Sulfuryl-containing nylon and preparation method thereof

Abstract

The sulfonyl-containing nylon is mainly characterized in that dihydroxy alkyl bisphenol S with a specific molar ratio is introduced into a nylon resin chain segment, so that the fluidity can be obviously improved, and the sulfonyl-containing nylon has good mechanical properties and is suitable for preparing thin-wall and precise workpieces; meanwhile, the sulfuryl-containing nylon disclosed by the invention has a dielectric constant lower than that of traditional nylon, and has good insulating property.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly to a sulfone-based nylon and a preparation method thereof. Background Art

[0002] Nylon is a type of polymer material containing amide groups, with excellent comprehensive properties and a wide range of application fields. However, in some applications, its heat resistance is slightly insufficient, and its toughness also fails to meet the usage requirements of the material. Polymers containing sulfone groups, such as polyethersulfone, polyphenylene sulfone, etc., have good heat resistance and excellent insulation properties.

[0003] The prior art has explored introducing sulfone structures into polyamides: Chinese Patent CN 104387587B synthesized a high-flow polyethersulfone / amide copolymer, which has the advantages of high temperature resistance, corrosion resistance, and flame retardancy. However, this patent did not discuss the dielectric properties.

[0004] Chinese Patent CN102337606A disclosed a polyarylsulfonamide spinning solution with a high multiple spinneret draw ratio, and its repeating unit structure is terephthalic acid, isophthalic acid, diaminodiphenyl sulfone, and diaminobisphenol S. The polyarylsulfonamide polymerization solution prepared by the method of segmental polymerization to prepare the polyarylsulfonamide polymerization solution has a high viscosity and is easier to control. However, this product can only be applied to spinning and is difficult to be applied to injection-molded products.

[0005] "Study on the Properties of MC Nylon 6 / Polysulfone In-situ Composites", Lin Xianshui, etc. "Engineering Plastics Application". 2012.1, Vol. 40 (No. 1), 4-7. described a preparation method for preparing nylon 6 / polysulfone composites. In this method, the polysulfone exists in an independent form in MC nylon 6 and is not incorporated into the molecular chain of MC nylon 6. It is actually an alloy material and has problems such as incompatibility between two phases. Summary of the Invention

[0006] The purpose of the present invention is to provide a sulfone-based nylon with good fluidity, good mechanical properties, and low dielectric constant, and a preparation method thereof.

[0007] The present invention is achieved through the following technical solutions: A sulfone-based nylon, in terms of mole percentage, is derived from the following units: Dicarboxylic acid 47 - 53 mol%; Diamine 40 - 48 mol%; Dihydroxyalkyl bisphenol S 0.1 - 10 mol%; The dibasic acid is selected from at least one of terephthalic acid, isophthalic acid, 1,4-butanedioic acid, 1,5-pentanedioic acid, 1,6-hexanedioic acid, 1,7-heptanedioic acid, 1,8-octanedioic acid, 1,9-nonanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, and 1,12-dodecanedioic acid; The diamine is selected from at least one of p-phenylenediamine, m-phenylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine; The dihydroxyalkyl bisphenol S is:

[0008] wherein, R3 and R4 are each one of saturated alkyl groups having 1 to 4 carbon atoms.

[0009] The repeating unit of the sulfone group-containing nylon of the present invention is as follows:

[0010] wherein, R1 and R2 are each one of 1,4-phenylene, 1,3-phenylene, and saturated alkyl groups having 4 to 12 carbon atoms. Preferably, the dibasic acid is 48 - 52 mol%, the diamine is 42 - 46 mol%, and the dihydroxyalkyl bisphenol S is 3 - 6 mol%.

[0011] Specifically, the saturated alkyl group having 1 to 4 carbon atoms is at least one of methylene, ethylene, 1,3-propylene, and 1,4-butylene.

[0012] Preferably, the dibasic acid is selected from at least one of 1,5-pentanedioic acid, 1,10-decanedioic acid, 1,11-undecanedioic acid, and 1,12-dodecanedioic acid; preferably, the diamine is selected from at least one of 1,5-pentanediamine, 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine.

[0013] The relative viscosity range of the sulfone group-containing nylon of the present invention is 1.8 - 2.8.

