Preparation method of organic silicon nylon elastomer

Abstract

The invention relates to the technical field of artificial fibers, and provides an organic silicon nylon elastomer preparation method, which comprises: an organic silicon modification stage: mixing isocyanate-terminated organic silicon and polyethyleneimine according to a predetermined ratio, and carrying out a banburying reaction to obtain modified organic silicon; in the organic silicon nylon elastomer synthesis stage, the modified organic silicon, nylon and a catalyst are mixed for 30 min according to a preset proportion; putting the mixed material into an extruder; and drawing the extrudate to obtain the organic silicon nylon elastomer. Therefore, isocyanate-terminated organic silicon is modified through polyethyleneimine, a C-C chain segment is introduced into the organic silicon, the C-C chain segment has similar compatibility with a C-C chain segment in nylon, and the compatibility of the organic silicon and the nylon is improved. In the synthesis stage of the organic silicon nylon elastomer, the reaction probability of terminal amino of organic silicon and terminal carboxyl of nylon is increased, the reaction conversion rate and the synthesis efficiency are improved, and the mechanical property of a finished product is remarkably improved.

Description

Technical Field

[0001] The invention belongs to the technical field of artificial fibers, and in particular relates to a method for preparing an organosilicon nylon elastomer. Background Art

[0002] Silicone nylon elastomer is a high-performance polymer material that combines the advantages of both silicone and nylon polymer materials and has excellent elasticity and tensile properties. In the fiber field, these properties allow silicone nylon elastomer to be used to manufacture high-performance textiles, such as work clothes that are resistant to high temperatures and wear, and sports and leisure clothing that require high elastic recovery.

[0003] However, due to the low surface energy of silicone and its poor compatibility with nylon melt, the dispersion of silicone in the nylon melt is poor, which reduces the reactivity of silicone and nylon and greatly affects the mechanical properties of the synthesized silicone nylon elastomer.

[0004] In summary, the prior art obviously has inconveniences and defects in practical use, so it is necessary to improve it. Summary of the invention

[0005] In view of the above-mentioned defects, the present invention mainly provides a method for preparing a silicone nylon elastomer to solve the technical problem that the compatibility of silicone and nylon melt is poor, which affects the mechanical properties of the material.

[0006] In order to solve the above problems, the present invention provides a method for preparing an organosilicon nylon elastomer, comprising an organosilicon modification stage and an organosilicon nylon elastomer synthesis stage; 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 silicone nylon elastomer synthesis stage includes: S1, mixing the modified silicone, nylon and catalyst in a predetermined ratio for 30 min; 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.

[0007] According to the method for preparing an organosilicon nylon elastomer of the present invention, the mixing ratio of the isocyanate-terminated organosilicon and polyethyleneimine in the organosilicon modification stage is: a molar ratio of 1:10 to 1:200.

[0008] According to the method for preparing an organosilicon nylon elastomer of the present invention, the polymerization degree of the isocyanate-terminated organosilicon in the organosilicon modification stage is 5-20, and the polymerization degree of the polyethyleneimine is 10-200.

[0009] According to the method for preparing an organosilicon nylon elastomer of the present invention, the polymerization degree of the isocyanate-terminated organosilicon in the organosilicon modification stage is 8-12, and the polymerization degree of the polyethyleneimine is 20-80.

[0010] According to the method for preparing an organosilicon nylon elastomer of the present invention, the banburying temperature in the organosilicon modification stage is 180° C. to 210° C., and the banburying time is 30 to 60 min.

[0011] According to the method for preparing a silicone nylon elastomer of the present invention, 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; and the catalyst is sodium hypophosphite.

[0012] According to the method for preparing an organosilicon nylon elastomer of the present invention, the step S1 uses a high-speed mixer to mix the modified organosilicon, nylon and the catalyst.

[0013] According to the method for preparing a silicone nylon elastomer of the present invention, the extruder in step S2 is a twin-screw extruder, and the main screw speed is 50-300 rpm.

[0014] According to the method for preparing a silicone nylon elastomer of the present invention, the extrusion temperature is 200°C to 280°C.

[0015] According to the method for preparing an organosilicon 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.

[0016] In summary, the present invention modifies the isocyanate-terminated silicone by polyethyleneimine and introduces CC segments into the silicone. The CC segments in the modified silicone have similar compatibility with the CC segments in nylon, thereby improving the compatibility of silicone with nylon. In the synthesis stage of silicone nylon elastomer, the reaction probability of the terminal amine group of silicone and the terminal carboxyl group of nylon is increased, the reaction conversion rate and synthesis efficiency are improved, and the mechanical properties of the finished product are significantly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 Schematic diagram of the organosilicon modification reaction of the present invention; Figure 2 This is a schematic diagram of the reaction for preparing the organosilicon nylon elastomer of the present invention; DETAILED DESCRIPTION

[0018] See also Figure 1 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: The organosilicon modification stage comprises: mixing the isocyanate-terminated organosilicon and polyethyleneimine in a predetermined ratio, and performing a banburying reaction to obtain modified organosilicon; The mixing temperature is 150℃~250℃, and the mixing time is 10~200 min; The C=N bond in the isocyanate group at the end of the isocyanate-terminated silicone is an active group; the C=N bond reacts with the terminal OH in polyethyleneimine, such as Figure 1 or the C=N bond reacts with the NH group in polyethyleneimine, such as Figure 1 The B reaction in.

[0019] The invention modifies the isocyanate-terminated organosilicon by polyethyleneimine, and introduces CC segments into the organosilicon.

[0020] As a preferred embodiment, the mixing ratio of the isocyanate-terminated organosilicon and polyethyleneimine in the organosilicon modification stage is: molar ratio 1:10 to 1:200; Furthermore, the polymerization degree of the isocyanate-terminated silicone in the silicone modification stage is 5 to 20, and the polymerization degree of the polyethyleneimine is 10 to 200; Preferably, 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.

