CN109705792A - Shoes Aqueous Polyurethane Adhesives and preparation method thereof - Google Patents
Shoes Aqueous Polyurethane Adhesives and preparation method thereof Download PDFInfo
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- CN109705792A CN109705792A CN201811610060.XA CN201811610060A CN109705792A CN 109705792 A CN109705792 A CN 109705792A CN 201811610060 A CN201811610060 A CN 201811610060A CN 109705792 A CN109705792 A CN 109705792A
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- aqueous polyurethane
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- polyurethane adhesives
- polyether polyol
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Abstract
The present invention relates to adhesive for polyurethane technical fields, and in particular to a kind of shoes Aqueous Polyurethane Adhesives and preparation method thereof.The Aqueous Polyurethane Adhesives include the raw material of following mass fraction: A100 parts of polyether polyol, 60~80 parts of polytetrahydrofuran diol, 25~30 parts of isocyanates, 12~19 parts of hydrophilic chain extender, 50~80 parts of solvent, 17~20 parts of neutralizer, 11~15 parts of amine chain extender, 170~190 parts of distilled water.Wherein, polyether polyol A is using glycerol as initiator, and propylene oxide open loop is ethylene oxide-capped, degree of functionality 2.5-3.5, and number-average molecular weight is the polyether polyol of 4500-5500；Isocyanates is 1,4- cyclohexane diisocyanate.The Aqueous Polyurethane Adhesives have good early strength and tack in use, and adhesion strength is high, heat-resist, water-tolerant；The present invention also provides preparation methods.
Description
Technical field
The present invention relates to adhesive for polyurethane technical fields, and in particular to a kind of shoes Aqueous Polyurethane Adhesives and its system
Preparation Method.
Background technique
Currently, polyurethane in use for shoes adhesive mainly uses traditional solvent-borne adhesive, bonding force is strong and hydrolysis, in ring
Protect and health more and more attention has been paid to today, external shoemaking brand has begun the Aqueous Adhesives using more environmentally friendly health
Instead of traditional adhesive.Aqueous Adhesives have many advantages, such as that economy, safety, the five poisonous creatures: scorpion, viper, centipede, house lizard, toad, pollution-free, smell is small using water as dispersing agent,
But its slow-drying, tack is lower, and the water resistance of film forming is bad.Aqueous Polyurethane Adhesives replace solvent borne polyurethane gluing
Agent, performance also need to further increase.
Ye Jiacan etc. is using HDI, IPDI and poly adipate succinic acid ester as base stock, diamino benzene sulfonic acid sodium and dihydroxy first
Base propionic acid is internal emulsifying agent, prepares solid content by acetone method and uses higher than 50%, without the shoes of organic solvent and stable storing
Aqueous Polyurethane Adhesives (synthesis of high solids content shoes Aqueous Polyurethane Adhesives, Chinese adhesive).Patent
A kind of preparation method of shoes environment-friendly type high performance water adhesive for polyurethane is disclosed in CN201710270359.4, using poly-
The pure and mild diisocyanate of ester polyol, polyether polyols is base stock, and dimethylolpropionic acid, ethylenediamine base sulfonate are hydrophilic expansion
Chain agent introduces double hydroxy sulfonate dispersions on main chain and substitutes part hydrophilic chain extender, and leading-in end amino silicane coupling agent,
The Aqueous Polyurethane Adhesives of excellent combination property are prepared by acetone method.One kind is disclosed in patent CN201210310648.X
High solids content shoes Aqueous Adhesives add hydrophilic chain extender and crosslinking agent chain extension using polyalcohol and Isocyanate prepolymers,
It finally neutralized, emulsified, obtained high solids content, have excellent performance, environmental-friendly Aqueous Adhesives.
Prior art is all made of polyester polyol or polyester polyol is compounded with polyether polyol, to prepare solid content
Higher Aqueous Polyurethane Adhesives improve the tack of adhesive for polyurethane, but the water resistance of polyester polyol is poor, low temperature
Flexibility is bad, seriously affects the service life of aqueous polyurethane.
Summary of the invention
In view of the deficiencies of the prior art, it the object of the present invention is to provide a kind of shoes Aqueous Polyurethane Adhesives, is using
There is good early strength and tack in the process, adhesion strength is high, heat-resist, water-tolerant；The present invention also provides it
Preparation method.
Shoes Aqueous Polyurethane Adhesives of the present invention, the raw material including following mass fraction:
Wherein, polyether polyol A is using glycerol as initiator, and propylene oxide open loop is ethylene oxide-capped, and degree of functionality is
2.5-3.5, number-average molecular weight are the polyether polyol of 4500-5500, and preferably the federal chemical Industrial Co., Ltd of Zibo moral letter is raw
The polyether polyol DMD-5000 of production.
