CN110128616A - A kind of fluorine silicon is total to the preparation method of modified aqueous polyurethane - Google Patents
A kind of fluorine silicon is total to the preparation method of modified aqueous polyurethane Download PDFInfo
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- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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Abstract
A kind of fluorine silicon is total to the preparation method of modified aqueous polyurethane, include the following steps: that (1) diisocyanate, polymer diatomic alcohol, double hydroxy silicon oils, hydrophilic chain extender, catalyst dibutyltin dilaurylate are added in reaction kettle, 90~120min is stirred at 50~70 DEG C, obtains performed polymer；(2) acetone dilution is added in resulting performed polymer, adds small molecule fluorine substituted alcohols, small molecule dihydric alcohol, crosslinking agent, the reaction was continued at 50~70 DEG C 90~120min；(3) reaction temperature is reduced to 30~40 DEG C, and neutralizer triethylamine is added and stirs evenly；Diamine chain extenders and water is added, high speed emulsifies, and decompression pumps acetone and obtains product.The method that this preparation method is modified altogether due to using fluorine silicon, gained aqueous polyurethane water proof anti-soil performance can be improved 30% or more, while gained polyurethane is with good stability, lower production cost.
Description
Technical field
The present invention relates to polyurethane to synthesize field, and a kind of fluorine silicon is total to the preparation method of modified aqueous polyurethane.
Background technique
Aqueous polyurethane takes water as a solvent, and has nontoxic, environmentally friendly, and has and processes the advantages such as easy to use, therefore,
Fabric coating, leather top finishing etc. tool have been widely used.But common aqueous polyurethane is due to being added hydrophily
Monomer, water proof anti-soil ability are poor.With the simple organic-silicon-modified hydrophobicity that can improve polyurethane to a certain extent, reduce
The surface energy of polyurethane, but its antifouling waterproof ability raising is limited.And simple organic fluorine richness can also be reduced largely
The surface energy of polyurethane, but need to add more Organic fluoride to reach higher water proof anti-soil ability, and add excessive meeting
The water solubility and long-time storage stability of aqueous polyurethane are influenced, and production cost also greatly improves.Chinese patent application
201010115181.4 describing a kind of single-component silicon/fluorine modified aqueous polyurethane resin and preparation method thereof, Chinese patent Shen
201310368406.0 it please describe a kind of fluosilicic Modified Waterborne Polyurethane lotion and preparation method thereof, above-mentioned two document
What is introduced is all the fluosilicic modified water with the fluosilicic modified aqueous polyurethane on building emulsion and coating, on textile cloth
Property polyurethane there is not yet report.
Summary of the invention
The present invention mentions to overcome the problems, such as that the existing aqueous polyurethane obtained by organosilicon or organic fluorine richness merely exists
A kind of fluorine silicon is total to the preparation method of modified aqueous polyurethane out, and gained aqueous polyurethane is anti-for that can greatly improve on textile cloth
Water anti-pollution, while gained polyurethane is with good stability, lower production cost.
The preparation method that this fluorine silicon is total to modified aqueous polyurethane includes the following steps:
(1) by diisocyanate, polymer diatomic alcohol, double hydroxy silicon oils, hydrophilic chain extender, two fourth of catalyst dibutyltin cinnamic acid
Ji Xi is added in reaction kettle, and 90~120min is stirred at 50~70 DEG C, obtains performed polymer；
(2) acetone dilution is added in the resulting performed polymer of upper step, adds small molecule fluorine substituted alcohols, small molecule binary
Alcohol, crosslinking agent, the reaction was continued at 50~70 DEG C 90~120min；
(3) reaction temperature is reduced to 30~40 DEG C, and neutralizer is added and stirs evenly；Diamine chain extenders and water is added, it is high
Speed emulsification, decompression pump acetone, obtain fluorine silicon and be total to modified aqueous polyurethane.
This fluorine silicon is total to the method that the preparation method of modified aqueous polyurethane is modified altogether due to using fluorine silicon, and gained is aqueous
Polyurethane can be improved 30% or more for water proof anti-soil performance on textile cloth, while gained aqueous polyurethane is with good steady
It is qualitative, lower production cost.
Specific embodiment
The preparation method that this fluorine silicon is total to modified aqueous polyurethane includes the following steps:
(1) by diisocyanate, polymer diatomic alcohol, double hydroxy silicon oils, hydrophilic chain extender, two fourth of catalyst dibutyltin cinnamic acid
Ji Xi is added in reaction kettle, and 90~120min is stirred at 50~70 DEG C, obtains performed polymer；
(2) acetone dilution is added in the resulting performed polymer of upper step, adds small molecule fluorine substituted alcohols, small molecule binary
Alcohol, crosslinking agent, the reaction was continued at 50~70 DEG C 90~120min；
(3) reaction temperature is reduced to 30~40 DEG C, and neutralizer is added and stirs evenly；Diamine chain extenders and water is added, it is high
Speed emulsification, decompression pump acetone, obtain fluorine silicon and be total to modified aqueous polyurethane.
