CN107163277A - A kind of method that ultraviolet light prepares hydrophobic polyurethane film - Google Patents
A kind of method that ultraviolet light prepares hydrophobic polyurethane film Download PDFInfo
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- CN107163277A CN107163277A CN201710338358.9A CN201710338358A CN107163277A CN 107163277 A CN107163277 A CN 107163277A CN 201710338358 A CN201710338358 A CN 201710338358A CN 107163277 A CN107163277 A CN 107163277A
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- C08J2375/04—Polyurethanes
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Abstract
The present invention relates to a kind of method that ultraviolet light prepares hydrophobic polyurethane film, including step are as follows：(1) by diisocyanate and PolyTHF hybrid reaction；Crosslinking agent, chain extender are added, dihydromethyl propionic acid and catalyst reaction is added, obtains PU；Then film forming and it is heat-treated, obtains polyurethane film；(2) 4,4 ' dihydroxy benaophenonels and 1 bromododecane are reacted, obtains 4,4 ' double dodecyloxy benzophenones；4,4 ' double dodecyloxy benzophenones obtain 4,4 ' double dodecyloxy benzophenones hydrazones with hydration hydrazine reaction；4,4 ' double dodecyloxy benzophenones hydrazones are oxidized to react to obtain chain alkyl diazomethane；(3) chain alkyl diazomethane is dissolved in solvent, is uniformly coated to polyurethane film surface, through ultraviolet light, produced.This invention simplifies course of reaction, it is to avoid the problem of hydrophobic polyurethane synthesis difficulty is big.
Description
Technical field
The present invention relates to a kind of method that ultraviolet light prepares hydrophobic polyurethane film, belong to polyurethane material technology
Field.
Background technology
Polyurethane is the important high polymer material of a class, and its chemical synthesis is mainly by diisocyanate and dihydric alcohol
Sudden reaction is carried out.The structure design of polymer is not only the basis of polymer chemistry with synthesis, also gradually extends to material
Expect the fields such as, Journal of Molecular Catalysis, biological medicine.Therefore, polyurethane synthetic method, exploitation new polyurethane material are explored, is had
Important theory significance and potential application value.
With coating safety and the pay attention to day by day of environmental protection index, aqueous polyurethane because the characteristics such as its less harmful, low stain by
Gradually received by market.The decentralized medium of aqueous polyurethane is low with low toxicity, pollution-free, odorlessness, VOC content based on water
The advantages of, it is much smaller to the damage ratio solvent borne polyurethane of environment.But, limited by synthesis technique, point of aqueous polyurethane
Son, which is measured in relatively low, film, has the hydrophilic radicals such as carboxyl.Therefore, water resistance is not good after aqueous polyurethane film forming, physics, chemically
Solvent borne polyurethane can be not so good as.
It is the important channel for improving polymer thin film properties that surface hydrophobicity, which is modified, and the hydrophobic membrane of modified formation can be carried significantly
The water resistance of high water paint, therefore obtained research extensively and profoundly.At present, the research that the surface hydrophobicity of polymer is modified
Special chemical reaction is depended on, i.e., obtains the polyurethane with specific function group first, is then implemented on its surface
Incident click reactions, introduce hydrophobic performance group and are modified.Fournier et al. (Fournier D, De Geest
B G,Du Prez F E.On-demand click functionalization of polyurethane films and
foams[J].Polymer,2009,50(23):5362-5367.) it have purchased surface work from Belgian Recticel companies first
The polyurethane sponge (surface group is alkynyl) of energyization, then carries out 1,3- with the azido compound with hydrophobic alkyl chain with it
Dipolar Cycloaddition, so that obtaining surface has the polyurethane sponge material of hydrophobic performance.Nystrom et al. (Nystrom
D,Lindqvist J,Ostmark E,et al.Superhydrophobic and self-cleaning bio-fiber
surfaces via ATRP and subsequent postfunctionalization[J].ACS applied
materials&interfaces,2009,1(4):816-823.), Xu et al. (Xu J, Boyer C.Visible light
photocatalytic thiol–ene reaction:an elegant approach for fast polymer
postfunctionalization and step-growth polymerization[J].Macromolecules,2015,
48(3):520-529.) also respectively on the functional fiber element purchased from Sigma-Aldrich companies, functional poly butadiene surface
Hydrophobic alkyl chain is introduced, the hydrophobic purpose of raising is reached.However, this hydrophobically modified mode is required to polymer surfaces band
There is special functional group, moreover, in order to ensure the smooth implementation of successive modified reaction, these functional group (such as alkynyls, alkene
Base, nitrine etc.) chemical property it is often more active, be prone to side reaction and go bad, cause the synthesis hardly possible of this kind of polymer
Degree is big, is not particularly suited for the surface modification of polyurethane material generally used at present.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides the side that a kind of ultraviolet light prepares hydrophobic polyurethane film
Method.