[0014] The preparation method of the sulfone group-containing nylon of the present invention includes, but is not limited to, the following steps: Step A: Add dibasic acid, diamine, and deionized water into a reaction kettle in proportion. Replace the air in the reaction kettle with an inert gas, fill it with an inert gas at 0.05 - 0.5 MPa, heat up to 120°C - 180°C, keep the pressure stable at 0.3 - 1.6 MPa, react for 1 - 2 h, then raise the temperature to 220°C - 300°C, keep the pressure stable at 1.5 - 4.8 MPa, react for 2 h - 6 h, then reduce the pressure in the kettle to atmospheric pressure within 1 - 2 h and simultaneously raise the temperature in the kettle to 250 - 350°C, continue to react for 1 - 2 h. Subsequently, reduce the pressure in the kettle to 60 - 100 Pa, maintain the pressure, continue to react for 3 - 10 h, then fill in an inert gas, and adjust the pressure in the kettle to -0.02 MPa - 0 MPa; Step B: Add a catalyst and dihydroxyalkyl bisphenol S, keep the temperature at 250 - 350°C and react for 2 - 5 h, then reduce the pressure in the kettle to 60 - 100 Pa and continue to react for 5 - 10 h. After the reaction is completed, introduce an inert gas, open the bottom valve of the reaction kettle, and after the material flows out from the bottom of the reaction kettle, quickly draw it into strips, pass it through a water trough, air-dry it, and cut it into pellets to obtain sulfone-based nylon.

[0015] The catalyst described above includes one of methyl titanate, ethyl titanate, butyl titanate, germanium dioxide, ethylene glycol antimonate, antimony trioxide, and manganese acetate, and the addition amount relative to dihydroxyalkyl bisphenol S is 5 - 100 ppm.

[0016] The addition amount of deionized water is 10% - 100% of the total mass of dibasic acid, diamine, and comonomer; the inert gas is one of nitrogen, carbon dioxide, or argon.

[0017] The present invention has the following beneficial effects: By introducing dihydroxyalkyl bisphenol S with a specific molar ratio and a specific structure into the nylon resin chain segment, the present invention can significantly improve the fluidity, and has good mechanical properties, which is suitable for preparing thin-walled and precision parts; at the same time, the sulfone-based nylon of the present invention has a dielectric constant lower than that of traditional nylon and has good insulation performance. Specific Embodiments

[0018] The present invention will be described in detail below in conjunction with specific embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made. These all belong to the protection scope of the present invention.

[0019] The sources of the experimental raw materials used in the present invention are as follows: Dihydroxyalkyl bisphenol S-A: Commercially available; Dihydroxyalkyl bisphenol S-B: , commercially available; Dihydroxyalkyl bisphenol S-C: , commercially available; Bisphenol S, other dibasic acids, diamines, solvents, catalysts, etc. are sourced commercially.

[0020] Preparation method of sulfone group-containing nylon in the examples and comparative examples: Add dibasic acid, diamine, and deionized water to the reaction kettle in proportion, displace the air in the kettle with an inert gas, fill with an inert gas at 0.05 - 0.5 MPa, heat up to 120°C - 180°C, keep the pressure stable at 0.3 - 1.6 MPa, react for 1 - 2 h, then raise the temperature to 220°C - 300°C, keep the pressure stable at 1.5 - 4.8 MPa, after reacting for 2 h - 6 h, slowly release the gas, release the pressure in the kettle to atmospheric pressure within 1 - 2 h and simultaneously raise the temperature in the kettle to 250 - 350°C, continue to react for 1 - 2 h, then reduce the pressure in the kettle to 60 - 100 Pa, keep the pressure, continue to react for 3 - 10 h, then fill with an inert gas, adjust the pressure in the kettle to -0.02 MPa~0 MPa; add 50 ppm tetrabutyl titanate and dihydroxyalkyl bisphenol (or bisphenol S), keep the temperature at 250 - 350°C and react for 2 - 5 h, then reduce the pressure in the kettle to 60 - 100 Pa and continue to react for 5 - 10 h, complete the reaction, introduce an inert gas, open the bottom valve of the reaction kettle, and the material flows out from the bottom of the reaction kettle, then quickly draw it into strips, pass through a water bath, air dry, and pelletize to obtain sulfone group-containing nylon.

[0021] Testing methods for each item: (1) Melt index: Tested according to ISO 1133, test conditions 2.16 kg, temperature as shown in the table; (2) Notched impact strength: Tested according to ISO 180 / 1A; (3) Tensile strength: Tested according to ISO 527-1 / -2; (4) Dielectric constant: Tested according to ASTM D150.

[0022] Table 1: mol% content of each unit and test results of sulfone group-containing nylon in Examples 1 - 6

[0023] It can be seen from Examples 1 - 6 that the sulfone group-containing nylon resin of the present invention has high melt fluidity, good mechanical properties, and a dielectric constant lower than 4.0 (10 3 Hz).

[0024] Table 2: mol% content of each unit and test results of sulfone group-containing nylon in Examples 7 - 13

[0025] It can be seen from Examples 7-13 and Comparative Example 2 that the sulfone group-containing nylon of the present application has higher melt fluidity, significantly improved mechanical properties, and significantly decreased dielectric constant. At the same time, it can be known that the dielectric constant is the lowest when the molar percentages of each unit are optimized, and the notched impact strength > 7 kJ / m 2 , and the tensile strength > 60 MPa.