This fluorine silicon is total in the preparation method of modified aqueous polyurethane, the diisocyanate, polymer diatomic alcohol, double
Hydroxy silicon oil, hydrophilic chain extender, catalyst, small molecule fluorine substituted alcohols, small molecule dihydric alcohol, crosslinking agent, neutralizer, diamine expand
Chain agent, water, acetone weight ratio can for (15~20) ︰ (40~50) ︰ (5~10) ︰ (3~6) ︰ (0.1~0.5) ︰ (0.5~
0.8) ︰ (0.3~0.8) ︰ (3~8) ︰ (2~5) ︰ (3~6) ︰ (130~150) ︰ (10~30).
This fluorine silicon is total in the preparation method of modified aqueous polyurethane, and the diisocyanate can be isophorone two
Isocyanates, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, hexa-methylene
One or more of diisocyanate, insoluble substance is in 1000ppm or less in diisocyanate.
This fluorine silicon is total in the preparation method of modified aqueous polyurethane, and the molecular weight of double hydroxy silicon oils can be
1000~5000.
This fluorine silicon is total in the preparation method of modified aqueous polyurethane, the small molecule fluorine substituted alcohols be can be octafluoro
For the fluoro monohydric alcohol such as amylalcohol, hexafluoroisopropanol, the catalyst can be different for dibutyl tin dilaurate or other catalysis
Cyanate and catalyst containing active hydrogen reaction, the neutralizer can be the tertiary amines such as triethylamine.
This fluorine silicon is total in the preparation method of modified aqueous polyurethane, and the hydrophilic chain extender can be double methylols third
One or more of alkane, double methylol butane etc., the small molecule dihydric alcohol can be ethylene glycol, butanediol, hexylene glycol
One or more of, the crosslinking agent can be one of glycerol, trimethylolpropane, polyethers N330, polyethers N303
Or it is several.
Below by embodiment, invention is further described in detail.
Embodiment 1
Using the raw material of following weight: (insoluble substance exists 17.5kg isophorone diisocyanate in diisocyanate
800ppm or less), the bis- hydroxymethyl-propanes of the bis- hydroxy silicon oils -1000,4.5kg of 45kg polytetrahydrofuran diol -2000,7.5kg,
0.2kg dibutyl tin dilaurate, 0.7kg hexafluoroisopropanol, 0.7kg butanediol, 5kg trimethylolpropane, 4kg triethylamine,
5kg ethylenediamine, 145kg water and 20kg acetone.
It is prepared using following steps:
Step 1: by isophorone diisocyanate, polytetrahydrofuran diol -2000, double hydroxy silicon oils -1000, double hydroxyls
Methylpropane, dibutyl tin dilaurate are added in reaction kettle, stir 90min at 60 DEG C, obtain performed polymer.
Step 2: being added acetone dilution in the performed polymer obtained by step 1, octafluoro is added for amylalcohol, butanediol, three hydroxyl first
Base propane, the reaction was continued at 60 DEG C 90min.
Step 3: reducing reaction temperature to 30 DEG C, and neutralizer triethylamine is added and stirs 20min；Ethylenediamine and water is added, it is high
Speed emulsification 15min, decompression, which pumps acetone and obtains fluorine silicon, is total to modified aqueous polyurethane 235kg.Water is connect after products obtained therefrom film forming
Feeler is greater than 113 °.
Embodiment 2
Use the raw material of following weight: 18kg toluene di-isocyanate(TDI) (in diisocyanate insoluble substance 600ppm with
Under), the bis- hydroxymethyl-propanes of the bis- hydroxy silicon oils -1000,4kg of 47kg polyethers N220,7.5kg, 0.2kg dibutyl tin dilaurate,
0.7kg octafluoro is for amylalcohol, 0.65kg butanediol, 4.8kg trimethylolpropane, 4.2kg triethylamine, 5.2kg ethylenediamine, 145kg
Water and 20kg acetone.
It is prepared using following steps:
Step 1: by toluene di-isocyanate(TDI), polyethers N220, double hydroxy silicon oils -1000, double hydroxymethyl-propanes, two laurels
Sour dibutyl tin is added in reaction kettle, stirs 120min at 50 DEG C, obtains performed polymer.
Step 2: being added acetone dilution in the performed polymer obtained by step 1, octafluoro is added for amylalcohol, butanediol, three hydroxyl first
Base propane, the reaction was continued at 50 DEG C 120min.