[0021] Preferably, the banburying temperature in the organosilicon modification stage of the present invention is: 180°C~210°C, and the banburying time is: 30~60 min; The silicone nylon elastomer synthesis stage includes: S1, mixing the modified silicone, nylon and catalyst in a predetermined ratio for 30 min; As an embodiment, the mass ratio of modified silicone to nylon is 1:1 to 1:10; the catalyst accounts for 0.1% to 1% of the total mass of modified silicone and nylon; The catalyst of the present invention is preferably sodium hypophosphite.

[0022] As an embodiment, the step S1 uses a high-speed mixer to mix the modified silicone, nylon and the catalyst; S2, putting the mixed material into an extruder and extruding it at a predetermined extrusion temperature; Combination Figure 2The amine group in the modified silicone reacts with the carboxyl group at the end of the nylon macromolecular chain under the action of a catalyst, connecting the silicone to the nylon through a covalent bond to obtain a silicone nylon elastomer.

[0023] As an embodiment, the extruder in step S2 is a twin-screw extruder, and the main screw speed is 50-300 rpm; Furthermore, the extrusion temperature is 200°C to 280°C, preferably 220°C to 250°C.

[0024] The CC segment in the modified silicone of the present invention has similar compatibility with the CC segment in nylon, thereby improving the compatibility of silicone with nylon. The reaction probability of the terminal amine group of silicone and the terminal carboxyl group of nylon is increased. Compared with the 50 to 100 hours required by the existing production process, the reaction synthesis time of the twin-screw extruder used in the present invention is 5 to 10 minutes. The reaction conversion rate and synthesis efficiency are greatly improved.

[0025] S3, drawing the extrudate into strips, cooling it, and pelletizing it to obtain a silicone nylon elastomer; 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.

[0026] The present invention has multiple embodiments, using terminal isocyanate group silicone and polyethylene imine to prepare multiple modified silicone samples through modification reaction, and reacting the modified silicone samples with multiple nylons to synthesize multiple silicone nylon elastomer samples.

[0027] At the same time, a comparative sample without silicone modification was set up. Afterwards, the synthesized silicone nylon elastomer samples were subjected to multiple mechanical property tests to verify the material performance.

[0028] The specific experimental parameters of each embodiment and comparative example are shown in Table 1, and the test results are shown in Table 2. (Table 1 only lists the changed parameters, and the same components and steps can be found in the previous text, which will not be repeated here.) In order to simplify the table text, the complex expressions in the table are simplified as follows;

[0029] Silicone modification stage:

[0030] "The molar ratio of the isocyanate-terminated silicone and polyethyleneimine", referred to as "modified material ratio" in the table; "Degree of polymerization of isocyanate-terminated silicone", referred to as "degree of polymerization of silicone" in the table; The “degree of polymerization of polyethylene imine” is referred to as “degree of polymerization of imine” in the table.

[0031] Silicone nylon elastomer synthesis stages:

[0032] “Mass ratio of modified silicone to nylon”, referred to as “synthetic material ratio” in the table; “The proportion of catalyst to the total mass of modified silicone and nylon”, referred to as “catalyst amount” in the table; To make the experimental results comparable, the nylon used in each embodiment and comparative example is nylon 6; and the extrusion step is completed by a twin-screw extruder in the synthesis stage of the organosilicon nylon elastomer.

[0033] "The speed of the main screw of the twin-screw extruder" is referred to as "screw speed" in the table.

[0034] Table 1 Parameters of various embodiments and comparative examples

[0035]

[0036] Note: The preparation process of the comparative samples in Table 1 does not include a silicone modification stage, so the composition of the "synthetic material ratio" of the comparative examples in Table 1 is: the mass ratio of terminal amino silicone to nylon 6, and the steps and parameters are the same as above.

[0037] Table 2 Mechanical properties test results of silicone nylon elastomers prepared in various embodiments and comparative examples

[0038]

[0039] Referring to Table 1 and Table 2, compared with the comparative example without silicone modification, the embodiment of the present invention modifies the terminal isocyanate silicone by polyethyleneimine, and introduces CC segments into the silicone. The CC segments in the modified silicone have similar compatibility with the CC segments in nylon, which improves the compatibility of silicone and nylon. In the synthesis stage of silicone nylon elastomer, the reaction probability of the terminal amine group of silicone and the terminal carboxyl group of nylon is increased, the reaction conversion rate and synthesis efficiency are improved, and the mechanical properties of the finished product are significantly improved.

[0040] In summary, the present invention provides a method for preparing a silicone nylon elastomer, in which the terminal isocyanate silicone is modified by polyethyleneimine, and a CC segment is introduced into the silicone. The CC segment in the modified silicone has similar compatibility with the CC segment in nylon, thereby improving the compatibility of silicone with nylon. In the synthesis stage of the silicone nylon elastomer, the reaction probability of the terminal amine group of the silicone 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.

[0041] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims attached to 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 silicone nylon elastomer synthesis stage includes: S1, mixing the modified silicone, nylon and catalyst in a predetermined ratio for 30 min; 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 mixing ratio of the isocyanate-terminated silicone and polyethyleneimine in the silicone modification stage is: molar ratio 1:10-1:

200.

3. 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.

4. The method for preparing a silicone nylon elastomer according to claim 3, 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.

5. 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.

6. The method for preparing a silicone nylon elastomer according to claim 1, characterized in that: 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; and the catalyst is sodium hypophosphite.

7. 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.

8. 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.

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

10. The method for preparing a silicone nylon elastomer according to any one of claims 1 to 9, 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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