CN107446151A - A kind of silicon fluoride modified polyurethane hydrophobic film and preparation method thereof - Google Patents
A kind of silicon fluoride modified polyurethane hydrophobic film and preparation method thereof Download PDFInfo
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- CN107446151A CN107446151A CN201710763936.3A CN201710763936A CN107446151A CN 107446151 A CN107446151 A CN 107446151A CN 201710763936 A CN201710763936 A CN 201710763936A CN 107446151 A CN107446151 A CN 107446151A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The present invention discloses a kind of silicon fluoride modified polyurethane hydrophobic film and preparation method thereof.Methods described includes：2~4h is reacted under the conditions of 60~80 DEG C after diisocyanate and polyether Glycols are mixed, adding solvent reduces system viscosity；It is cooled to 30~50 DEG C and adds 1~2h of fluorinated polysiloxane reaction；50~60 DEG C are warming up to, small molecule chain extender is added and reacts 1~2h, product is cast on the glass plate of horizontal, dry, that is, polyurethane hydrophobic film is made.The polyurethane hydrophobic film of the present invention has excellent hydrophobicity, and preparation method is easy, can be applied to automatically cleaning, field of waterproof materials.
Description
Technical field
The present invention relates to the hydrophobically modified technical field of polyurethane material, and in particular to a kind of silicon fluoride modified polyurethane is dredged
Water film and preparation method thereof
Background technology
Polyurethane is a kind of alternate block type polymer material of soft and hard segments, and this unique molecular structure makes polyurethane
Combination property is very superior, has the advantages that tensile strength is big, tearing strength is big, chemical resistance.But due to containing in chain
The groups such as substantial amounts of ester group, urea groups, there is also the shortcomings that hydrophobicity difference, limit it in the field such as waterproof, antifouling for polyurethane
Application.
At present, the hydrophobically modified of polyurethane mainly introduces hydrophobic grouping on segment, and fluorine and silicon are all to have low surface
The material of energy, therefore become a main research direction using Organic fluoride, organic silicon modified polyurethane.
Organosilicon refers to the polysiloxanes containing Si-O-Si unit structures in main chain, has good resistant of high or low temperature, resistance to
Hou Xing and the features such as excellent hydrophobicity.Organic silicon modified polyurethane mainly utilizes the poly- silica with reactive pattern group
Silicone segments with low-surface-energy are introduced into polyurethane segment by alkane and isocyanate terminated reaction.
It by the fluorinated polyether of bifunctionality is Material synthesis that most fluorochemical urethane, which is, this product molecule structure
Contain fluorine atom on main chain, but acted on by molecular backbone, it is more difficult to move to surface, it is difficult to excellent hydrophobic performance is obtained,
And fluorinated polyether price is generally expensive.Patent CN106750077A discloses a kind of system of side chain type hydrophobic oleophobic fluorochemical urethane
Preparation Method, the patent is to synthesize fluorochemical urethane with base polyurethane prepolymer for use as with fluorine-containing end-capping reagent and fluorine-containing chain extender, but the party
The synthesis step of fluorine-containing end-capping reagent and fluorine-containing chain extender is complex in method.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, it is an object of the invention to provide a kind of silicon fluoride modified polyurethane is hydrophobic
Film and preparation method thereof.This method will be incorporated into polyurethane backbone with the fluorine-containing siloxanes of low-surface-energy, side chain, due to
Thermodynamically microphase-separated easily occurs for incompatibility for both, and silicon fluoride is easy to, to surface migration, reduce due to its low-surface-energy
The surface free energy of polyurethane, polyurethane film made from this method has excellent hydrophobicity, and this method has operation letter
The characteristics of easy row.
The present invention is achieved through the following technical solutions.
A kind of preparation method of silicon fluoride modified polyurethane hydrophobic film, comprises the following steps：Take polyether Glycols, two different
Cyanate and catalyst, under nitrogen protection, solvent are added after 60~80 DEG C of 2~4h of stirring reaction, is cooled to 30~50 DEG C,
Fluorinated polysiloxane 1~2h of stirring reaction under nitrogen protection is added, is warming up to 50~60 DEG C, adds small molecule chain extender,
Nitrogen protection 1~2h of lower reaction, product is cast on the glass plate of horizontal, dried, i.e., a kind of obtained silicon fluoride is modified poly-
Urethane hydrophobic film；
Described diisocyanate and the mol ratio of polyether Glycols are 1.5:1~3:1；Described fluorinated polysiloxane is used
Measure as the 0.5%~5% of polyether Glycols quality.