Step 3: reducing reaction temperature to 30 DEG C, and neutralizer triethylamine is added and stirs 20min；Ethylenediamine and water is added, it is high
Speed emulsification 15min, decompression, which pumps acetone and obtains fluorine silicon, is total to modified aqueous polyurethane 237kg.Water is connect after products obtained therefrom film forming
Feeler is greater than 112 °.
Embodiment 3
Using the raw material of following weight: (insoluble substance exists 17.3kg hexamethylene diisocyanate in diisocyanate
1000ppm or less), the bis- methylol butane of the bis- hydroxy silicon oils -1000,4.2kg of 46kg polypropylene glycol ether -2000,7.5kg, 0.2kg
Dibutyl tin dilaurate, 0.7kg octafluoro is for amylalcohol, 0.65kg butanediol, 4.8kg glycerol, 4.5kg triethylamine, 5.5kg second two
Amine, 145kg water and 20kg acetone.
It is prepared using following steps:
Step 1: by hexamethylene diisocyanate, polypropylene glycol ether -2000, double hydroxy silicon oils -1000, double methylols
Butane, dibutyl tin dilaurate are added in reaction kettle, stir 90min at 70 DEG C, obtain performed polymer.
Step 2: being added acetone dilution in the performed polymer obtained by step 1, octafluoro is added for amylalcohol, butanediol, glycerol, and 70
The reaction was continued at DEG C 90min.
Step 3: reducing reaction temperature to 30 DEG C, and neutralizer triethylamine is added and stirs 20min；Ethylenediamine and water is added, it is high
Speed emulsification 15min, decompression, which pumps acetone and obtains fluorine silicon, is total to modified aqueous polyurethane 237kg.Water is connect after products obtained therefrom film forming
Feeler is greater than 111 °.
Embodiment 4
Using the raw material of following weight: (insoluble substance exists 17.8kg dicyclohexyl methyl hydride diisocyanate in diisocyanate
1000ppm or less), the bis- methylol butane of the bis- hydroxy silicon oils -1000,4.2kg of 46kg polypropylene glycol ether -2000,7.5kg, 0.2kg
Dibutyl tin dilaurate, 0.7kg octafluoro is for amylalcohol, 0.65kg butanediol, 4.8kg glycerol, 4.5kg triethylamine, 5.5kg second two
Amine, 145kg water and 20kg acetone.
It is prepared using following steps:
Step 1: by dicyclohexyl methyl hydride diisocyanate, polypropylene glycol ether -2000, double hydroxy silicon oils -1000, double hydroxyls
Methybutane, dibutyl tin dilaurate are added in reaction kettle, stir 90min at 70 DEG C, obtain performed polymer.
Step 2: being added acetone dilution in the performed polymer obtained by step 1, octafluoro is added for amylalcohol, butanediol, glycerol, and 70
The reaction was continued at DEG C 90min.
Step 3: reducing reaction temperature to 30 DEG C, and neutralizer triethylamine is added and stirs 20min；Ethylenediamine and water is added, it is high
Speed emulsification 15min, decompression, which pumps acetone and obtains fluorine silicon, is total to modified aqueous polyurethane 237kg.Water is connect after products obtained therefrom film forming
Feeler is greater than 114 °.
Embodiment 5
Using the raw material of following parts by weight: (insoluble substance exists 17.8kg isophorone diisocyanate in diisocyanate
800ppm or less), the bis- methylol butane of the bis- hydroxy silicon oils -1000,4.2kg of 46kg polypropylene glycol ether -2000,7.5kg, 0.2kg
Dibutyl tin dilaurate, 0.7kg octafluoro is for amylalcohol, 0.6kg1,3-propanediol, 4.8kg glycerol, 4.5kg triethylamine, 5.5kg
Ethylenediamine, 145kg water and 20kg acetone.
It is prepared using following steps:
Step 1: by dicyclohexyl methyl hydride diisocyanate, polypropylene glycol ether -2000, double hydroxy silicon oils -1000, double hydroxyls
Methybutane, dibutyl tin dilaurate are added in reaction kettle, stir 90min at 70 DEG C, obtain performed polymer.
Step 2: being added acetone dilution in the performed polymer obtained by step 1, octafluoro is added for amylalcohol, 1,3-PD, sweet
Oil, the reaction was continued at 70 DEG C 90min.
Step 3: reducing reaction temperature to 30 DEG C, and neutralizer triethylamine is added and stirs 20min；Ethylenediamine and water is added, it is high
Speed emulsification 15min, decompression, which pumps acetone and obtains fluorine silicon, is total to modified aqueous polyurethane 237kg.Water is connect after products obtained therefrom film forming
Feeler is greater than 113 °.
