CN107163277B - Method for preparing hydrophobic polyurethane film by ultraviolet irradiation - Google Patents
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Abstract
The invention relates to a method for preparing a hydrophobic polyurethane film by ultraviolet irradiation, which comprises the following steps: (1) mixing diisocyanate and polytetrahydrofuran for reaction; adding a cross-linking agent and a chain extender, and then adding dimethylolpropionic acid and a catalyst for reaction to obtain PU; then forming a film and carrying out heat treatment to obtain a polyurethane film; (2) reacting 4,4 '-dihydroxy benzophenone with 1-bromododecane to obtain 4, 4' -bis-dodecyloxy benzophenone; 4,4 '-bis-dodecyloxy benzophenone reacts with hydrazine hydrate to obtain 4, 4' -bis-dodecyloxy benzophenone hydrazone; 4, 4' -bis-dodecyloxy benzophenone hydrazone is subjected to oxidation reaction to obtain long-chain alkyl diazomethane; (3) dissolving long-chain alkyl diazomethane in a solvent, uniformly coating the solvent on the surface of the polyurethane film, and irradiating the polyurethane film by ultraviolet light to obtain the polyurethane film. The invention simplifies the reaction process and avoids the problem of high synthesis difficulty of the hydrophobic polyurethane.
Description
Technical Field
The invention relates to a method for preparing a hydrophobic polyurethane film by ultraviolet irradiation, belonging to the technical field of polyurethane materials.
Background
Polyurethanes are an important class of polymeric materials, and their chemical synthesis is primarily carried out by the polyaddition of diisocyanates with diols. The structural design and synthesis of polymers are not only the basis of polymer chemistry, but also gradually extend to the fields of materials science, molecular catalysis, biomedicine and the like. Therefore, the method for exploring the polyurethane synthesis method and developing a novel polyurethane material has important theoretical significance and potential application value.
With the increasing importance of the safety and environmental protection indexes of the coating, the waterborne polyurethane is gradually accepted by the market due to the characteristics of low harm, low pollution and the like. The dispersion medium of the waterborne polyurethane is mainly water, has the advantages of low toxicity, no pollution, no odor, low VOC content and the like, and has much less pollution to the environment than solvent-based polyurethane. However, the molecular weight of the aqueous polyurethane is low and hydrophilic groups such as carboxyl groups are present in the coating film due to the restriction of the synthesis process. Therefore, the water resistance of the aqueous polyurethane after film formation is poor, and the physical and chemical properties are inferior to those of the solvent-borne polyurethane.
The surface hydrophobic modification is an important way for improving the performance of the polymer film, and the hydrophobic film formed after the modification can greatly improve the water resistance of the water-based paint, so that extensive and intensive research is carried out. At present, the research on the hydrophobic modification of the surface of the polymer mainly depends on a special chemical reaction, namely, firstly, polyurethane with a specific functional group is obtained, then, a click reaction which is easy to occur is carried out on the surface of the polyurethane, and a hydrophobic performance group is introduced for modification. Fournier et al (Fournier D, De Geest B G, Du Prez F E.on-detailed click catalysis of polyurethane films and foams [ J ]. Polymer,2009,50(23):5362-5367.) first purchased a surface functionalized polyurethane sponge (surface group is alkynyl) from Recticel corporation of Belgium, and then subjected to 1, 3-dipolar cycloaddition reaction with an azide compound having a hydrophobic alkyl chain, thereby obtaining a polyurethane sponge material having hydrophobic surface properties. Nystrom et al (Nystromem D, Lindqvist J, Ostmark E, et al. Superhydrophthalic and self-cleaning bio-fibersurfaces via ATRP and subsequent post-treatment catalysis [ J ]. ACS applied materials & interfaces,2009,1(4):816-823.), Xu et al (Xu J, Boyer C. visible light photocatalytic reaction: an elastomer approach for surface polymerization [ J ]. Macromolecules,2015,48(3): 529.) also achieve the goal of introducing hydrophobic chains in functionalized butadiene from Sigma-cellulose, surface polymerization and step-growth polymerization [ J ]. 520, respectively, for the purpose of increasing the hydrophobicity of the chains. However, the hydrophobic modification method requires that the surface of the polymer has special functional groups, and in order to ensure the smooth implementation of the subsequent modification reaction, the chemical properties of the functional groups (such as alkynyl, alkenyl, azide, and the like) are often more active and are prone to side reactions to deteriorate, so that the synthesis difficulty of the polymer is high, and the method is not suitable for the surface modification of the currently commonly used polyurethane material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing a hydrophobic polyurethane film by ultraviolet irradiation.