Preferably, the diisocyanate is one or more of IPDI, toluene di-isocyanate(TDI).
Preferably, the polyether Glycols are included in PTMG class polytetramethylene oxides dihydric alcohol, PPG class polyether Glycols
More than one；The molecular weight of the polyether Glycols is 1000~3000.
Preferably, vacuum drying removes water 2h at 90~120 DEG C before the reaction of described polyether Glycols.
Preferably, described catalyst is dibutyl tin laurate.
Preferably, the solvent is one or more of toluene, dimethylformamide, tetrahydrofuran, acetone.
Preferably, described small molecule chain extender is small molecule glycol HO-R-OH, small molecule diamines NH2-R-NH2In one
More than kind, wherein R=CnH2n, n=1~6.
Preferably, the drying refers to be dried at room temperature for 12h~36h and then 60 DEG C~80 DEG C dry 8h~24h.
Preferably, the fluorinated polysiloxane is the fluorinated polysiloxane with double hydroxyl reaction active groups, is had such as
Under formula：
Wherein n=20~40.
Compared with prior art, advantage of the invention is that：
(1) present invention utilizes silicon fluoride modified polyurethane, has low surface free energy by being introduced in polyurethane segment
Fluorine element, element silicon can effectively reduce the surface free energy of material, and fluorine element is in the side chain of silicon fluoride, is easy to fluorine chain
Section improves its hydrophobicity to surface migration.
(2) present invention is hydrophobic thin using the synthesis silicon fluoride modified polyurethane such as commercially available isocyanates, fluorinated polysiloxane
Film, its raw material are easy to get, and cost is cheap, have the characteristics of technique is simple, expand application field of the polyurethane as hydrophobic material.
(3) fluorinated polysiloxane that the present invention uses has had the excellent properties of both fluorine element and polysiloxanes concurrently, due to
Polysiloxanes has the characteristics that preferable wearability, flexibility, good hand touch, silicon fluoride modified polyurethane hydrophobic material of the invention
It can be applicable to fields such as flexibility and the hydrophobic field for having particular/special requirement, such as textile, leathers.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the polyurethane that silicon fluoride is modified in embodiment 1；
Fig. 2 is the infrared spectrum of the polyurethane that silicon fluoride is modified in embodiment 2；
Fig. 3 is the infrared spectrum of the polyurethane in comparative example.
Embodiment
Further detailed description is done to the present invention with embodiment and accompanying drawing below, but embodiments of the present invention are not limited to
This.
The contact angle method of testing of polyurethane film described in following examples is as follows：Using upper marine morning JC2000D1
Type contact angle tester is tested, and using 5 μ L deionized waters, water droplet is dripped and tested after film surface, each sample
Take 3 points to be tested, take its average value.Water removal is dried in vacuo before ether diol reaction in following examples at 120 DEG C
2h。
Embodiment 1
By polyether Glycols (PTMG) of the molecular weight vacuum dried 40g for 2000,9g IPDIs
(IPDI) added with a drop dibutyltin dilaurate catalyst in the three-necked flask with condenser pipe, nitrogen (N2) rise under protection
Temperature is to 80 DEG C and 40ml anhydrous dimethyl formamide (DMF) reduction system viscosity is slowly added dropwise, and reacts 2h, is cooled to 30 DEG C,
The fluorinated polysiloxane that addition 1g molecular weight is 3000 is in nitrogen (N2) the lower stirring reaction 1.5h of protection；60 DEG C are warming up to, is added
The agent of 1,4- chain expansion of succinic acid is in nitrogen (N2) protection lower reaction 1h (addition of 1,4- butanediols and system residual isocyanate
Mol ratio is 1:2), product is cast on the glass plate of horizontal, is dried at room temperature for 24h and then 60 DEG C of dry 8h, that is, is made
The polyurethane hydrophobic film that a kind of silicon fluoride is modified.
The silicon fluoride modified polyurethane hydrophobic film of above-mentioned preparation is characterized, Fig. 1 is the polyurethane that silicon fluoride is modified
The infrared spectrum of film, contact angle test are shown in Table 1.By can see in infrared spectrum, 2270cm-1Place-feature of NCO group
Peak disappears, and illustrates that isocyanates is reacted completely；3329cm-1Place is hydrogen bonding-NH- stretching vibration peak, 1533cm-1Place
It is-NH- deformation vibration peak, 1714cm-1Place is the stretching vibration peak of the C=O in-NHCOO-, in 780cm-1Place is Si-
CH3Swing adsorption peak, in 1049cm-1The peak that place occurs is Si-O-Si stretching vibration peak, may be with 1112cm-1Place
C-O-C characteristic absorption peak overlaps, and causes peak area to become big；CF3The absworption peak of stretching vibration be 898cm-1Place, the peak of the above
Show that fluorinated polysiloxane has been accessed in polyurethane segment.