Technical scheme is as follows：
A kind of method that ultraviolet light prepares hydrophobic polyurethane film, including step are as follows：
(1) preparation of polyurethane film
Diisocyanate and PolyTHF are mixed, 1-10h is reacted in 80-120 DEG C；Crosslinking agent, chain extender are added, then
Dihydromethyl propionic acid and catalyst are added, 1-10h is reacted in 60-90 DEG C, obtains polyurethane solutions (PU)；Then film forming and heat at
Reason, produces polyurethane film；
(2) preparation of chain alkyl diazomethane
4,4 '-dihydroxy benaophenonel and Dodecyl Bromide are reacted, 4,4 '-bis--dodecyloxy benzophenones are obtained；
4,4 '-bis--dodecyloxy benzophenones obtain 4,4 '-bis--dodecyloxy benzophenones hydrazone with hydration hydrazine reaction；4,4 '-bis--
Dodecyloxy benzophenones hydrazone is oxidized to react to obtain chain alkyl diazomethane；
(3) preparation of hydrophobic polyurethane film
Chain alkyl diazomethane is dissolved in solvent, polyurethane film surface is uniformly coated to, through ultraviolet light 1-
30min, produces hydrophobic polyurethane film.
, according to the invention it is preferred to, the diisocyanate described in step (1) is 4, the isocyanide of 4 '-dicyclohexyl methyl hydride two
Acid esters, described crosslinking agent is trimethylolpropane, and described chain extender is 1,6- hexylene glycols, and described catalyst is silicon in February
Sour dibutyl tin；
It is preferred that, diisocyanate, PolyTHF, crosslinking agent, chain extender, the quality of dihydromethyl propionic acid and catalyst
Than for 1：(0.8-1.2)：(0.01-0.1)：(0.1-1)：(0.01-0.1)：(0.001-0.01)；
It is preferred that, crosslinking agent and chain extender are dissolved in acetone add reaction system respectively, the acetone of crosslinking agent and chain extender
In solution, the ratio between volume of quality and acetone of crosslinking agent or chain extender is 1：(5-100)g/mL；
It is preferred that, heat-treatment temperature range is 25-200 DEG C after film forming, and the time of heat treatment is 1-10h.
, according to the invention it is preferred to, the long-chain alkyl halide described in step (2) is Dodecyl Bromide；
It is preferred that, 4, the mass ratio of 4 '-dihydroxy benaophenonel and long-chain alkyl halide is 1：(2-20)；
It is preferred that, reaction temperature is 80-200 DEG C, and the reaction time is 10-100h；
4,4 '-dihydroxy benaophenonel after the reaction of long-chain alkyl halide with generating hydrogen chloride, it is preferred that adding potassium carbonate is used for
Hydrogen chloride is neutralized, accelerates reaction rate.The mass ratio of 4,4 '-dihydroxy benaophenonel and potassium carbonate is 1：(2-20).
, according to the invention it is preferred to, 4,4 ' in step (2)-quality of bis--long-chain alkoxy base benzophenone and hydrazine hydrate
Volume ratio is 1：(1-10)g/mL；
It is preferred that, using ethanol as solvent in the course of reaction of 4,4 '-bis--long-chain alkoxy base benzophenone and hydrazine hydrate, second
Acid is catalyst, and 10-100h is reacted in 70-100 DEG C；It is further preferred that 4, the matter of 4 '-bis--long-chain alkoxy base benzophenone
Amount and the volume of ethanol are prepared as 1：(10-100), the quality and the volume ratio of acetic acid of 4,4 '-bis--long-chain alkoxy base benzophenone
For 1：(0.05-0.5)g/mL.
