TW201120078A - Honeycomb-like polymeric films base on dendritic side-chain polyurethane - Google Patents

Abstract

The present invention discloses a dendron with hydrophobic functional of end group in the polyurethane systems, and the honeycomb-like structure thin films were obtained by a breath-figure process. The structures of dendron and dendritic side-chain polyurethanes of formula (A), (I) are as the follows: wherein, the end-groups(R) of the dendron are long alkyl chains or perfluoroalkyl derivatives.

Description

201120078 VI. Description of the Invention: [Technical Field] The present invention is a dendrimer having a hydrophobic functional group at the end, and is prepared by introducing a dendrimer into a polyurethane, wherein the dendrimer terminal group is The alkyl chain is either a perfluoroalkyl chain, such as a derivative of the above-described alkyl group compound of CiQ~Ci8 or 疋C4. [Prior Art] In recent years, the number of related literatures on dendritic chemistry has been as high as 2 or more. 'The dendrimer has a highly regular branching structure, and the molecular size is precisely controlled by step reaction. And a variety of designs. In 1978, Buhleier et al. used a acrylonitrile addition and reduction reaction to prepare a branched amine compound similar to a dendrimer, which is a hyperbranched polymer. T〇lnana et al. first published a dendrimer of poly(amidoamine, PAMAM) in 1984, and also made the earliest commercial record. Dendrimers are composed of two basic structures, including: (1) core (c〇re) (2) repeating unit (3) peripheral group (periphery group). The synthetic path is divided into two categories: divergent type and convergent type according to the growth direction. In order to avoid the cumbersome protection and deprotection steps, increase the yield and the growth of effective extension algebra, the prior art utilizes the high reactivity of isocyanate and azetidine-2,4-based on the bifunctional building block IDD. The reaction selectivity of dione' is matched with different alcohols and amines for the 201120078 parental synthesis reaction, developing a series of regular dendrimers of mal〇namide and urethane derivatives. molecule. The flow is as follows.

Alkyl or aromatic alcohol °V / .

Alkyl or aromatic amine (〇CN : f / ^ Alkyl primary amine

IDD Lu's other side chain dendritic polymers can be considered as "structural copolymers" of linear polymers and dendrimers. Beginning with the 1987 Tomalia et al. patent, the first mention of linear polyethylene Imine (PEI) is a dendrimer of the main chain. It is known from the literature that side chain dendrimers can be used in the fields of self-assembly, single molecule nanowires, luminescent materials, and catalysts. SUMMARY OF THE INVENTION The present invention introduces a long alkyl chain segment and a perfluoroalkane chain in a dendritic structure, and has a Valent force effect between the molecules; in addition, a Hunan dendritic polymer structure, a long alkyl chain or a perfluoroalkane The chains are bound and bundled to form two molecules of waxy dendrites, and the structure has hydrophobic properties. On the other hand, the dendrimer is a urea/maloxime structure having a strong hydrogen bond inside and the hydrogen bond between the inside and outside of the dendrimer as the dendrimer polymer number increases. Van der Valli also increased. After the ring-opening addition reaction, the present invention prepares dendrimers of different algebras into a polyurethane system to form a series of side 201120078 chain rules, dendritic poly(4). Due to the nitrogen bond outside the dendritic polymer phase and the van der Waals force, the side chain regular dendritic urethane can be prepared by the Breath_ figure method; in addition, in order to increase the material application feasibility, the present invention regulates the side chain dendritic The soft and hard segments of the polyurethane are composed to reinforce the mechanical properties of the porous film. One aspect of the invention is the introduction of a tree stalk into the side chain of the polyurethane, the general formula of which is shown in the structure of (I):

N wherein Ri represents diisocyanate and R2 represents a polyol. The above diisocyanate may be Methylene di-p-phenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI) or isophor. Isophorone diisocyanate (IPDI); and polyol (p〇iy〇i) can be polypropyl glycol (PPG), polycaprolacton (PCL) or polytetrahydrofuran (p〇lytetramethylene ether glycol, PTMEG). According to a specific embodiment, when R1 uses MDI and R2 uses PPG, the structural formula of the compound of formula (1) can be: 201120078

According to another specific embodiment, when the above R1 uses HDI and R2 uses PPG, the structural formula of the compound of the formula (I) can be:

0-2-1-

NH

(I-B) According to another specific embodiment, when the above R1 uses IPDI and R2 uses PPG, the structural formula of the compound of the formula (I) may be:

-Λ

(I-C)

According to another embodiment, when the above R1 uses MDI and R2 uses PCL for 201120078, the structural formula of the compound of the formula (1) can be: • KTCu

°\^c NH 0 (I-D) According to another embodiment, when the above R1 uses MDI and PTMEG, the structural formula of the compound of the formula (I) can be:

CT 0〆(IE) breath flgure The following is a detailed description of the invention and [Embodiment] 8 201120078 According to a specific embodiment, the side branch polymer of the polyurethane of the present invention has a general formula of (I) structure. Shown: Key import into a tree

N 0 wherein Ri represents a diisocyanate (diiso, cyanate), and R 2 represents that the above diisocyanate may be a di-p-phenyl isocyanate (Methylene di-) P-phenyl diisocyanate, MDI), Hexamethylene diisocyanate (HDI) or Isophorone diisocyanate (IPDI); and polyol can be polypropyl glycol (polypropyl glycol, PPG), polycaprolacton (PCL) or polytetramethylene ether glycol (PTMEG), the above-mentioned process of introducing a dendrimer into the side chain of the polyurethane can be represented by the flow chart one, and This process will be described in detail in the following specific examples. 9 201120078

Flowchart 1 Specific Example 1: Synthesis of dendrimer (A) In a specific embodiment, the reaction process of monomer IDD having a reaction selectivity is as shown in the second scheme:

Flowchart 2 uses IDD and stearyl alcohol to carry out the reaction, and then 201120078 uses a primary amine to open-loop the azetidine-2,4-dione. This stepwise synthesis step can synthesize dendrimers of different algebras. The reaction process is shown in flow chart three:

The three-layer polymer of the flow chart can be prepared by the following steps: First, the double & b b-table table unit (idd) is dissolved in tetrahydrofuran (THF) to form a first solution, and then An alcohol is added to the first solution and passed through, and the gas is at 7. . (: The reaction was carried out for 4 hours, and after the reaction was completed, it was dropped into methanol to: ▲ precipitated ' and continuously stirred at 70 ° C for 6 hours, and the first product was collected by suction filtration, and the first product was dried to obtain a first intermediate. [G_0.5;j. «, 'take the first-intermediate [G-0.5] in the reaction flask, dissolved in an appropriate amount of water, to form a "second solution, pass nitrogen and 7 〇〇c 11 201120078 The second solution was stirred and slowly added with diethylethylene triamine (DETA). After a second product was precipitated, the reaction was continued for 3 hours, then cooled to room temperature and washed with a large amount of tetrahydrofuran. The second product is filtered by air and dried to obtain a first dendrimer. Thereafter, the first dendrimer [G-1] is mixed with dehydrogenated tetrahydrofuran to form a third solution of 'nitrogen gas at 75 〇. The third solution was stirred under C, and after the first dendrimer [G-1] was completely dissolved, the difunctional building block IDD was added and reacted for 4 hours, after which part of the tetrahydrofuran was taken out and dropped into methanol to precipitate. , by suction filtration and drying to obtain a second intermediate body [G-1.5] After the hydrazine, 'the above steps are repeated' to prepare a third intermediate [G_2.5] and a fourth intermediate [G-3.5]. Finally, the first intermediate [G-0.5] is dissolved in tetrahydrofuran, which is dehydrated, and the first a second intermediate [Gi.5], the third intermediate [G_2.5], and the ruthenium intermediate [〇-3.5] and mixed with 卩0£) to form a third solution, the third solution is passed Nitrogen was reacted at 75 ° C for 48 hours. After the second intermediate [G-1.5] was completely reacted, methanol was precipitated and the unreacted element of APDEA was washed off, followed by stirring for 6 hours, then evacuating and drying to obtain a tree. Sound branches to molecules. In order to introduce a dendrimer into a system of polyurethane, it must be chemically modified. In this embodiment, a ring-opening reaction can be carried out using a single amine of ADPEA and azetidine-2,4-dione to synthesize an intermediate [G-1.5]-diol having a glycol functional group, so that It is used as a chain extender in polyurethane. The above flow is shown in the fourth flow chart: 12 201120078, similar to the synthesis of dendrimers in the series of alkyl chains from the scheme of 'CCl', the introduction of perfluoroalkylethyl alcohol-related derivatives to the end with perfluorooctane Since the ethyl group has a low surface energy relationship, the organic material will make the film superhydrophobic; the schematic diagram of the dendrimer is as follows:

HO

Schematic 1 Synthesis Example 2: Synthesis of compound (Ι-A) The number of grams of each raw material is taken according to the ratio of soft and hard segments; MDI is heated and melted at 50 ° C, the supernatant portion of the upper layer is taken, and PPG is vacuum-baked. 13 201120078 Dehydration of water' and heating to 80 ° C and pumping for 6 hours; then using DM (DMF) as solvent, MDI and PPG dissolved, reacted under nitrogen for half an hour, then added dendritic high The molecule was passed through and dibutyltin dilaurate was used as a catalyst. The temperature was raised to 80 ° C and the reaction was continued for 3.5 hours. After the reaction was completed, the solution was poured into a Teflon tray and placed in an oven to remove the solvent. membrane. 1 Gold Example 3: Compound (I-B) combines the number of grams of each raw material according to the ratio of soft and hard segments; HDI is used directly without pure φ, PPG is dehydrated in a vacuum oven and heated to 8 Torr.匸 and pumping for 6 hours; then use dimethylformamide (DMF) as a solvent, dissolve the pull and PPG, react with nitrogen at 60 ° C for half an hour, then add dendrimer [G-1.5 ]-diol and dibmyltin dilaurate as catalyst, heat up to 80qC, continue the reaction for 35 hours, after the reaction is finished, pour the solution into the Teflon tray and put it into the oven to remove the solvent. Film formation.

Synthesis Example 4: Synthesis of chemistry (t_c) The number of grams of each raw material was taken according to the ratio of soft and hard segments; IPDI was used without purification, and PPG was dewatered in a vacuum oven and heated to 80. (: and pumping for 6 hours; then dissolving IPDI and PPG with dimethylformamide (DMF) as solvent, reacting with nitrogen at 60 ° C for half an hour, then adding dendrimer [G-1.5 ]-diol and dibutyltin dilaurate as catalyst, heat up to 80 ° C, continue the reaction for 3.5 hours. After the reaction is completed, pour the solution into the Teflon tray and place it in the oven 14 201120078 The solvent is removed to form a film. Gold Example 5: The ruthenium of the compound is taken according to the ratio of the soft and hard segments. The MDI is heated and melted at = ° C, and the clear liquid portion of the upper layer is taken, and the PCL is vacuum-twisted. The tank was dehydrated and heated to 8 ° C and pumped for 6 hours; then dimethyl hydrazine, (DMF} as solvent 'will dissolve _ and pCL, at 6 〇 <

The reaction was carried out for half an hour with nitrogen, followed by the addition of a dendrimer-s-diol and a butyl laurate (Dibutyltin sinensis (6) as a catalytic temperature f 8G ° C, continued reaction 3.5, when the reaction is over The solution is dissolved in a Teflon plate and placed in an oven to remove the solvent to form a film. Gold Example 6: 么h thing (τ_Ε, the combination of red, according to the ratio of soft and hard segments to take the grams of each raw material; MDI Heat and melt at 5 ° ° f, take the upper part of the clear liquid part, PTMEG vacuum fire, phase water, and heat to 8 () σ (: and pumping 6 hours two (four) (four) 'MDI and down II gas The reaction, half an hour, followed by adding a dendrimer to promote the second 7 such as dibutyltin dilaurate (9) (four) such as dilaurate) as a catalyst, heating up to the reaction + LM continued to react for 3.5 hours, after the reaction is over, the cold liquid is poured In the Teflon plate, the solvent is removed from the container for film formation. The details of the specific embodiment of the corpse are expected to be more clear about the miscellaneous and spiritual spirit of the field, * not the preferred one disclosed above. The embodiment of the invention is intended to limit the scope of the invention. Conversely, the purpose is to The scope of the patent application is intended to cover the various modifications and equivalents of the scope of the invention. The scope of the patent scope of the invention should be construed broadly Possible changes and arrangements of equality.