The technical scheme of the invention is as follows:
a method for preparing a hydrophobic polyurethane film by ultraviolet irradiation comprises the following steps:
(1) preparation of polyurethane films
Mixing diisocyanate and polytetrahydrofuran, and reacting at 80-120 ℃ for 1-10 h; adding a cross-linking agent and a chain extender, then adding dimethylolpropionic acid and a catalyst, and reacting for 1-10h at the temperature of 60-90 ℃ to obtain a polyurethane solution (PU); then forming a film and carrying out heat treatment to obtain a polyurethane film;
(2) preparation of long-chain alkyl diazomethane
Reacting 4,4 '-dihydroxy benzophenone with 1-bromododecane to obtain 4, 4' -bis-dodecyloxy benzophenone; 4,4 '-bis-dodecyloxy benzophenone reacts with hydrazine hydrate to obtain 4, 4' -bis-dodecyloxy benzophenone hydrazone; 4, 4' -bis-dodecyloxy benzophenone hydrazone is subjected to oxidation reaction to obtain long-chain alkyl diazomethane;
(3) preparation of hydrophobic polyurethane film
Dissolving long-chain alkyl diazomethane in a solvent, uniformly coating the solvent on the surface of the polyurethane film, and irradiating the polyurethane film for 1 to 30min by ultraviolet light to obtain the hydrophobic polyurethane film.
According to the present invention, preferably, the diisocyanate in step (1) is 4, 4' -dicyclohexylmethane diisocyanate, the crosslinking agent is trimethylolpropane, the chain extender is 1, 6-hexanediol, and the catalyst is dibutyltin dilaurate;
preferably, the mass ratio of diisocyanate, polytetrahydrofuran, cross-linking agent, chain extender, dimethylolpropionic acid and catalyst is 1: (0.8-1.2): (0.01-0.1): (0.1-1): (0.01-0.1): (0.001-0.01);
preferably, the cross-linking agent and the chain extender are respectively dissolved in acetone and added into the reaction system, the acetone solution of the cross-linking agent and the chain extender is prepared, and the ratio of the mass of the cross-linking agent or the chain extender to the volume of the acetone is 1: (5-100) g/mL;
preferably, the temperature range of the heat treatment after film formation is 25-200 ℃, and the time of the heat treatment is 1-10 h.
According to the present invention, it is preferred that the long-chain alkyl halide described in the step (2) is 1-bromododecane;
preferably, the mass ratio of the 4, 4' -dihydroxy benzophenone to the long-chain alkyl halide is 1: (2-20);
preferably, the reaction temperature is 80-200 ℃, and the reaction time is 10-100 h;
the 4, 4' -dihydroxybenzophenone reacts with the long chain alkyl halide to form hydrogen chloride, and preferably potassium carbonate is added to neutralize the hydrogen chloride, thereby accelerating the reaction rate. The mass ratio of the 4, 4' -dihydroxy benzophenone to the potassium carbonate is 1: (2-20).
According to the present invention, it is preferred that the ratio of the mass of the 4, 4' -bis-long-chain alkoxybenzophenone to the volume of hydrazine hydrate in step (2) is 1: (1-10) g/mL;
preferably, in the reaction process of the 4, 4' -double-long-chain alkoxy benzophenone and the hydrazine hydrate, ethanol is used as a solvent, acetic acid is used as a catalyst, and the reaction is carried out for 10 to 100 hours at the temperature of 70 to 100 ℃; further preferably, the mass of 4, 4' -bis-long-chain alkoxybenzophenone and the volume of ethanol are prepared in a ratio of 1: (10-100), the volume ratio of the mass of the 4, 4' -bis-long-chain alkoxy benzophenone to the volume of the acetic acid is 1: (0.05-0.5) g/mL.
According to the present invention, it is preferable that the oxidizing agent used in the oxidation reaction of the 4, 4' -bis-long-chain alkoxybenzophenone hydrazone in the step (2) is manganese dioxide, the water absorbent is anhydrous sodium sulfate, and the base is potassium hydroxide.