, according to the invention it is preferred to, 4,4 ' in step (2)-oxidation reaction process of bis--long-chain alkoxy base Benzophenonehydrazones
The middle oxidant that uses is that manganese dioxide, water absorbing agent are that anhydrous sodium sulfate, alkali are potassium hydroxide.
It is preferred that, 4,4 '-bis--long-chain alkoxy base Benzophenonehydrazones, manganese dioxide, the matter of anhydrous sodium sulfate and potassium hydroxide
Amount is than being 1：(0.2-2)：(0.25-1)：(0.01-0.1)；
It is preferred that, lucifuge is reacted in course of reaction, and reaction temperature is -40-40 DEG C, and the reaction time is 1-10h.
, according to the invention it is preferred to, ultraviolet ray intensity is 500-3000mW/cm in step (3)2, the ultraviolet light time
For 1-30min.
, according to the invention it is preferred to, the solvent described in step (3) is hexamethylene, the quality of chain alkyl diazomethane
It is 1 with the ratio between the volume of solvent：(1-10)g/mL.
The principle of the present invention：
The present invention separately wards off new footpath, and surface modification is carried out to the polyurethane material being molded with chain alkyl diazomethane,
Make one layer of hydrophobic grouping of its surface uniform fold, because the preparation difficulty of existing hydrophobic polyurethane is big, therefore the present invention will
The application field of polyurethane material can be expanded.
The present invention chain alkyl diazomethane high activity Cabbeen can be generated after ultraviolet light, then rapidly with poly- ammonia
The carboxyl on ester film surface is reacted, and occurs intercalation reaction with the c h bond of polyurethane chain, and poly- ammonia is arrived in chain alkyl modification
Ester surface, makes its surface have hydrophobicity.
The principle of the synthesis of chain alkyl diazomethane of the present invention and the hydrophobic modification of polyurethane film is as follows：
Beneficial effects of the present invention are as follows：
1st, then the present invention utilizes the c h bond and aqueous polyurethane of macromolecular chain itself by first preparing polyurethane film
The carboxyl carried realizes the hydrophobic surface modification of polyurethane material.High activity need not be introduced in polyurethane molecular in advance anti-
Group is answered, simplify course of reaction, it is to avoid the problem of hydrophobic polyurethane synthesis difficulty is big.
2nd, dihydromethyl propionic acid is added in the preparation process of polyurethane film of the present invention, gained polyurethane film has hydrophilic
Property, it is less than 85 ° with the contact angle of water；By the hydrophobically modified of the inventive method, gained hydrophobic polyurethane film and water connect
Feeler significantly increase (>100 °), show that the modified polyurethane film of hydrophobic surface is changed into hydrophobicity.
Brief description of the drawings
Fig. 1 is that the mass fraction of dihydromethyl propionic acid in test example 1 is the water of 1% polyurethane film without hydrophobically modified
Contact angle photo.
Fig. 2 is that the mass fraction of dihydromethyl propionic acid in test example 1 is the 1% poly- ammonia for passing through ultraviolet light hydrophobically modified
The water contact angle photo of ester film.
Embodiment
Below by specific embodiment, the present invention will be further described, but not limited to this.
Raw materials used in embodiment is conventional commercial products unless otherwise specified.
Embodiment 1-3
A kind of method that ultraviolet light prepares hydrophobic polyurethane film, including step are as follows：
(1) preparation of polyurethane film
4,4 '-dicyclohexyl methyl hydride diisocyanate (7.5g) and poly- tetrahydrochysene furan are added in 100mL there-necked flask
Mutter (7.9g), carries out prepolymerization within 2 hours with stirring at 90 DEG C of digital display electric mixer constant temperature, after completion of the reaction drops temperature
To 70 DEG C；Trimethylolpropane (0.178g), 1,6-HD (2.21g) are dissolved in acetone (15mL) and three-necked flask is poured into
In, it is respectively 1% (embodiment 1), 3% (embodiment 2), the dihydroxymethyl third of 5% (embodiment 3) that mass percent is added afterwards
Acid, dibutyl tin dilaurate 3 is dripped, and temperature rises to 80 DEG C and continues to react 3h.The most of acetone of revolving removing is molten after completion of the reaction
Agent, when solution temperature to be mixed is reduced to room temperature, uniformly pours into Teflon mould, the forced air drying at 60 DEG C by it.It is used
Each raw material ratio it is as shown in table 1.