[0026] Table 3: mol% content of each unit of the sulfone group-containing nylon in the comparative example and test results

[0027] It can be seen from Comparative Example 1 that bisphenol S failed to participate in the polymerization successfully, resulting in low molecular weight and low mechanical properties.

[0028] When Comparative Example 2 does not contain dihydroxyalkyl bisphenol S, the notched impact strength is low, the melt fluidity is poor, and the dielectric properties are high.

[0029] When the content of dihydroxyalkyl bisphenol S in Comparative Example 3 is too high, the tensile strength is severely reduced instead.

Claims

1. A sulfone group-containing nylon, characterized in that, Deriving from the following units in mole percentages: Dicarboxylic acid: 47 - 53 mol%; Diamine: 40 - 48 mol%; Dihydroxyalkyl bisphenol S: 0.1 - 10 mol%; The dicarboxylic acid is selected from at least one of terephthalic acid, isophthalic acid, 1,4 - butanedioic acid, 1,5 - pentanedioic acid, 1,6 - hexanedioic acid, 1,7 - heptanedioic acid, 1,8 - octanedioic acid, 1,9 - nonanedioic acid, 1,10 - decanedioic acid, 1,11 - undecanedioic acid, 1,12 - dodecanedioic acid; The diamine is selected from at least one of p - phenylenediamine, m - phenylenediamine, 1,4 - butanediamine, 1,5 - pentanediamine, 1,6 - hexanediamine, 1,7 - heptanediamine, 1,8 - octanediamine, 1,9 - nonanediamine, 1,10 - decanediamine, 1,11 - undecanediamine, 1,12 - dodecanediamine; The dihydroxyalkyl bisphenol S is: ， R3 and R4 are each one of saturated alkyl groups with 1 - 4 carbon atoms.

2. The sulfone group-containing nylon according to claim 1, wherein Dicarboxylic acid: 48 - 52 mol%, diamine: 42 - 46 mol%, dihydroxyalkyl bisphenol S: 3 - 6 mol%.

3. The sulfone group-containing nylon according to claim 1, wherein, The saturated alkyl group with 1 - 4 carbon atoms is at least one of methylene, ethylene, 1,3 - propylene, 1,4 - butylene.

4. The sulfone group-containing nylon according to claim 1, wherein The dicarboxylic acid is selected from at least one of 1,5 - pentanedioic acid, 1,10 - decanedioic acid, 1,11 - undecanedioic acid, 1,12 - dodecanedioic acid; the diamine is selected from at least one of 1,5 - pentanediamine, 1,6 - hexanediamine, 1,9 - nonanediamine, 1,10 - decanediamine, 1,11 - undecanediamine, 1,12 - dodecanediamine.

5. The sulfone group-containing nylon according to claim 1, wherein The relative viscosity range of the sulfone - containing nylon is 1.8 - 2.

8.

6. The preparation method of the sulfone group-containing nylon according to any one of claims 1-5, characterized in that, Including the following steps: Step A: Add the dicarboxylic acid, diamine, and deionized water into the reaction kettle in proportion, displace the air in the reaction kettle with an inert gas, fill in 0.05 - 0.5 MPa of inert gas, heat up to 120°C - 180°C, keep the pressure stable at 0.3 - 1.6 MPa, react for 1 - 2 h, then raise the temperature to 220°C - 300°C, keep the pressure stable at 1.5 - 4.8 MPa, react for 2 h - 6 h, then reduce the pressure in the kettle to atmospheric pressure within 1 - 2 h and simultaneously raise the temperature in the kettle to 250 - 350°C, continue to react for 1 - 2 h, then reduce the pressure in the kettle to 60 - 100 Pa, keep the pressure, continue to react for 3 - 10 h, then fill in an inert gas, and adjust the pressure in the kettle to - 0.02 MPa - 0 MPa; Step B: Add the catalyst and dihydroxyalkyl bisphenol S, keep the temperature at 250 - 350°C and react for 2 - 5 h, then reduce the pressure in the kettle to 60 - 100 Pa and continue to react for 5 - 10 h, then complete the reaction, introduce an inert gas, open the bottom valve of the reaction kettle, and after the material flows out from the bottom of the reaction kettle, quickly carry out strand - making, pass through a water trough, air - dry, and pelletize to obtain the sulfone - containing nylon.

7. The preparation method of the sulfone group-containing nylon according to claim 6, wherein, The catalyst includes one of methyl titanate, ethyl titanate, butyl titanate, germanium dioxide, antimony glycolate, antimony trioxide, manganese acetate, and the addition amount relative to the dihydroxyalkyl bisphenol S is 5 - 100 ppm.

8. The preparation method of the sulfone group-containing nylon according to claim 6, characterized in that, The addition amount of ionic water is 10% to 100% of the total mass of the dibasic acid, diamine and comonomer; the inert gas is one of nitrogen, carbon dioxide or argon.

Images