Preferably, the mass ratio of the 4, 4' -double-long-chain alkoxy benzophenone hydrazone to the manganese dioxide to the anhydrous sodium sulfate to the potassium hydroxide is 1: (0.2-2): (0.25-1): (0.01-0.1);
preferably, the reaction is carried out in the dark, the reaction temperature is-40-40 ℃, and the reaction time is 1-10 h.
According to the present invention, it is preferred that the intensity of the ultraviolet light in step (3) is 500-3000mW/cm2The ultraviolet irradiation time is 1-30 min.
According to the present invention, it is preferable that the solvent in the step (3) is cyclohexane, and the ratio of the mass of the long-chain alkyldiazomethane to the volume of the solvent is 1: (1-10) g/mL.
The principle of the invention is as follows:
the invention develops a new path, uses long-chain alkyl diazomethane to modify the surface of the formed polyurethane material, and uniformly covers a layer of hydrophobic groups on the surface of the formed polyurethane material.
The long-chain alkyl diazomethane can generate high-activity carbene after being irradiated by ultraviolet light, then quickly reacts with carboxyl on the surface of a polyurethane film, and has insertion reaction with a C-H bond of a polyurethane chain, so that the long-chain alkyl is modified on the surface of the polyurethane, and the surface of the polyurethane has hydrophobicity.
The principles of the synthesis of the long-chain alkyl diazomethane and the hydrophobic modification of the polyurethane film are as follows:
the invention has the following beneficial effects:
1. the hydrophobic surface modification method comprises the steps of firstly preparing the polyurethane film, and then utilizing the C-H bond of the polymer chain and the carboxyl of the waterborne polyurethane to realize the hydrophobic surface modification of the polyurethane material. Namely, high-activity reaction groups do not need to be introduced into polyurethane molecules in advance, so that the reaction process is simplified, and the problem of high difficulty in synthesizing hydrophobic polyurethane is solved.
2. Dimethylol propionic acid is added in the preparation process of the polyurethane film, and the obtained polyurethane film has hydrophilicity and a contact angle with water is less than 85 degrees; through the hydrophobic modification of the method, the contact angle between the obtained hydrophobic polyurethane film and water is obviously increased (100 degrees), which indicates that the polyurethane film after the hydrophobic surface modification becomes hydrophobic.
Drawings
FIG. 1 is a photograph showing the water contact angle of a polyurethane film without hydrophobic modification in test example 1 in which the mass fraction of dimethylolpropionic acid was 1%.
FIG. 2 is a photograph showing the water contact angle of the polyurethane film hydrophobically modified by UV irradiation in test example 1 in which dimethylolpropionic acid was present in an amount of 1% by mass.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The starting materials used in the examples are, unless otherwise specified, conventional commercial products.
Examples 1 to 3
A method for preparing a hydrophobic polyurethane film by ultraviolet irradiation comprises the following steps:
(1) preparation of polyurethane films
Adding 4, 4' -dicyclohexylmethane diisocyanate (7.5g) and polytetrahydrofuran (7.9g) into a 100mL three-necked flask, stirring for 2 hours at a constant temperature of 90 ℃ by using a digital display electric stirrer to perform prepolymerization, and reducing the temperature to 70 ℃ after the reaction is finished; trimethylolpropane (0.178g) and 1, 6-hexanediol (2.21g) were dissolved in acetone (15mL) and poured into a three-necked flask, and then 1% (example 1), 3% (example 2) and 5% (example 3) dimethylolpropionic acid and 3 drops of dibutyltin dilaurate were added in mass%, and the temperature was raised to 80 ℃ to continue the reaction for 3 hours. After the reaction is finished, most of the acetone solvent is removed by rotary evaporation, when the temperature of the mixed solution is reduced to room temperature, the mixed solution is uniformly poured into a polytetrafluoroethylene mold, and forced air drying is carried out at the temperature of 60 ℃. The proportions of the respective raw materials used are shown in table 1.