The PU films and its mechanical property of the different formulations of table 1
(2) synthesis of chain alkyl diazomethane
1. the synthesis of 4,4 '-bis--dodecyloxy benzophenones
The addition dimethylformamide (30mL) in single-necked flask, 4,4 '-dihydroxy benaophenonel (2.14g,
0.01mol), Dodecyl Bromide (5g, 0.02mol), potassium carbonate (6.9g, 0.05mol), 24h is reacted at 80 DEG C, is then returned
Stream stirring 24h, is cooled to room temperature, obtains White Flocculus solid, 12h is dried in vacuum drying chamber after completion of the reaction.
Yield:70%；1H-NMR：0.878(t,3H,-CH2CH3),1.238(m,2H,-CH2-CH2),1.465(m,2H,O-CH2-
CH2-CH 2), 1.789 (m, 2H, O-CH2 CH 2),4.040(t,2H,O-CH 2),6.962(d,1H,ph-H),7.794(d,1H,ph-
H)；13C-NMR(50MHz,CDCl3):193.8(1C,CO)161.9,131.6,130.1,113.4(4C,C-ph),67.8(1C,
O-CH2),31.3,29.1,28.8,25.5(4C,-CH2),22.1(1C,-CH2CH3),13.5(1C,-CH2 CH3)；IR(KBr,
cm-1):3398.57,2954.95,2850.79,1633.71,1602.85,1309.67,1253.73.
2. the synthesis of 4,4 '-bis--dodecyloxy benzophenones hydrazone
The reacted solid of the first step (1.39g, 2.53mmol) is dissolved in 20mL ethanol, 100mL single port is poured into
In bottle, hydrazine hydrate (2.45mL, 50.6mmol) is added, a few drop glacial acetic acids (0.4mL) is added as catalyst, is heated to 80 DEG C
Return stirring 48h, is after completion of the reaction evaporated ethanol, is then dissolved in dichloromethane (60mL), with distilled water (60mL)
Washing 4 times, adds anhydrous magnesium sulfate and dries organic layer, revolving obtains faint yellow solid, and 24h is dried in vacuum drying chamber.
Yield:75%；1H-NMR：0.88(t,3H,-CH2-CH 3),1.277(m,2H,-CH 2CH3),1.453(m,2H,O-CH 2),
1.754(m,2H,O-CH2-CH 2),4.06(t,2H,O-CH2), 7.0 (s, 2H, C=N-NH2),7.405,7.248,7.023,
6.837(d,1H,ph-H)；12C-NMR：158.9 (1C, C=N), 161.9,130.9,124.4,114.6 (4C, C-ph), 67.7
(1C,O-CH2),31.4(1C,-CH2-CH2-CH3),29.1(4C,-CH2),25.6(1C,O-CH2-CH2-CH2),13.6(1C,-
CH2-CH3).IR(KBr:cm-1):3471.86,2954.95,2850.79,1604.71,1508.33,1247.94.
3. the synthesis of 4,4 '-bis--dodecyloxy diazomethane
Second step product (1.015g, 1.8mmol) is dissolved in dichloromethane (15mL), addition manganese dioxide (0.57g,
6.51mmol), anhydrous sodium sulfate (0.50g, 3.50mmol), potassium hydroxide (0.15g, 2.75mmol), lucifuge is stirred at room temperature
2h is mixed, after completion of the reaction suction filtration, organic layer will obtain violet solid after revolving.Yield:50%；1H-NMR：0.89(t,
3H,-CH2-CH 3),1.26(m,2H,-CH 2),1.29(m,2H,-CH2),1.43(m,2H,O-CH2-CH2-CH 2),1.77(m,
2H,O-CH2-CH 2),3.97(t,2H,O-CH 2),6.95(d,1H,ph-H),7.19(d,1H,ph-H)。13C-NMR：156.8,
126.0,120.8,114.9(4C,C-ph),67.7(1C,O-CH2),31.4(1C,-CH2-CH2-CH3),29.1(4C,-CH2),
25.6(1C,O-CH2-CH2-CH2),13.6(1C,-CH2CH3).IR(KBr:cm-1):3361.93,2918.30,2852.72,
2059.71,1510.26,1473.62,1249.87,1024.20.
