Dynamically-repairable polyurethane based on oxime and preparation method thereof

A technology of polyurethane and agglomerate oxime, applied in the field of polyurethane materials, can solve the problems of lack of recycling and reprocessing, unfavorable environmental protection and energy saving, and no reports on polyurethane.

Active Publication Date: 2018-07-24
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although the catalyst required in the polyurethane preparation process has so many disadvantages, the method of preparing polyurethane at room temperature without catalyst action has not yet been reported.
In addition, f

Method used

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  • Dynamically-repairable polyurethane based on oxime and preparation method thereof
  • Dynamically-repairable polyurethane based on oxime and preparation method thereof
  • Dynamically-repairable polyurethane based on oxime and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0086] Embodiment 1 bifunctional oxime B-(S-R) 2 preparation of

[0087] a) p-hydroxyacetophenone (compound shown in formula (II), wherein, R 1 is phenylene, R 2 Methyl) (52.37g) was dissolved in tetrahydrofuran solution (300mL), then allyl bromide (compound shown in formula (III), wherein, m is 1, X is Br) (37.3mL) and sodium carbonate (79g), reacted at 30°C for 3h; the reaction system was concentrated, diluted with water (200mL), extracted with ethyl acetate (3×200mL), concentrated, and dried over anhydrous sodium sulfate to prepare the intermediate product a;

[0088] b) The above intermediate product a was dissolved in 270mL H 2 O / EtOH (1:1, v / v), and add hydroxylamine hydrochloride (40.1g) and sodium carbonate (78.9g), react at 40 ℃ for 5h; Ethanol was washed three times to obtain a white solid, which was a compound (71.36g) shown in formula (IV), wherein, R 1 is phenylene, R 2 is methyl, m is 1; the two-step yield of the compound is 97%.

[0089] The structural c...

Embodiment 2 3

[0097] Example 2 Trifunctional oxime B-(S-R) 3 preparation of

[0098] The compound shown in formula (IV) (wherein, R 1 is phenylene, R 2 is methyl, m is 1; 13.22g) was dissolved in 100mL ethyl acetate, and 1,1,1-trimethylolpropane tris(3-mercaptopropionate) (9.67g) and 0.01 equivalents (for alkenes) were added Benzoin dimethyl ether (0.09g) was reacted for 3h under ultraviolet light irradiation; the solvent was concentrated and removed to obtain the trifunctional oxime B-(S-R) 3 , the specific structure of the prepared multifunctional oxime is shown in the following formula (IX):

[0099]

[0100] The structural confirmation data are as follows:

[0101] 1 H NMR (300MHz, CDCl 3 , ppm) δ9.10 (br s, 3H), 7.56 (d, J = 11.6Hz, 6H), 6.88 (d, J = 9Hz, 6H), 4.06-4.03 (m, 9H), 2.79 (t, J =7.2Hz,6H),2.72(t,J=7.2Hz,6H),2.64(t,J=6.9Hz,6H),2.27(s,9H),2.05(m,6H),1.49(q,J =7.5Hz, 2H), 0.88(t, J=7.5Hz).

[0102] figure 2 It is the infrared spectrogram of the trifunctional oxim...

Embodiment 3

[0103] The preparation of embodiment 3 thermoplastic oxime-based polyurethanes

[0104] The bifunctional oxime (21 g) prepared in Example 1 was dissolved in 80 mL of tetrahydrofuran solution, hexamethylene diisocyanate (62 g) was added, stirred for 6 h, and the solvent was removed in vacuo to prepare thermoplastic oxime-based polyurethane.

[0105] The chemical reaction equation of the process is shown as follows:

[0106]

[0107] M of the thermoplastic oxime-based polyurethane prepared in this embodiment n = 60,000, PDI = 1.8.

[0108] The structural confirmation data are as follows:

[0109] 1H NMR (400MHz, CDCl 3 ,ppm)δ7.60(d,J=8.4Hz,4H),6.90(d,J=8.4Hz,4H),6.48(s,2H),4.07(t,J=5.6Hz,4H),3.65- 3.60(8H),3.40-3.20(4H),2.74-2.70(8H),2.36(s,6H),2.05(t,J=6.4Hz,4H),1.65-1.55(1H),1.40-1.30(4H ).

[0110] The mechanical properties were tested and the results are shown in Table 1.

[0111] image 3 It is the infrared spectrogram of the thermoplastic oxime-based polyuretha...

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Abstract

The invention provides a polyfunctional group oxime and a preparation method thereof, and novel dynamically-repairable polyurethane based on the oxime and a preparation method thereof, the oxime is ahighly reactive organic substance, the oxime and an isocyanate can be prepared into the polyurethane at room temperature without a catalyst. It is noteworthy that the oxime is usually obtained by reacting a carbonyl compound (an aldehyde or a ketone) with hydroxylamine under mild conditions, and the process is an atomically-economic, high-yield and simple reaction. The thermosetting oxime-based polyurethane is cut into small pieces, and the small pieces can be hot-pressed again for molding under the conditions of 90-120 DEG C and 1-100 MPa, and the obtained thermosetting polyurethane substantially restores original mechanical properties; the reaction for preparing the polyurethane can be carried out without the catalyst at the room temperature. The preparation method is simple, the preparation process has wide sources of raw materials and low production cost, and the method has a prospect of large-scale industrial production.

Description

technical field [0001] The invention relates to an oxime-based dynamically repairable polyurethane and a preparation method thereof, belonging to the field of polyurethane materials. Background technique [0002] Polyurethane is mainly prepared by addition polymerization of diisocyanate or polyisocyanate and dihydroxyl or polyhydroxyl compound. The molecular structure of polyurethane contains carbamate group (—NH—COO—). It has excellent properties such as high elasticity, wear resistance, low temperature resistance, solvent resistance and aging resistance, so it is widely used in various fields of national economy. The existing polyurethane resin preparation method is to polymerize isocyanate and polyol as raw materials under the condition of catalyst and / or heating (generally >60°C) to obtain the product. The catalysts used mainly include organic tertiary amine catalysts and organic metal compound catalysts. Among them, most organic tertiary amine catalysts have ammoni...

Claims

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Application Information

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IPC IPC(8): C08G18/32C07C319/18C07C323/12C07C323/52
CPCC07C45/61C07C249/08C07C319/18C08G18/3868C07C49/84C07C251/24C07C323/12C07C323/52
Inventor 刘文星张欢赵宁徐坚
Owner INST OF CHEM CHINESE ACAD OF SCI
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