A preparation method of organosilicon nylon elastomer

Abstract

The present invention relates to the technical field of man-made fibers, and provides a method for preparing an organosilicon nylon elastomer, including an organosilicon modification stage: mixing terminal isocyanate organosilicon with polyethyleneimine in a predetermined ratio, performing banburying reaction, and obtaining modified organosilicon; an organosilicon nylon elastomer synthesis stage: mixing modified organosilicon, nylon, and a catalyst in a predetermined ratio for 30 min; placing the mixed material into an extruder; and drawing the extrudate to obtain an organosilicon nylon elastomer. By this, the present invention modifies terminal isocyanate organosilicon by polyethyleneimine, introduces a C-C segment into the organosilicon, and the C-C segment has similar compatibility with the C-C segment in nylon, thereby improving the compatibility of organosilicon with nylon. In the synthesis stage of the organosilicon nylon elastomer, the reaction probability of the terminal amine group of the organosilicon and the terminal carboxyl group of the nylon is increased, the reaction conversion rate and the synthesis efficiency are improved, and the mechanical properties of the finished product are significantly improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of man - made fibers, and particularly relates to a method for preparing an organosilicon - nylon elastomer. Background Art

[0002] Organosilicon - nylon elastomer is a high - performance polymer material, combining the advantages of two polymer materials, namely organosilicon and nylon, and having excellent elasticity and tensile properties. In the field of fibers, these properties enable organosilicon - nylon elastomer to be used in the manufacture of high - performance textiles, such as work clothes with high temperature resistance and wear resistance, and sports and leisure clothing requiring high elastic recovery.

[0003] However, due to the low surface energy of organosilicon, its compatibility with nylon melt is poor, resulting in poor dispersion of organosilicon in nylon melt, reducing the reactivity between organosilicon and nylon, and greatly affecting the mechanical properties of the synthesized organosilicon - nylon elastomer.

[0004] In summary, the existing technology obviously has inconveniences and defects in practical use, so it is necessary to be improved. Summary of the Invention

[0005] Aiming at the above - mentioned defects, the present invention mainly provides a method for preparing an organosilicon - nylon elastomer to solve the technical problem that the poor compatibility between organosilicon and nylon melt affects the mechanical properties of the material.

[0006] To solve the above problems, the present invention provides a method for preparing an organosilicon - nylon elastomer, including an organosilicon modification stage and an organosilicon - nylon elastomer synthesis stage; specifically:

[0007] The organosilicon modification stage includes: mixing terminal isocyanate - group organosilicon and polyethyleneimine in a predetermined ratio, and carrying out kneading reaction to obtain modified organosilicon; the kneading temperature is: 150°C - 250°C, and the kneading time is: 10 - 200 min;

[0008] The organosilicon - nylon elastomer synthesis stage includes:

[0009] S1, mixing the modified organosilicon, nylon, and catalyst in a predetermined ratio for 30 min;

[0010] S2, putting the mixed material into an extruder and extruding at a predetermined extrusion temperature;

[0011] S3, carrying out strand drawing on the extrudate, cooling and pelletizing to obtain the organosilicon - nylon elastomer.

[0012] According to the method for preparing an organosilicon - nylon elastomer of the present invention, the mixing ratio of terminal isocyanate - group organosilicon and polyethyleneimine in the organosilicon modification stage is: molar ratio 1:10 - 1:200.

[0013] According to the preparation method of the silicone nylon elastomer of the present invention, the degree of polymerization of the terminal isocyanate group silicone in the silicone modification stage is 5-20, and the degree of polymerization of polyethyleneimine is 10-200.

[0014] According to the preparation method of the silicone nylon elastomer of the present invention, the degree of polymerization of the terminal isocyanate group silicone in the silicone modification stage is 8-12, and the degree of polymerization of polyethyleneimine is 20-80.

[0015] According to the preparation method of the silicone nylon elastomer of the present invention, the kneading temperature in the silicone modification stage is: 180°C - 210°C, and the kneading time is: 30 - 60 min.

[0016] According to the preparation method of the silicone nylon elastomer of the present invention, the mass ratio of the modified silicone to nylon is 1:1 - 1:10; the catalyst accounts for 0.1% - 1% of the total mass of the modified silicone and nylon; the catalyst is sodium hypophosphite.

[0017] According to the preparation method of the silicone nylon elastomer of the present invention, in the S1 step, a high-speed mixer is used to mix the modified silicone, nylon, and catalyst.

[0018] According to the preparation method of the silicone nylon elastomer of the present invention, the extruder in the S2 step is a twin-screw extruder, and the main screw speed is 50 - 300 revolutions / min.

[0019] According to the preparation method of the silicone nylon elastomer of the present invention, the extrusion temperature is 200°C - 280°C.

[0020] According to the preparation method of the silicone nylon elastomer of the present invention, the nylon is one or more of nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, nylon 1010, and nylon 1212.