(3) preparation of hydrophobic polyurethane film
The polyurethane film prepared is first cut into 2 × 2cm blockage.Then film is entered using uv irradiation method
Row surface modification：
Uv irradiation method：The hexamethylene that will be dissolved in first on 4,4 '-bis--dodecyloxy diazomethane (0.1g)
In (15mL), then solution dripped to the surface of hydrophobically modified polyurethane film with glue head dropper, will after solvent volatilization is clean
Hydrophobically modified polyurethane film ultraviolet light 30min, ultraviolet ray intensity is 500mW/cm2；It is cooled to after room temperature and uses hexamethylene
Alkane is rinsed, and produces hydrophobically modified polyurethane film.
Embodiment 4
As described in Example 1, unlike：
Prepolymerization temperature is 100 DEG C in step (1), is added anti-after dihydromethyl propionic acid and dibutyl tin dilaurate
It is 70 DEG C to answer temperature；
The intensity of ultraviolet light is 1500mW/cm in step (3)2。
Embodiment 5
As described in Example 1, unlike：
Diisocyanate in step (1), PolyTHF, crosslinking agent, chain extender, the matter of dihydromethyl propionic acid and catalyst
Amount is than being 1：1.1：0.024：0.28：0.02：0.003.
Test example 1, hydrophobicity test
In order to verify the hydrophobic performance of hydrophobic polyurethane film produced by the present invention, employ contact angle tester to survey
The water contact angle of film surface.Before polyurethane film is unmodified, because the carboxyl that dihydromethyl propionic acid monomer is introduced makes film be parent
It is aqueous.In order to study the influence of the content of dihydromethyl propionic acid to the hydrophobic properties of the surface of polyurethane film, dihydroxy first is tested
The mass percent of base propionic acid is respectively the water contact angle of 1%, 3%, 5% polyurethane film；Test result is as shown in table 2.
The water contact angle data of the polyurethane film of table 2
As shown in Table 2, because the preparation process of polyurethane is usually added into dihydromethyl propionic acid, gained polyurethane film generally has
There is hydrophily.Polyurethane film contact angle before modification is respectively less than 85 °, the water for the polyurethane film modified by ultraviolet light
Contact angle significantly increase (>90 °), show that the polyurethane film after modification is changed into hydrophobicity.With dihydromethyl propionic acid content
Increase, the water contact angle change of film is little, and this illustrates that influence of the content of dihydromethyl propionic acid to thin-film hydrophobic performance is little.
The water contact angle photo of polyurethane film is as shown in Figure 1-2 in this test example.From Fig. 1-2 it can also be seen that by
The water contact angle increase on the polyurethane film surface after modification, it was demonstrated that film is changed into hydrophobicity from hydrophily.
Claims (10)
1. a kind of method that ultraviolet light prepares hydrophobic polyurethane film, including step are as follows：
(1) preparation of polyurethane film
Diisocyanate and PolyTHF are mixed, 1-10h is reacted in 80-120 DEG C；Crosslinking agent, chain extender are added, is added
Dihydromethyl propionic acid and catalyst, react 1-10h in 60-90 DEG C, obtain polyurethane solutions (PU)；Then film forming and it is heat-treated, i.e.,
Obtain polyurethane film；
(2) preparation of chain alkyl diazomethane
4,4 '-dihydroxy benaophenonel and Dodecyl Bromide are reacted, 4,4 '-bis--dodecyloxy benzophenones are obtained；4,
4 '-bis--dodecyloxy benzophenones obtain 4,4 '-bis--dodecyloxy benzophenones hydrazone with hydration hydrazine reaction；4,4 '-bis--ten
Dialkoxy-benzophenones hydrazone is oxidized to react to obtain chain alkyl diazomethane；
(3) preparation of hydrophobic polyurethane film
Chain alkyl diazomethane is dissolved in solvent, polyurethane film surface is uniformly coated to, through ultraviolet light 1-
30min, produces hydrophobic polyurethane film.
2. the method that ultraviolet light according to claim 1 prepares hydrophobic polyurethane film, it is characterised in that step
(1) diisocyanate described in is 4,4 '-dicyclohexyl methyl hydride diisocyanate, and described crosslinking agent is trihydroxy methyl third
Alkane, described chain extender is 1,6- hexylene glycols, and described catalyst is dibutyl tin dilaurate.