Embodiment 6
Using the raw material of following parts by weight: (insoluble substance exists 17.8kg isophorone diisocyanate in diisocyanate
800ppm or less), the bis- methylol butane of the bis- hydroxy silicon oils -1000,4.2kg of 46kg polypropylene glycol ether -2000,7.5kg, 0.2kg
Dibutyl tin dilaurate, 0.7kg octafluoro is for amylalcohol, 0.6kg butanediol, 4.8kg glycerol, 4.5kg triethylamine, 6kg hexamethylene diamine,
145kg water and 20kg acetone.
It is prepared using following steps:
Step 1: by dicyclohexyl methyl hydride diisocyanate, polypropylene glycol ether -2000, double hydroxy silicon oils -1000, double hydroxyls
Methybutane, dibutyl tin dilaurate are added in reaction kettle, stir 90min at 70 DEG C, obtain performed polymer.
Step 2: being added acetone dilution in the performed polymer obtained by step 1, octafluoro is added for amylalcohol, butanediol, glycerol, and 70
The reaction was continued at DEG C 90min.
Step 3: reducing reaction temperature to 30 DEG C, and neutralizer triethylamine is added and stirs 20min；Hexamethylene diamine and water is added, it is high
Speed emulsification 15min, decompression, which pumps acetone and obtains fluorine silicon, is total to modified aqueous polyurethane 237.5kg.To water after products obtained therefrom film forming
Contact angle is greater than 113 °.
The measurement of contact angle in above-described embodiment is carried out by the standard of GB/T30447-2013.
Six kinds of aqueous polyurethanes that six embodiments are prepared, which are respectively coated, is made sample in scrim surfaces, according to state
The method for marking GB/T4100-2600 uses the cleaning method of program A, (divides the base fabric of six kinds of embodiment aqueous polyurethanes processing
Be not denoted as base fabric 1-6), untreated base fabric (being denoted as base fabric 7) and the base fabric with common commercially available aqueous polyurethane processing (be denoted as base
Cloth 8) antifouling capacity test is carried out, obtain result as shown in the table:
The antifouling result of base fabric after the different aqueous polyurethane processing of table 1
Prevented compared with common artificial leather facing material using artificial leather facing material made of this aqueous polyurethane as seen from the above table
Water anti-pollution significantly improves.
Claims (6)
1. the preparation method that a kind of fluorine silicon is total to modified aqueous polyurethane, which comprises the steps of:
(1) by diisocyanate, polymer diatomic alcohol, double hydroxy silicon oils, hydrophilic chain extender, catalyst dibutyltin dilaurylate
It is added in reaction kettle, 90~120min is stirred at 50~70 DEG C, obtains performed polymer；
(2) acetone dilution is added in the resulting performed polymer of upper step, adds small molecule fluorine substituted alcohols, small molecule dihydric alcohol, hand over
Join agent, the reaction was continued at 50~70 DEG C 90~120min；
(3) reaction temperature is reduced to 30~40 DEG C, and neutralizer triethylamine is added and stirs evenly；Diamine chain extenders and water is added,
High speed emulsifies, and decompression pumps acetone, obtains fluorine silicon and is total to modified aqueous polyurethane.
2. the preparation method that fluorine silicon according to claim 1 is total to modified aqueous polyurethane, it is characterised in that described two are different
Cyanate, polymer diatomic alcohol, double hydroxy silicon oils, hydrophilic chain extender, catalyst, small molecule fluorine substituted alcohols, small molecule dihydric alcohol,
Crosslinking agent, neutralizer, diamine chain extenders, water, acetone weight ratio be (15~20) ︰ (40~50) ︰ (5~10) ︰ (3~6) ︰
(0.1~0.5) ︰ (0.5~0.8) ︰ (0.3~0.8) ︰ (3~8) ︰ (2~5) ︰ (3~6) ︰ (130~150) ︰ (10~30).
3. the preparation method that fluorine silicon according to claim 1 or 2 is total to modified aqueous polyurethane, it is characterised in that described two
Isocyanates is isophorone diisocyanate, toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, dicyclohexyl methyl hydride
One or more of diisocyanate, hexamethylene diisocyanate, insoluble substance is in 1000ppm or less in diisocyanate.
4. the preparation method that fluorine silicon according to claim 3 is total to modified aqueous polyurethane, it is characterised in that double hydroxyls
The molecular weight of base silicone oil is 1000-5000.
5. the preparation method that fluorine silicon according to claim 4 is total to modified aqueous polyurethane, it is characterised in that described small point
Sub- fluorine substituted alcohols are octafluoro for amylalcohol or hexafluoroisopropanol.
6. the preparation method that fluorine silicon according to claim 5 is total to modified aqueous polyurethane, it is characterised in that described is hydrophilic
Chain extender is one or more of double hydroxymethyl-propane, double methylol butane etc., the small molecule dihydric alcohol be ethylene glycol,
One or more of butanediol, hexylene glycol, the crosslinking agent are glycerol, trimethylolpropane, polyethers N330, polyethers N303
One or more of.
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