Polyether polyol B be degree of functionality 1.5-2.5, the polytetrahydrofuran diol of number-average molecular weight 1500-2500, preferably
PTMEG-2000。
Isocyanates is 1,4- cyclohexane diisocyanate (CHDI).
CHDI is a kind of extraordinary diisocyanate, compared with other aliphatic isocyanates, molecular structure high degree of symmetry
With it is regular, thus crystallinity is strong, and the polyurethane of preparation has fabulous microphase-separated degree, and polyurethane is made to have unique flexibility
With excellent physical property, also there is water resistance outstanding, temperature tolerance, wearability, solvent resistance and resilience；With aromatic series isocyanic acid
Ester is compared, and phenyl ring is free of, and Yellowing will not occur for long-time illumination.
Hydrophilic chain extender is dihydromethyl propionic acid (DMPA) or dimethylolpropionic acid (DMBA).
Solvent is acetone, butanone or ethyl acetate.
Neutralizer is triethylamine.
Amine chain extender is ethylenediamine.
The preparation method of polyurethane in use for shoes adhesive of the present invention, comprising the following steps:
(1) polyether polyol A and polytetrahydrofuran diol are mixed, vacuum dehydration 1.5-2h at 90-100 DEG C is cooled to
50-60 DEG C, lead to nitrogen protection, isocyanates, hydrophilic chain extender is added, 1.5-2h is reacted at a temperature of 80-90 DEG C, then be cooled to
50-60 DEG C, solvent adjustment system viscosity is added, obtains base polyurethane prepolymer for use as；
(2) neutralizer and water are added in the base polyurethane prepolymer for use as made from step (1), the high speed under high shear effect
Dispersion adds chain extension after amine chain extender carries out, and finally decompression steams solvent, obtains shoes Aqueous Polyurethane Adhesives.
Compared with prior art, the invention has the following beneficial effects:
(1) present invention does not add polyester polyol component, is compounded, is made using polyether polyol A and polytetrahydrofuran diol
Aqueous polyurethane has good water resistance, low-temperature flexibility, extends the service life of Aqueous Polyurethane Adhesives, and two kinds
Polyether polyol is used in compounding the tack and adhesion strength for improving Aqueous Polyurethane Adhesives；
(2) present invention uses CHDI for base stock, and for CHDI compared with other aliphatic isocyanates, molecular structure is high
Degree is symmetrically and regular, thus crystallinity is strong, and the polyurethane of preparation has fabulous microphase-separated degree, has polyurethane unique
Flexibility and excellent physical property also have water resistance outstanding, temperature tolerance, wearability, solvent resistance and resilience；With aromatic series
Isocyanates is compared, and phenyl ring is free of, and Yellowing will not occur under long-time illumination for the polyurethane products of preparation.
Specific embodiment
The present invention will be further described with reference to embodiments, but protection scope of the present invention is not limited only to this.
Embodiment 1
(1) 100 parts of DMD-5000 and 60 part of polytetrahydrofuran diols are mixed, vacuum dehydration 1.5h at 90 DEG C is cooled to
50 DEG C, lead to nitrogen protection, 25 parts of CHDI, 12 parts of DMPA are added, react 1.5h at a temperature of 80 DEG C, be cooled to 50 DEG C, is added third
Ketone regulation system viscosity, obtains base polyurethane prepolymer for use as；
(2) 17 parts of triethylamines and 170 parts of water are added in the base polyurethane prepolymer for use as made from step (1), in high shear
Lower high speed dispersion is acted on, chain extension after 11 parts of ethylenediamines carry out is added, finally decompression steams acetone, obtains shoes with aqueous poly- ammonia
Ester adhesive.
Embodiment 2
(1) 100 parts of DMD-5000 and 80 part of polytetrahydrofuran diols are mixed, vacuum dehydration 2h at 100 DEG C is cooled to 60
DEG C, lead to nitrogen protection, 30 parts of CHDI, 19 parts of DMBA are added, react 2h at a temperature of 90 DEG C, be cooled to 50 DEG C, butanone tune is added
System viscosity is saved, base polyurethane prepolymer for use as is obtained；
(2) 20 parts of triethylamines and 190 parts of water are added in the base polyurethane prepolymer for use as made from step (1), in high shear
Lower high speed dispersion is acted on, chain extension after 15 parts of ethylenediamines carry out is added, finally decompression steams butanone, obtains shoes with aqueous poly- ammonia
Ester adhesive.