TABLE 1 PU films of different formulations and their mechanical properties
(2) Synthesis of long-chain alkyl diazomethane
Synthesis of 4, 4' -bis-dodecyloxybenzophenone
Dimethylformamide (30mL), 4, 4' -dihydroxybenzophenone (2.14g,0.01mol), 1-bromododecane (5g,0.02mol), potassium carbonate (6.9g,0.05mol) were added to a single-neck flask, reacted at 80 ℃ for 24h, then stirred under reflux for 24h, cooled to room temperature after the reaction was completed to obtain a white flocculent solid, and dried in a vacuum drying oven for 12 h. 70 percent of Yield;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.
synthesis of 4, 4' -bis-dodecyloxybenzophenone hydrazone
Dissolving the solid (1.39g,2.53mmol) obtained in the first step in 20mL of ethanol, pouring into a 100mL single-neck bottle, adding hydrazine hydrate (2.45mL,50.6mmol), adding a few drops of glacial acetic acid (0.4mL) as a catalyst, heating to 80 ℃, refluxing and stirring for 48h, evaporating the ethanol after the reaction is finished, dissolving the ethanol in dichloromethane (60mL), washing with distilled water (60mL) for 4 times, and adding anhydrous ethanolThe organic layer was dried over magnesium sulfate, rotary evaporated to give a pale yellow solid, and dried in a vacuum oven for 24 h. 75 percent of Yield;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.
synthesis of 4, 4' -bis-dodecyloxy diazomethane
The second step product (1.015g,1.8mmol) was dissolved in dichloromethane (15mL), manganese dioxide (0.57g,6.51mmol), anhydrous sodium sulfate (0.50g,3.50mmol), potassium hydroxide (0.15g,2.75mmol) were added, stirred at room temperature away from light for 2h, after the reaction was complete, suction filtered, and the organic layer was rotary evaporated to give a purple solid. 50 percent of Yield;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
Firstly, cutting the prepared polyurethane film into small blocks of 2X 2 cm. Then, carrying out surface modification on the film by adopting an ultraviolet irradiation method:
ultraviolet irradiation method: firstly dissolving 4, 4' -bis-dodecyloxydiazomethane (0.1g) in cyclohexane (15mL), then dripping the solution on the surface of the hydrophobic modified polyurethane film by using a rubber head dropper, and after the solvent is completely volatilized, irradiating the hydrophobic modified polyurethane film for 30min by using ultraviolet light with the intensity of 500mW/cm2(ii) a Cooling to room temperature, and washing with cyclohexane to obtain the hydrophobic modified polyurethane film.
Example 4
As described in example 1, except that:
the prepolymerization reaction temperature in the step (1) is 100 ℃, and the reaction temperature is 70 ℃ after dimethylolpropionic acid and dibutyltin dilaurate are added;
the intensity of the ultraviolet light in the step (3) is 1500mW/cm2。
Example 5
As described in example 1, except that:
in the step (1), the mass ratio of diisocyanate, polytetrahydrofuran, a cross-linking agent, a chain extender, dimethylolpropionic acid and a catalyst is 1: 1.1: 0.024: 0.28: 0.02: 0.003.
test example 1, hydrophobicity test
In order to verify the hydrophobic property of the hydrophobic polyurethane film prepared by the invention, a contact angle tester is adopted to measure the water contact angle of the surface of the film. Before the polyurethane film is not modified, the film is hydrophilic due to carboxyl introduced by dimethylolpropionic acid monomer. In order to study the influence of the content of dimethylolpropionic acid on the surface hydrophobic property of the polyurethane film, the water contact angles of the polyurethane film with dimethylolpropionic acid of 1%, 3% and 5% by mass respectively were tested; the test results are shown in table 2.
Table 2 water contact angle data for polyurethane films
As can be seen from Table 2, since dimethylolpropionic acid is generally added in the preparation of polyurethane, the resulting polyurethane film is generally hydrophilic. The contact angles of the polyurethane films before modification are all smaller than 85 degrees, and the water contact angle of the polyurethane film modified by ultraviolet light irradiation is remarkably increased (>90 degrees), which shows that the modified polyurethane film becomes hydrophobic. The water contact angle of the film did not change much with increasing dimethylolpropionic acid content, indicating that the hydrophobic properties of the film were not greatly affected by dimethylolpropionic acid content.
The photographs of the water contact angles of the polyurethane films in this test example are shown in FIGS. 1-2. As can also be seen from FIGS. 1-2, the water contact angle of the modified polyurethane film surface was increased, demonstrating that the film changed from hydrophilic to hydrophobic.