Embodiment 2
By polyether Glycols (PTMG) of the molecular weight vacuum dried 40g for 2000,9g IPDIs
(IPDI) added with a drop dibutyltin dilaurate catalyst in the three-necked flask with condenser pipe, nitrogen (N2) rise under protection
Temperature is to 60 DEG C and 40ml anhydrous dimethyl formamide (DMF) reduction system viscosity is slowly added dropwise, and reacts 3h；40 DEG C are cooled to,
The fluorinated polysiloxane that addition 0.8g molecular weight is 3000 is in nitrogen (N2) the lower stirring reaction 1h of protection；50 DEG C are warming up to, is added
(addition of 1,4- butanediols is 1 with the mol ratio of system residual isocyanate to the agent of 1,4- chain expansion of succinic acid:2) stirring reaction
2h；Product is cast on the glass plate of horizontal, is dried at room temperature for 24h and then 60 DEG C of dry 8h, that is, a kind of silicon fluoride is made
Modified polyurethane hydrophobic film.
The silicon fluoride modified polyurethane hydrophobic film of above-mentioned preparation is characterized, Fig. 2 is the polyurethane that silicon fluoride is modified
The infrared spectrum of film, contact angle test are shown in Table 1.By can see in infrared spectrum, 2270cm-1Place-feature of NCO group
Peak disappears, and illustrates that isocyanates is reacted completely, 3338cm-1Place be hydrogen bonding-NH- stretching vibration peak, 1535cm-1
Place is-NH- deformation vibration peak, 1721cm-1What is located is the stretching vibration peak of C=O in-NHCOO-, in 777cm-1What place occurred
It is Si-CH3Swing adsorption peak, in 1047cm-1Place occurs that Si-O-Si stretching vibration peak, may be with 1110cm-1Place
C-O-C characteristic absorption peak overlap, cause peak area to become big；CF3The absworption peak of stretching vibration be 950cm-1Place, the above
Peak shows that fluorinated polysiloxane has been accessed in polyurethane segment.
Comparative example
Polyurethane film prepared by this comparative example does not add fluorinated polysiloxane during the course of the reaction, especially by following sides
It is prepared by method：
By polyether Glycols (PTMG) of the molecular weight vacuum dried 40g for 2000,12g IPDIs
(IPDI) added with a drop dibutyltin dilaurate catalyst in the three-necked flask with condenser pipe, nitrogen (N2) rise under protection
Temperature is to 60 DEG C and 80ml anhydrous tetrahydro furan (THF) reduction system viscosity is slowly added dropwise, and reacts 3h；60 DEG C are cooled to, is added
The agent of 1,4- chain expansion of succinic acid is in nitrogen (N2) protection lower reaction 1h (addition of 1,4- butanediols and system residual isocyanate
Mol ratio is 1:2)；Product is cast on the glass plate of horizontal, is dried at room temperature for 24h and then 60 DEG C of dry 8h, that is, is made
Unmodified polyurethane film.
The unmodified polyurethane film of above-mentioned preparation is characterized, Fig. 3 is the INFRARED SPECTRUM of unmodified polyurethane film
Figure, contact angle test are shown in Table 1.By can see in infrared spectrum, 2270cm-1Place-characteristic peak of NCO group disappears, explanation
Isocyanates is reacted completely；3348cm-1Place is hydrogen bonding-NH- stretching vibration peak, 1570cm-1What is located is-NH- change
Shape vibration peak, 1716cm-1Locate the stretching vibration peak for the-C=O in-NHCOO-, in 1112cm-1Place occurs that C-O-C's
Characteristic absorption peak, the infrared spectrum in contrast implementation, peak area are narrower.