[0021] In summary, the present invention modifies the terminal isocyanate group silicone with polyethyleneimine to introduce a C-C chain segment into the silicone. The C-C chain segment in the modified silicone has similar compatibility with the C-C chain segment in nylon, improving the compatibility between silicone and nylon. In the synthesis stage of the silicone nylon elastomer, the reaction probability between the terminal amino group of silicone and the terminal carboxyl group of nylon is increased, improving the reaction conversion rate and synthesis efficiency, and significantly enhancing the mechanical properties of the finished product. Description of the Drawings

[0022] Figure 1 is a schematic diagram of the silicone modification reaction of the present invention;

[0023] Figure 2 is a schematic diagram of the preparation reaction of the silicone nylon elastomer of the present invention; Detailed implementation mode

[0024] See Figure 1 , the present invention provides a preparation method of a silicone nylon elastomer, including a silicone modification stage and a silicone nylon elastomer synthesis stage; specifically:

[0025] The silicone modification stage includes: mixing terminal isocyanate group silicone with polyethyleneimine in a predetermined ratio, and carrying out kneading reaction to obtain modified silicone;

[0026] The kneading temperature is: 150°C to 250°C, and the kneading time is: 10 to 200 min;

[0027] The C=N bond in the isocyanate group at the end of the terminal isocyanate group silicone is an active group; the C=N bond undergoes an addition reaction with the terminal OH in the polyethyleneimine, such as Figure 1 Reaction A in; or the C=N bond undergoes an addition reaction with the N-H group in the polyethyleneimine, such as Figure 1 Reaction B in.

[0028] The present invention modifies the terminal isocyanate group silicone with polyethyleneimine to introduce a C-C segment into the silicone.

[0029] As a preferred scheme, the mixing ratio of the terminal isocyanate group silicone to the polyethyleneimine in the silicone modification stage is: molar ratio 1:10 to 1:200;

[0030] Furthermore, the degree of polymerization of the terminal isocyanate group silicone in the silicone modification stage is 5 to 20, and the degree of polymerization of the polyethyleneimine is 10 to 200;

[0031] Preferably, the degree of polymerization of the terminal isocyanate group silicone in the silicone modification stage is 8 to 12, and the degree of polymerization of the polyethyleneimine is 20 to 80.

[0032] Preferably, the kneading temperature in the silicone modification stage of the present invention is: 180°C to 210°C, and the kneading time is: 30 to 60 min;

[0033] The silicone nylon elastomer synthesis stage includes:

[0034] S1, mixing the modified silicone, nylon and catalyst in a predetermined ratio for 30 min;

[0035] As an example, the mass ratio of the modified silicone to the nylon is 1:1 to 1:10; the catalyst accounts for 0.1% to 1% of the total mass of the modified silicone and the nylon;

[0036] The catalyst of the present invention is preferably sodium hypophosphite.

[0037] As an embodiment, in the step S1, a high-speed mixer is used to mix the modified silicone, nylon, and catalyst;

[0038] S2. Put the mixed material into an extruder and extrude it at a predetermined extrusion temperature;

[0039] Combined with Figure 2 , the amino group in the modified silicone reacts with the carboxyl group at the end of the nylon macromolecular chain under the action of the catalyst, and the silicone is connected to the nylon through a covalent bond to obtain a silicone nylon elastomer.

[0040] As an embodiment, the extruder in the step S2 is a twin-screw extruder, and the main screw speed is 50 - 300 revolutions / min;

[0041] Furthermore, the extrusion temperature is 200°C - 280°C, preferably 220°C - 250°C.

[0042] The C-C chain segment in the modified silicone of the present invention has similar compatibility with the C-C chain segment in the nylon, improving the compatibility between the silicone and the nylon. The reaction probability between the terminal amino group of the silicone and the terminal carboxyl group of the nylon is increased. Compared with the 50 - 100 h required by the existing production process, the reaction synthesis time of the present invention using a twin-screw extruder is 5 - 10 min. The reaction conversion rate and synthesis efficiency are greatly improved.

[0043] S3. Draw the extrudate, cool it, and pelletize it to obtain a silicone nylon elastomer;

[0044] As an embodiment, the nylon of the present invention is one or more of nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, nylon 1010, and nylon 1212.

[0045] The present invention sets multiple embodiments, and multiple modified silicone specimens are prepared by subjecting terminal isocyanate group silicone and polyethyleneimine to a modification reaction. And the modified silicone specimens are respectively reacted with various nylons to synthesize multiple silicone nylon elastomer specimens.

[0046] At the same time, a control sample without the silicone modification stage is set. Then, multiple mechanical property tests are performed on the synthesized silicone nylon elastomer specimens to verify the material properties.

[0047] The specific experimental parameters of each embodiment and the control example are shown in Table 1, and the test results are shown in Table 2. (Only the changed parameters are listed in Table 1. For the same components and steps, please refer to the previous text and will not be elaborated here.)

[0048] To simplify the table text, the complex expressions in the table are simplified as follows;

[0049] Silicone modification stage:

[0050] "Molar ratio of terminal isocyanate group-containing silicone and polyethyleneimine", abbreviated as "modified material ratio" in the table;

[0051] "Degree of polymerization of terminal isocyanate group-containing silicone", abbreviated as "silicone degree of polymerization" in the table;

[0052] "Degree of polymerization of polyethyleneimine", abbreviated as "imine degree of polymerization" in the table.