Embodiment 3
(1) 100 parts of DMD-5000 and 70 part of polytetrahydrofuran diols are mixed, vacuum dehydration 2h at 100 DEG C is cooled to 60
DEG C, lead to nitrogen protection, 28 parts of CHDI, 15 parts of DMBA are added, react 2h at a temperature of 90 DEG C, be cooled to 50 DEG C, acetic acid second is added
Ester regulation system viscosity, obtains base polyurethane prepolymer for use as；
(2) 18 parts of triethylamines and 180 parts of water are added in the base polyurethane prepolymer for use as made from step (1), in high shear
Lower high speed dispersion is acted on, chain extension after 13 parts of ethylenediamines carry out is added, finally decompression steams ethyl acetate, obtains shoes with aqueous
Adhesive for polyurethane.
Comparative example 1
This comparative example is substantially the same manner as Example 1, only difference is that isocyanates is HDI, the specific steps are as follows:
(1) 100 parts of DMD-5000 and 60 part of polytetrahydrofuran diols are mixed, vacuum dehydration 1.5h at 90 DEG C is cooled to
50 DEG C, lead to nitrogen protection, 25 parts of HDI, 12 parts of DMPA are added, react 1.5h at a temperature of 80 DEG C, be cooled to 50 DEG C, acetone is added
Regulation system viscosity, obtains base polyurethane prepolymer for use as；
(2) 17 parts of triethylamines and 170 parts of water are added in the base polyurethane prepolymer for use as made from step (1), in high shear
Lower high speed dispersion is acted on, chain extension after 11 parts of ethylenediamines carry out is added, finally decompression steams acetone, obtains shoes with aqueous poly- ammonia
Ester adhesive.
Comparative example 2
Aqueous Polyurethane Adhesives are prepared using method disclosed in patent 201210310648.X, the specific steps are as follows:
100 parts of polycaprolactone glycols, 40 parts of IPDI are heated to 70 DEG C, add 1 part of dibutyl tin dilaurate catalyst,
React 3h, 30 parts of DMPA, 10 parts of trimethylolpropanes be added, the reaction was continued 2h cools to 30 DEG C, be added 3 parts of acetone adjust it is viscous
Degree, adds 8 parts of triethylamines, 281 parts of deionized waters and 500 parts of aqueous polyurethane emulsions, stirs evenly to get aqueous polyurethane
Adhesive.
Comparative example 3
Aqueous Polyurethane Adhesives are prepared using method disclosed in patent 201710270359.4, the specific steps are as follows:
(1) it polymerize: by 106g polycaprolactone polyol, 34g propylene oxide polyether polyalcohol, the bis- hydroxy sulfonates of 20.4g
It mixes, vacuum dehydration 2h at 110 DEG C is cooled to 80 DEG C, and 20gHDI, 27.8g IPDI, 3.1g1,4- butanediol and 0.4g is added
Organic bismuth catalyst reacts 2h at 90 DEG C, adds 5.1g dimethylolpropionic acid the reaction was continued 2.5h, drop after nco value is qualified
To 55 DEG C hereinafter, 140g acetone viscosity reduction is added, addition 3.6g triethylamine neutralizes temperature, and after neutralization, 14.4g ethylenediamine base is added
Sodium sulfonate and 1.8g Amino End Group silane coupling agent are to get base polyurethane prepolymer for use as；
(2) it emulsifies: 250g deionized water, high speed shearing emulsification being added in the base polyurethane prepolymer for use as that step (1) obtains
2.7g isophorone diamine chain extension is added dropwise in 30min, and finally decompression steams acetone to get aqueous polyurethane emulsion；
(3) impregnation: 8g aqueous polyisocyanate curing agent is added in the aqueous polyurethane emulsion that step (2) obtains, stirs
Up to Aqueous Polyurethane Adhesives after addition 10.5g environment-friend auxiliaries after mixing uniformly, stirring 2h, viscosity and solid content qualification.
Aqueous Polyurethane Adhesives made from embodiment 1-3 and comparative example 1-3 are used for the fitting of different footwear materials, it is specific right
Than the results are shown in Table 1.
Properties of product test result made from table 1 embodiment 1-3 and comparative example 1-3
As seen from the above table, Aqueous Polyurethane Adhesives prepared by the present invention are used for the fitting of different footwear materials, show excellent
Different tack, cohesive force, water resistance and heat resistance, and preparation method of the present invention is simple, is not necessarily to impregnation, lower production costs,
It is convenient for industrialized production.