The embodiment of table 1 and comparative example Static water contact angles test data
As it can be seen from table 1 by the polyurethane film that silicon fluoride is modified relative to the water of unmodified polyurethane film
Contact angle lifts more than 30 °, and hydrophobicity is significantly improved.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of silicon fluoride modified polyurethane hydrophobic film, it is characterised in that comprise the following steps：Take polyethers two
First alcohol, diisocyanate and catalyst, under nitrogen protection, solvent are added after 60~80 DEG C of 2~4h of stirring reaction, is cooled to
30~50 DEG C, fluorinated polysiloxane 1~2h of stirring reaction under nitrogen protection is added, is warming up to 50~60 DEG C, adds small molecule
Chain extender, 1~2h is reacted under nitrogen protection, product is cast on the glass plate of horizontal, dried, that is, a kind of silicon fluoride is made
Modified polyurethane hydrophobic film；
Described diisocyanate and the mol ratio of polyether Glycols are 1.5:1~3:1；Described fluorinated polysiloxane dosage is
The 0.5%~5% of polyether Glycols quality.
A kind of 2. silicon fluoride modified polyurethane hydrophobic film according to claim 1 and preparation method thereof, it is characterised in that
The diisocyanate is one or more of IPDI, toluene di-isocyanate(TDI).
3. the preparation method of silicon fluoride modified polyurethane hydrophobic film according to claim 1, it is characterised in that the polyethers
Dihydric alcohol includes one or more of PTMG class polytetramethylene oxides dihydric alcohol, PPG class polyether Glycols；The polyether Glycols
Molecular weight be 1000~3000.
4. the preparation method of silicon fluoride modified polyurethane hydrophobic film according to claim 1, it is characterised in that described is poly-
Vacuum drying removes water 2h at 90~120 DEG C before ether diol reaction.
5. the preparation method of silicon fluoride modified polyurethane hydrophobic film according to claim 1, it is characterised in that described urges
Agent is dibutyl tin laurate.
6. the preparation method of silicon fluoride modified polyurethane hydrophobic film according to claim 1, it is characterised in that the solvent
For one or more of toluene, dimethylformamide, tetrahydrofuran, acetone.
7. the preparation method of silicon fluoride modified polyurethane hydrophobic film according to claim 1, it is characterised in that described is small
Molecule chain extender is small molecule glycol HO-R-OH, small molecule diamines NH2-R-NH2One or more of, wherein R=CnH2n, n=1
~6.
8. the preparation method of silicon fluoride modified polyurethane hydrophobic film according to claim 1, it is characterised in that the drying
Refer to be dried at room temperature for 12h~36h and then 60 DEG C~80 DEG C dry 8h~24h.
9. the preparation method of silicon fluoride modified polyurethane hydrophobic film according to claim 1, it is characterised in that described fluorine-containing
Polysiloxanes is the fluorinated polysiloxane with double hydroxyl reaction active groups, has following formula：
Wherein n=20~40.
10. silicon fluoride modified polyurethane hydrophobic film is prepared by any one of claim 1~9 preparation method.
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Cited By (8)
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| CN109762459A (en) * | 2019-01-10 | 2019-05-17 | 陕西科技大学 | A kind of reversible hydrophobic selfreparing no-solvent polyurethane and preparation method thereof of light |
| CN109988281A (en) * | 2019-04-24 | 2019-07-09 | 陕西科技大学 | A kind of preparation method of the hydrophobic performance containing disulfide bond and the dual selfreparing no-solvent polyurethane of mechanical property |
| CN110066378A (en) * | 2019-04-17 | 2019-07-30 | 浙江华峰合成树脂有限公司 | Modified clothing leather polyurethane resin of fluorine-containing organic silicon and preparation method thereof |
| CN111574822A (en) * | 2020-06-04 | 2020-08-25 | 北京浦江兄弟科技有限公司 | Polyurethane hydrophobic film, preparation method and application thereof |
| CN111662428A (en) * | 2020-05-22 | 2020-09-15 | 中国船舶重工集团公司第七二五研究所 | Self-curing modified organic fluorine-silicon antifouling resin and preparation method thereof |
| CN112760025A (en) * | 2021-01-18 | 2021-05-07 | 陕西科技大学 | Hydrophobic and light-controlled antibacterial waterborne polyurethane composite emulsion as well as preparation method and application thereof |
| CN113527614A (en) * | 2021-07-05 | 2021-10-22 | 重庆交通大学 | Water-based polymer emulsion with self-compensation hydrophobic surface function and preparation method thereof |
| CN115368531A (en) * | 2022-07-09 | 2022-11-22 | 苏州净涵新材料科技有限公司 | Self-lubricating stain-resistant thermoplastic polyurethane elastomer and preparation method thereof |
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| CN110066378A (en) * | 2019-04-17 | 2019-07-30 | 浙江华峰合成树脂有限公司 | Modified clothing leather polyurethane resin of fluorine-containing organic silicon and preparation method thereof |
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