[0053] Synthesis stage of silicone nylon elastomer:

[0054] "Mass ratio of modified silicone and nylon", abbreviated as "synthesis material ratio" in the table;

[0055] "Catalyst accounts for the total mass of modified silicone and nylon", abbreviated as "catalyst dosage" in the table;

[0056] To make the experimental results comparable, the nylon in each example and comparative example is nylon 6; the extrusion step in the synthesis stage of silicone nylon elastomer is completed by a twin-screw extruder.

[0057] "Rotation speed of the main screw of the twin-screw extruder", abbreviated as "screw speed" in the table.

[0058] Table 1 Parameters of each example and comparative example

[0059]

[0060] Note: In the preparation process of the comparative example samples in Table 1, there is no silicone modification stage. Therefore, the component of the "synthesis material ratio" in the comparative examples in Table 1 is: the mass ratio of terminal amine group-containing silicone and nylon 6, and its steps and parameters are the same as those above.

[0061] Table 2 Mechanical property test results of silicone nylon elastomers prepared in each example and comparative example

[0062]

[0063] Referring to Table 1 and Table 2, compared with the comparative example without silicone modification, the examples of the present invention modify terminal isocyanate group-containing silicone with polyethyleneimine to introduce C-C chain segments into the silicone. The C-C chain segments in the modified silicone have similar compatibility with the C-C chain segments in nylon, improving the compatibility between silicone and nylon. In the synthesis stage of silicone nylon elastomer, the reaction probability between the terminal amine group of silicone and the terminal carboxyl group of nylon is increased, improving the reaction conversion rate and synthesis efficiency, and significantly enhancing the mechanical properties of the finished product.

[0064] In summary, the present invention provides a method for preparing a silicone-nylon elastomer. By modifying the terminal isocyanate group silicone with polyethyleneimine, a C-C segment is introduced into the silicone. The C-C segments in the modified silicone have similar compatibility with the C-C segments in the nylon, improving the compatibility between the silicone and the nylon. During the synthesis stage of the silicone-nylon elastomer, the reaction probability between the terminal amino group of the silicone and the terminal carboxyl group of the nylon is increased, improving the reaction conversion rate and synthesis efficiency, and significantly enhancing the mechanical properties of the finished product.

[0065] Of course, the present invention may also have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and deformations according to the present invention. However, these corresponding changes and deformations should all fall within the protection scope of the appended claims of the present invention.

Claims

1. A method for preparing a silicone nylon elastomer, characterized in that: It includes the stage of organosilicon modification and the stage of organosilicon nylon elastomer synthesis; specifically: The organosilicon modification stage comprises: mixing the isocyanate-terminated organosilicon and polyethyleneimine in a predetermined ratio, and performing banburying reaction to obtain modified organosilicon; the banburying temperature is 150° C. to 250° C., and the banburying time is 10 to 200 min; The mixing ratio of the isocyanate-terminated silicone and polyethyleneimine in the silicone modification stage is: a molar ratio of 1:10 to 1:200; The silicone nylon elastomer synthesis stage includes: S1, mixing the modified silicone, nylon and catalyst in a predetermined ratio for 30 min; The mass ratio of the modified silicone to nylon is 1:1 to 1:10; the catalyst accounts for 0.1% to 1% of the total mass of the modified silicone and nylon; the catalyst is sodium hypophosphite; S2, putting the mixed material into an extruder and extruding it at a predetermined extrusion temperature; S3, drawing the extrudate into strips, cooling it, and pelletizing it to obtain a silicone nylon elastomer.

2. The method for preparing a silicone nylon elastomer according to claim 1, characterized in that: The polymerization degree of the isocyanate-terminated silicone in the silicone modification stage is 5-20, and the polymerization degree of the polyethyleneimine is 10-200.

3. The method for preparing a silicone nylon elastomer according to claim 2, characterized in that: The polymerization degree of the isocyanate-terminated silicone in the silicone modification stage is 8-12, and the polymerization degree of the polyethyleneimine is 20-80.

4. The method for preparing a silicone nylon elastomer according to claim 1, characterized in that: The banburying temperature in the organosilicon modification stage is 180°C to 210°C, and the banburying time is 30 to 60 min.

5. The method for preparing a silicone nylon elastomer according to claim 1, characterized in that: In the step S1, a high-speed mixer is used to mix the modified silicone, nylon and the catalyst.

6. The method for preparing a silicone nylon elastomer according to claim 1, characterized in that: The extruder in step S2 is a twin-screw extruder, and the main screw speed is 50-300 rpm.

7. The method for preparing a silicone nylon elastomer according to claim 1, characterized in that: The extrusion temperature is 200°C to 280°C.

8. The method for preparing a silicone nylon elastomer according to any one of claims 1 to 7, characterized in that: The nylon is one or more of nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, nylon 1010 and nylon 1212.

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