16 201120078 [Simple description of the diagram] Figure 1 shows the 1H NMR spectrum of Compound A. Figure 2 shows the 1H NMR spectrum of the compound 图. Figure 3 shows the AFM of the pore film formed by Ι-A. Figure 4 is a schematic diagram showing the AFM of the pore film formed by Ι-Β. • [Main component symbol description]

Claims (1)

201120078 VII. Patent application scope: 1. A polyurethane containing a side chain regular dendrimer having a structure of the general formula (I): N 0 , wherein 'R1 is diisocyanates, and R2 is polyols. 2. The polyurethane according to claim 1, wherein R1 comprises Methylene di-p-phenyl diisocyanate (MDI), bismuth 1,6-hexane diisocyanate. One of a group consisting of Hexamethylene diisocyanate (HDI) and isolphantrone diisocyanate (IPDI), and R2 contains polypropyl glyc (pg), One of a group consisting of polycaprolactone polyol (PCL) and polytetrahydropyridinol (pylene). 3. A method for preparing a polyurethane containing a side chain regular dendrimer for preparing a polyurethane containing a side chain regular dendrimer having a structure of the formula (1): 18 201120078 The method consists of the following steps: (a) In a first-stage reaction, the purified diisocyanate and the dehydrated polyol (p〇ly〇ls) are placed in a round bottom flask at 60 ° C under nitrogen. Forming a reaction system, the reaction system is refluxed for half an hour; and (b) adding a dendrimer as a chain extender and a dilauric acid as a catalyst in a second stage reaction Dibutyltin dilaurate in the reaction system, then the reaction system was heated to 80 ° C and continued to react for 3.5 hours. After the reaction was completed, the solution in the reaction system was poured into an iron tray and placed in an oven. The solvent is removed to further obtain the polyamine. , 4, 2: the dendritic high score of the long agent Wherein R is a C1G~Cl8 burnt chain or a total a-alkylethyl derivative on W 19 201120078. 5. The dendrimer according to claim 4, wherein R comprises CioK^i-, and (Ι; 18Η37-one of the group consisting of 6.), as in claim 4 a dendrimer, wherein r comprises one of c4f9ch2ch2-, c6f13ch2ch2-, c8f17ch2ch2-, C10F21CH2CH2-, and C12F25CH2CH2-hujin. 7. A method for preparing a dendrimer (Dendron) for preparation Dendrimer which is one of the chain extenders of polyurethane. The dendrimer has a structure of the formula (A): (A) The method comprises the following steps: (a) in a first-stage reaction, a bifunctional building block (IDD) is dissolved in tetrahydrofuran (THF) to form a first solution, and then an alcohol is added to the solution. The first solution was reacted with nitrogen at 70 ° C for 4 hours 'to be reacted, and then dropped into sterols' to precipitate, and stirred at 70 ° C for 6 hours, and a first product was collected by suction filtration. Drying the first product to obtain a first medium = body [G-0.5] θ 20 201120078 (b) in a second stage reaction, taking the first intermediate [g_〇.5] in the reaction flask, The tetrahydrofuran, which is dehydrated with water, is dissolved to form a solution of the first solution, and the second solution is stirred under nitrogen at 7 ° C and slowly added with diethylethylene triamine (DETA). After the product was precipitated, the reaction was continued for 3 hours, then cooled to room temperature, and the second product was washed with a large amount of tetrahydrofuran and evacuated. Filtered and dried to obtain a first dendrimer [G4]; (c) In the third stage of the reaction, the first dendrimer [G_i] is mixed with water to remove tetrahydrogen. Forming a third solution, stirring the third solution at 75 ° C with nitrogen, adding the first dendrimer [gj] to the difunctional building block IDD and reacting for 4 hours, after which the portion is reacted for 4 hours. The tetrahydrofuran is removed, and the precipitate is precipitated by dropping into a methanol, and dried by suction filtration to obtain a second intermediate [G_ 1.5]; (d) repeating the above steps to prepare a third intermediate [G_2 5] and a fourth intermediate [G-3.5]; and (e) dissolving the first intermediate [G_〇5], the second intermediate [G-1.5], the third, with water-depleted tetrahydrofuran Intermediate [G-2.5] and the fourth intermediate [G-3.5] and mixing APDEA to form a third solution, and the third solution is reacted with nitrogen at 75 ° C for 48 hours, to be the second intermediate [G-1.5] After complete reaction, the unreacted APREA was precipitated and washed off with decyl alcohol, followed by stirring for 6 hours, followed by suction filtration and drying to obtain the stalk-like southern molecule. twenty one