29 | 2021-06-01 | 昆山市冠宝化学有限公司 | Novel water-based polyurethane adhesive and preparation method thereof |
| CN111057213A (en) * | 2019-12-31 | 2020-04-24 | 北京市市政工程研究院 | Latent curing polyurethane material for maintaining hinge joint of fabricated concrete hollow slab bridge and preparation method thereof |
| CN112592455A (en) * | 2020-12-09 | 2021-04-02 | 湖南林特新材料科技有限责任公司 | Synthesis method of single-component water-based epoxy emulsion |
| CN112592455B (en) * | 2020-12-09 | 2022-06-07 | 湖南林特科技有限公司 | Synthesis method of single-component water-based epoxy emulsion |
| CN114133533A (en) * | 2021-12-17 | 2022-03-04 | 鹤山市金润纳新型材料有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
| CN114085638A (en) * | 2021-12-22 | 2022-02-25 | 南宝树脂（佛山）有限公司 | Water-based hydrolysis-resistant polyurethane adhesive for shoes and preparation method thereof |
| CN114085638B (en) * | 2021-12-22 | 2023-02-21 | 南宝树脂（佛山）有限公司 | Water-based hydrolysis-resistant polyurethane adhesive for shoes and preparation method thereof |
| CN115595035A (en) * | 2022-10-31 | 2023-01-13 | 浙江兴土桥梁专用装备制造有限公司（Cn） | Road surface anti-skid coating |
| CN116622326A (en) * | 2023-06-29 | 2023-08-22 | 东莞市艺辉胶粘剂有限公司 | Modified polyurethane adhesive and preparation method thereof |
| CN116622326B (en) * | 2023-06-29 | 2023-11-14 | 东莞市艺辉胶粘剂有限公司 | Modified polyurethane adhesive and preparation method thereof |
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