3. the method that ultraviolet light according to claim 1 prepares hydrophobic polyurethane film, it is characterised in that step
(1) diisocyanate in, PolyTHF, crosslinking agent, chain extender, the mass ratio of dihydromethyl propionic acid and catalyst are 1：
(0.8-1.2)：(0.01-0.1)：(0.1-1)：(0.01-0.1)：(0.001-0.01).
4. the method that ultraviolet light according to claim 1 prepares hydrophobic polyurethane film, it is characterised in that step
(2) the long-chain alkyl halide described in is Dodecyl Bromide；
It is preferred that, 4, the mass ratio of 4 '-dihydroxy benaophenonel and long-chain alkyl halide is 1：(2-20).
5. the method that ultraviolet light according to claim 1 prepares hydrophobic polyurethane film, it is characterised in that step
(2) reaction temperature is 80-200 DEG C in, and the reaction time is 10-100h.
6. the method that ultraviolet light according to claim 1 prepares hydrophobic polyurethane film, it is characterised in that step
(2) 4,4 ' in-volume ratio of the quality of bis--long-chain alkoxy base benzophenone and hydrazine hydrate is 1：(1-10)g/mL.
7. the method that ultraviolet light according to claim 1 prepares hydrophobic polyurethane film, it is characterised in that step
(2) 4,4 ' in-course of reaction of bis--long-chain alkoxy base benzophenone and hydrazine hydrate in using ethanol as solvent, acetic acid is catalyst,
10-100h is reacted in 70-100 DEG C；
It is preferred that, 4,4 '-bis--quality of long-chain alkoxy base benzophenone and the volume of ethanol are prepared as 1：(10-100), 4,4 '-
The quality of double-long-chain alkoxy base benzophenone and the volume ratio of acetic acid are 1：(0.05-0.5)g/mL.
8. the method that ultraviolet light according to claim 1 prepares hydrophobic polyurethane film, it is characterised in that step
(2) 4,4 ' in-oxidation reaction process of bis--long-chain alkoxy base Benzophenonehydrazones in the oxidant that uses be manganese dioxide, water suction
Agent is that anhydrous sodium sulfate, alkali are potassium hydroxide；
It is preferred that, 4,4 '-bis--long-chain alkoxy base Benzophenonehydrazones, manganese dioxide, the mass ratio of anhydrous sodium sulfate and potassium hydroxide
For 1：(0.2-2)：(0.25-1)：(0.01-0.1).
9. the method that ultraviolet light according to claim 1 prepares hydrophobic polyurethane film, it is characterised in that step
(2) lucifuge is reacted in course of reaction in, and reaction temperature is -40~40 DEG C, and the reaction time is 1-10h.
10. the method that ultraviolet light according to claim 1 prepares hydrophobic polyurethane film, it is characterised in that step
Suddenly ultraviolet ray intensity is 500-3000mW/cm in (3)2, the ultraviolet light time is 1-30min；
It is preferred that, the solvent described in step (3) is hexamethylene, the ratio between the quality of chain alkyl diazomethane and the volume of solvent
For 1：(1-10)g/mL.
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| CN109535361A (en) * | 2018-11-12 | 2019-03-29 | 中山大学 | A kind of ultraviolet light irradiation mechanical response aqueous polyurethane and preparation method thereof |
| CN110186898A (en) * | 2019-06-06 | 2019-08-30 | 齐鲁工业大学 | A kind of hydrophobicity papery surface enhanced Raman substrate and its application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109535361A (en) * | 2018-11-12 | 2019-03-29 | 中山大学 | A kind of ultraviolet light irradiation mechanical response aqueous polyurethane and preparation method thereof |
| CN109535361B (en) * | 2018-11-12 | 2021-09-03 | 中山大学 | Ultraviolet light irradiation mechanical response waterborne polyurethane and preparation method thereof |
| CN110186898A (en) * | 2019-06-06 | 2019-08-30 | 齐鲁工业大学 | A kind of hydrophobicity papery surface enhanced Raman substrate and its application |
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| CN107163277B (en) | 2019-12-27 |
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