Claims (6)
1. a kind of shoes Aqueous Polyurethane Adhesives, it is characterised in that: the raw material including following mass fraction:
The polyether polyol A is using glycerol as initiator, and propylene oxide open loop is ethylene oxide-capped, degree of functionality 2.5-
3.5, number-average molecular weight is the polyether polyol of 4500-5500；
The polyether polyol B is degree of functionality 1.5-2.5, the polytetrahydrofuran diol of number-average molecular weight 1500-2500；
The isocyanates is 1,4- cyclohexane diisocyanate.
2. shoes Aqueous Polyurethane Adhesives according to claim 1, it is characterised in that: hydrophilic chain extender is dihydroxymethyl
Propionic acid or dimethylolpropionic acid.
3. shoes Aqueous Polyurethane Adhesives according to claim 1, it is characterised in that: solvent is acetone, butanone or second
Acetoacetic ester.
4. shoes Aqueous Polyurethane Adhesives according to claim 1, it is characterised in that: neutralizer is triethylamine.
5. shoes Aqueous Polyurethane Adhesives according to claim 1, it is characterised in that: amine chain extender is ethylenediamine.
6. a kind of preparation method of the described in any item shoes Aqueous Polyurethane Adhesives of claim 1-5, it is characterised in that: packet
Include following steps:
(1) polyether polyol A and polyether polyol B being mixed, vacuum dehydration 1.5-2h at 90-100 DEG C is cooled to 50-60 DEG C,
Isocyanates, hydrophilic chain extender is added, 1.5h is reacted at a temperature of 80-90 DEG C, then be cooled to 50-60 DEG C, solvent is added, obtains
Base polyurethane prepolymer for use as；
(2) neutralizer is added in the base polyurethane prepolymer for use as made from step (1) and water, high speed dispersion adds amine chain extender
Chain extension after progress, finally decompression steams solvent, obtained shoes Aqueous Polyurethane Adhesives.
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| CN201811610060.XA CN109705792A (en) | 2018-12-27 | 2018-12-27 | Shoes Aqueous Polyurethane Adhesives and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116858A (en) * | 2019-12-05 | 2020-05-08 | 黄晨笛 | High-solid-content polyether type waterborne polyurethane and preparation method thereof |
| CN111303822A (en) * | 2020-03-19 | 2020-06-19 | 嘉兴九健新材料科技有限公司 | Polyurethane water-based high-strength wig curtain adhesive and preparation method thereof |
| CN111978851A (en) * | 2020-08-31 | 2020-11-24 | 荆晓东 | High-temperature-resistant and water-resistant waterborne polyurethane coating and preparation method thereof |
| CN112280522A (en) * | 2020-11-04 | 2021-01-29 | 苏州言信新型材料有限公司 | Preparation method of water-based polyurethane adhesive for high-water-resistance purification equipment |
| CN113801292A (en) * | 2020-06-12 | 2021-12-17 | 万华化学集团股份有限公司 | Aqueous dispersion of polyurethane or polyurethane urea and preparation method thereof, aqueous space leather base and preparation method thereof |
| CN115124968A (en) * | 2022-07-28 | 2022-09-30 | 扬州市伟业消防器材有限公司 | Preparation method of adhesive for fire hose |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116858A (en) * | 2019-12-05 | 2020-05-08 | 黄晨笛 | High-solid-content polyether type waterborne polyurethane and preparation method thereof |
| CN111303822A (en) * | 2020-03-19 | 2020-06-19 | 嘉兴九健新材料科技有限公司 | Polyurethane water-based high-strength wig curtain adhesive and preparation method thereof |
| CN113801292A (en) * | 2020-06-12 | 2021-12-17 | 万华化学集团股份有限公司 | Aqueous dispersion of polyurethane or polyurethane urea and preparation method thereof, aqueous space leather base and preparation method thereof |
| CN113801292B (en) * | 2020-06-12 | 2022-08-05 | 万华化学集团股份有限公司 | Water dispersion of polyurethane or polyurethane urea and preparation method thereof, water-based space leather base and preparation method thereof |
| CN111978851A (en) * | 2020-08-31 | 2020-11-24 | 荆晓东 | High-temperature-resistant and water-resistant waterborne polyurethane coating and preparation method thereof |
| CN112280522A (en) * | 2020-11-04 | 2021-01-29 | 苏州言信新型材料有限公司 | Preparation method of water-based polyurethane adhesive for high-water-resistance purification equipment |
| CN115124968A (en) * | 2022-07-28 | 2022-09-30 | 扬州市伟业消防器材有限公司 | Preparation method of adhesive for fire hose |
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