Claims (9)
1. A method for preparing a hydrophobic polyurethane film by ultraviolet irradiation comprises the following steps:
(1) preparation of polyurethane films
Mixing diisocyanate and polytetrahydrofuran, and reacting at 80-120 ℃ for 1-10 h; adding a cross-linking agent and a chain extender, adding dimethylolpropionic acid and a catalyst, and reacting at 60-90 ℃ for 1-10h to obtain a polyurethane solution; then forming a film and carrying out heat treatment to obtain a polyurethane film;
(2) preparation of long-chain alkyl diazomethane
Reacting 4,4 '-dihydroxy benzophenone with 1-bromododecane to obtain 4, 4' -bis-dodecyloxy benzophenone; 4,4 '-bis-dodecyloxy benzophenone reacts with hydrazine hydrate to obtain 4, 4' -bis-dodecyloxy benzophenone hydrazone; 4, 4' -bis-dodecyloxy benzophenone hydrazone is subjected to oxidation reaction to obtain long-chain alkyl diazomethane;
(3) preparation of hydrophobic polyurethane film
Dissolving long-chain alkyl diazomethane in a solvent, uniformly coating the solvent on the surface of the polyurethane film, and irradiating the polyurethane film for 1 to 30min by ultraviolet light to obtain the hydrophobic polyurethane film.
2. The method for preparing a hydrophobic polyurethane film by ultraviolet irradiation according to claim 1, wherein the diisocyanate in step (1) is 4, 4' -dicyclohexylmethane diisocyanate, the crosslinking agent is trimethylolpropane, the chain extender is 1, 6-hexanediol, and the catalyst is dibutyltin dilaurate.
3. The method for preparing the hydrophobic polyurethane film by ultraviolet irradiation according to claim 1, wherein the mass ratio of the diisocyanate, the polytetrahydrofuran, the cross-linking agent, the chain extender, the dimethylolpropionic acid and the catalyst in the step (1) is 1: (0.8-1.2): (0.01-0.1): (0.1-1): (0.01-0.1): (0.001-0.01).
4. The method for preparing the hydrophobic polyurethane film by ultraviolet irradiation according to claim 1, wherein the reaction temperature of the 4, 4' -dihydroxybenzophenone and the 1-bromododecane in the step (2) is 80-200 ℃ and the reaction time is 10-100 h.
5. The method for preparing a hydrophobic polyurethane film by ultraviolet irradiation according to claim 1, wherein the ratio of the mass of 4, 4' -bis-dodecyloxybenzophenone to the volume of hydrazine hydrate in the step (2) is 1 g: (1-10) mL.
6. The method for preparing a hydrophobic polyurethane film by ultraviolet irradiation according to claim 1, wherein in the step (2), ethanol is used as a solvent and acetic acid is used as a catalyst in the reaction process of 4, 4' -bis-dodecyloxybenzophenone and hydrazine hydrate, and the reaction is carried out at 70-100 ℃ for 10-100 h;
the ratio of the mass of the 4, 4' -bis-dodecyloxybenzophenone to the volume of the ethanol is 1 g: (10-100) the ratio of the mass of 4, 4' -bis-dodecyloxybenzophenone to the volume of acetic acid was 1 g: (0.05-0.5) mL.
7. The method for preparing a hydrophobic polyurethane film by ultraviolet irradiation according to claim 1, wherein the oxidizing agent used in the oxidation reaction of 4, 4' -bis-dodecyloxybenzophenone hydrazone in the step (2) is manganese dioxide, the water absorbent is anhydrous sodium sulfate, and the base is potassium hydroxide;
the mass ratio of the 4, 4' -bis-dodecyloxybenzophenone hydrazone to the manganese dioxide to the anhydrous sodium sulfate to the potassium hydroxide is 1: (0.2-2): (0.25-1): (0.01-0.1).
8. The method for preparing the hydrophobic polyurethane film by ultraviolet irradiation according to claim 1, wherein the oxidation reaction process of the 4, 4' -bis-dodecyloxybenzophenonehydrazone in the step (2) is a dark reaction, the reaction temperature is-40 ℃ and ~ 40 ℃, and the reaction time is 1-10 h.
9. The method for preparing hydrophobic polyurethane film by ultraviolet irradiation as claimed in claim 1, wherein the intensity of the ultraviolet light in step (3) is 500-3000mW/cm2The ultraviolet irradiation time is 1-30 min;
the solvent in the step (3) is cyclohexane, and the mass ratio of the long-chain alkyl diazomethane to the volume of the solvent is 1 g: (1-10) mL.
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